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Microscopical Examination

and Interpretation of
Portland Cement and Clinker
Donald H. Campbell, Ph.D.

Construction Technology Laboratories


A Division of the Portland Cement Association
5420 Old Orchard Road
Skokie, Illinois 60077-4321
Contents
Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . V Chapter 6 0110s Method-History,
Acknowledgments. . . . . . . . . . . . . . . . . . . . . . . . . . V Explanation, and Pm&e .................. 30
History of Onos Theories of Kiln Control
Introduction .................................. VI Through Microscopy. . . . . . . . . . . . . . . . . . . . . 30
Chapter 1 History of Clinker Microscopy ....... 1 The Ono Method . . . . . . . . . . . . . . . . . . . . . . . . . . 32
Photomicrographs of Aspdin Paste . . . . . . . . . . . . 1 Alite Size . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
Chapter 2 Sampling and sample Storage ...... 6 Alite Birefringence . . . . . . . . . . . . . . . . . . . . . 33
Sampling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6 Photomicrographs Illustrating Onos
Sample Storage . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
Storage of Prepared Specimens . . . . . . . . . . . . . . 7 Belite Size . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
Belite Color . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
Chapter3 StainsandEtches.. ................ 8
Use of Onos Tables to Interpret Kiln
Aluminates and Free Lime . . . . . . . . . . . . . . . . . . . 8 Conditions and Predict 28-Day
Silicates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8 Mortar-Cube Strength . . . . . . . . . . . . . . . . 37
Calcium Fluoroaluminate . . . . . . . . . . . . . . . . . . . 10 Comments on the Ono Method. . . . . . . . . . . . . . 38
Examination of Stained Powders . . . . . . . . . . . . . 10 Alite Birefnngence . . . . . . . . . . . . . . . . . . . . . 38
Photomicrographs of Effects of Stains Alite Size . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
and Etches . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11 Belite Color. . . . . . . . . . . . . . . . . . . . . . . . . . . 40
Chapter 4 Preparation of Polished Sections,
Thin !kctions,and ParticleMounts ......... 14 Chapter 7 Microscopical Interpret&on
ofClinkers ................................ 42
Basic Steps for Rapid Polished Section
Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14 General Features of Clinkers . . . . . . . . . . . . . . . . 42
Encapsulation, Impregnation and Alite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
Particle Mounting . . . . . . . . . . . . . . . . . . . . . . . . 15 Belite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
Encapsulation and Impregnation. . . . . . . . . 16 Matrix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
Sawing, Grinding, and Polishing . . . . . . . . . . . . . 16 Free Lime . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
lsomet and Minimet Method. . . . . . . . . . . . . 16 Periclase . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
Use of the Ecomet . . . . . . . . . . . . . . . . . . . . . 17 Miscellaneous . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
Hamss Technique. . . . . . . . . . . . . . . . . . . . . 18 Cha ter 8 Misintetpretations in
Thin Sections . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19 aLdho~0p~ ......................... 93
Techniques with Hyrax . . . . . . . . . . . . . . . . . . . . . 20 Chapter 9 Scanning Electron Microscopy . . . . . . . . . 98
Particle Mounts on Thin Epoxy Film . . . . . . . . . . 21 Chapter 10 Recommended Procedures
Cha ter 5 Microscopic Chamctmistics of and Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
a Elkdhase~ ............................. 22 S u gested Procedure for Detailed
Alite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22 8 linker Examination . . . . . . . . . . . . . . . . . . . . 108
Belite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23 Quantitative Microscopy . . . . . . . . . . . . . . . . . . . 109
Comments on Belite Classification and Microscope Equipment, Supplies, and
PolymorphicVarieties . . . . . . . . . . . . . . . . 24 Thin-Section Services . . . . . . . . . . . . . . . . . . . 110
Tricalcium Aluminate . . . . . . . . . . . . . . . . . . . . . . 26
Chapter 11 Conclusions .................... 113
Alkali Aluminate. . . . . . . . . . . . . . . . . . . . . . . . . . . 26
Glo!BaIy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
Ferrite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
References ................................. 117
FreeLime . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
Author Index ............................... 125
Periclase . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
Subject fndex .............................. 126
Alkali Sulfates. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
Miscellaneous Phases . . . . . . . . . . . . . . . . . . . . . . 27
Preface
The aim of this handbook is to improve economical pro and cement from approximately 51 North American kilns
duction and quality control of portland cement Samples were studied and interpreted.
of clinker, cement, and raw materials can be prepared for One should not assume, however, that interpretive
microscopical examination with relative ease and rapidity. cement microscopy has an unalterable foundation in
Virtually immediate improvements in the production proc- optical fact, for much research remains to be done in
ess can result that quickly justify the costs of optical describing and defining the correlations between micro-
equipment and personnel training. Use of the micro- scopical observation and the production regime. Extensive
scope, therefore, can readily translate into energy savings systematic research is needed on the nature of portland
and a competitive cement while facilitating control or cement phases (in particular, the polymorphic varieties)
improvement of cement quality. The underlying variables discerned through combined observations utilizing trans-
in the equation of cement quality and performance are mitted- and reflected-light microscopes, scanning and
essentially those of many other chemical (mineral) indus- transmission electron microscopes, electron microprobe,
tries: nature of the raw materials, efficiency of treatment of and X-ray diffraction. An appreciation of the techniques,
those raw materials during product manufacture, and the problems, and applicability of these complementary
proper use of the product. Consequently, the answer to modes of analysis adds immeasurably to the depth of
the question How can we improve the quality of portland ones competence in clinker interpretation and conse-
cement? lies, to a great extent, in the sciences of miner- quently increases ones value in the economics of cement
alogy and chemistry. production. Modem methods of cement production,
The primary purposes, therefore, of this publication are therefore, virtually demand modem techniques of micros-
copy and chemical analysis.
1. To describe the methods of sample preparation for
microscopical study and to recommend the use of
certain methods of analysis and microchemical
techniques Acknowledgments
2. To describe the common phases in portland cement The writer is particularly grateful to the late George J.
clinker Vanisko of PCA who introduced the author to the subject
3. To present a set of microscopical observations of clinker and cement microscopy and who participated in
(illustrated with photomicrographs where Possible) the teaching of that subject in a course given at the PC4
with corresponding genetic interpretations drawn, laboratories in Skokie, Illinois. Vanisko was particularly
for the most part, from published sources. fortunate to have had instruction from Yoshio Ono and
An effort has been made to present information valu- persevered in the mastery of what he learned.
The writer is indebted to Stewart Tresouthick, director,
able in day-to-day cement manufacture and to separate
microscopical observation from interpretation. Even Chemical-Physical Research Department, PCA; JackProut,
though some interpretations may be somewhat contradic- St. Marys Cement Company, Toronto, Ontario, who
served as chairman of the PCA editorial committee; and
tory from author to author, such contradictions point out
the members of the editorial committee for their critical
directions for further research. The compilation of optical
data and interpretations is therefore considered prelimi- examination of the manuscript. Gratitude is also extended
to G. R. Long of the Blue Circle Research Laboratories in
nary and should serve as the basis for continued study of
clinker phases, preferably with statistical methods. Greenhithe, England, for assistance at numerous times,
especially for information on the calcium silicosulfates,
The publication is not meant to cover the theory of light
and to Dr. Peter Hawkins, California Portland Cement
transmission in solid crystalline and noncrystalline media
Company, for the procedure utilizing the Babinet com-
or optical mineralogy. These subjects are discussed by
pensator to determine alite birefringence. Yoshio Ono
Midgley* in Taylor (1964), Wahlstrom (1969), and Kerr
(Onoda Cement Company, Tokyo), Rong Far Lee (Tai-
(1977). The readers working knowledge of polarized-light
and reflected-light microscopy is assumed. College or wan Cement Corporation, Taipei), and lwao Maki (Nagoya
Institute of Technology, Japan) have been particularly
industrial courses or private study and experience in light
helpful through correspondence on several occasions. I
microscopy are required to derive optimum benefit from
am grateful to Hugh Love of PCA for valuable assistance
this material, which, for the most part, evolved from a
course in cement and clinker microscopy given for sev in the scanning electron microscopy and to Jean Ran
dolph, also of PCA, for aid in typing many of the observa-
eral years at the Portland Cement Association (PCA),
Skokie, Illinois. Consequently, this handbook was written tions and interpretations. My wife, Karen, kindly provided
expertise on text and photograph formats, and assisted in
for the practicing microscopist in the cement plant or in
the research laboratory. editing and checking references.
All of the photomicrographs were taken by the writer as
part of a PCA research project (HR-1404, Microscopical
Analysis of Clinker) in which samples of raw feed, clinker, *See references at the back of this publication.

V
Introduction
The fundamental use of the microscope in portland
cement clinker analysis is to bring to the observer a visual
appreciation of phase identities, sizes, conditions, and
mutual relationships. With only a basic assemblage of
equipment, microscopical analysis can be easily per-
formed, in many cases within a few minutes. The rapidity,
therefore, with which potentially energy-saving informa-
tion can be acquired clearly renders the analysis econom-
ically justifiable, especially in routine quality-control and
troubleshooting situations. In addition, the microscope
has obvious value in scientific research in the manufac-
turing process.
Study of a polished section or thin section of portland
cement clinker, for example, quickly reveals several
details of crystal size, morphology, abundance, and distri-
bution, leading almost intuitively to interpretations relating
these data to certain features of the raw material and
burning conditions. The microscopical method of analy-
sis, using polished sections or thin sections of clinkers, is
uniquely advantageous because the investigator can see
individual crystals, virtually undisturbed, in their place of
origin, and can interpret these observations in terms of the
microenvironment developed in that clinker nodule. These
interpretations are, consequently, related to characteris-
tics of the raw feed particles, leading eventually to an
interpretation of the predominant burning conditions in
the kiln. For example, nests of tightly packed belite crys-
tals form in silica-rich areas of the clinker and suggest the
possibility of coarse quartz grains in the raw feed. Alite
crystal sizes of 10 to 15 pm may indicate an undesir-
ably rapid rate of temperature rise in the clinker as it passes
through the kiln.
Following are some of the many aspects of portland
cement production in which microscopy can play an ana-
lytical and quality-controlling role:
1. Analysis of Raw Materials
A. Quarry rock analysis
(1) Areal and volume distribution of rock types
(2) Mineralogy and chemistry
(3) Potential grindability
B. Raw-mix analysis
(1) Mineralogy and chemistry of size fractions and
individual phases

VI
(2) Efficiency of grinding and homogenization C. Constitution of coal ash and slag
processes (1) As blended material in cement
(3) Estimation of bumability (2) As a raw material for kiln feed
2. Clinker and Cement Examination D. Gypsum and other sulfates
A. Phase changes and phase concentrations at var- ( 1) Purity (byproduct or natural deposit)
ious stages in the pyroprocessing system (includ- (2) Size distribution (grinding efficiency)
ing buildups, rings, coatings, and clinker- (3) Alterations in silo storage and grinding effects
refractory reactions) E. Metallography
B. Temperature profile-burning efficiency relation- ( 1) Kiln chain examination
ships in the calcining and burning zones of the kiln (2) Grinding-ball examination
(1) Rate of heating (rate of temperature change
Optimum use of the microscope requires certain skills
in the kiln feed through the approximate range
of the microscopist. Above all, one must be patient in the
of 1200C to 1600C)
(2) Maximum clinker temperature (above proper preparation of samples and diligent in perfecting
those analytical techniques that give reliable data. Of
1450C)
prime importance is the microscopists ability to quickly
(3) Time of clinker retention at high tempera- recognize many phases that are routinely investigated
ture (length of time above approximately without resort to the timeconsuming process of gather-
1400C) ing large amounts of optical data. In other words, sight
(4) Rate of clinker cooling (rate of temperature identification of phases with a minimum of data is clearly
change from maximum to approximately an asset. With accumulated experience, most of which
1200C) comprises long hours at the microscope, an ability for
(5) Effects of raw feed fineness variations sight identification of the common phases is attained,
C. Grinding and storage interpretations are refined, knowledge is acquired, and the
(1) Prediction of clinker grindability microscopist can confidently state the results of his or her
(2) Efficiency of clinker-grinding process (min- analysis. A critical eye, an appreciation of optical mineral-
eralogy of size fractions, estimate of Blaine ogy, and a knowledge of the chemical nature of the port-
surface area) land cement production process, therefore, are the pri-
(3) Clinker weathering during storage mary requirements for optimum use of the microscope in
D. Prediction of cement performance the cement industry.
(1) Hydration characteristics &to-date photographic equipment to provide a per-
manent record is practically mandatory. A television
(2) Strength gain camera attached to the microscope can be quite helpful in
(3) Sulfate resistance presenting microscopical data to others, especially in an
3. Analysis of Other Materials instructional and recordkeeping context Complementary
A. Dust mineralogy and chemistry use of X-ray diffraction and the scanning electron micro
( 1) Stack emission scope (with microprobe) add to the versatility of the
(2) Bag-house collection microscopist, strengthening and widening the inter-
B. Coal pretations.
(1) Mineralogy
(2) Fineness
(3) Grindability

VII
Chapter 1
History of clinker Microscopy
Microscopical descriptions of clinker phases had their 3. A dark brown intermediate substance of irregular
origins in 1887 with the work of the French chemist and ragged form with a lime-iron-aluminate compo-
LeChatelier. Following the methods of microscopical sition (later shown to be calcium aluminoferrite)
analysis of rocks developed by the English geologist H. C. 4. Another material, which, he inferred chemically,
Sorby, founder of petrography and metallography, should be tricalcium aluminate.
LeChatelier reported the presence of the following con Although it is not clear whether LeChatelier examined
stituents in a portland cement clinker thin section: cement made by Joseph Aspdin, who patented portland
1. Clear, colorless, angular crystals with a low birefrin- cement in England in 1824, a few comments on the
gence, identified as tricalcium silicate nature of the Aspdin cement appear relevant to the history
2. Rounded, turbid, yellowish crystals with moderate of clinker microscopy.
birefringence, identified as dicalcium silicate

Photomicrographs of Aspdin Paste


Photograph 1 Portland cement dinker particle in
Aspdin paste. Subhedral to euhedral pale-green
aiite; raggedy, round multicolored belite; coarsely
aystalline brightly reflecting fenite; and gray alum-
inate (left center). Edge of particle shows pseudo-
morphic hydration effects.

Polished section*
KOH followed by nital etch
Field Dimensions (FD) = 0.21x0.21 mm

*Polished section photomicrographs were taken in 14ected light


unless other&e indicated.
Photomicrographs of Aspdin Paste (continued)

Photograph 2 Unhydmted portland cement clinker


(UPC) in Aspdin paste. Large, blue-green, angular
alite; small, tan-orange round belite (Type II, Insley);
brightly reflecting fenite; and pinkish-gray alumi-
nate, presumabiy C$.

Polished section
Nital etch
m = 0.21x0.21 mm

Photograph 3 Unusually large belite in UPC in


Aspdin paste. Note prominent iameilar extensions
into fenitic mat&. Probably an effect of CaO
resorption during slow cooling.

Polished section
Nital etch
FD = 0.21xo.21 mm

Photograph 4 UPC in Aspdin paste. Water etch


reveals dark-blue, coarsely uystalline aluminate,
presumably C$.

Polished section
FD = 0.21xo.21 mm
In 1978 a sample of hardened paste was given to the ditions, firmly established the optical properties of pure
writer by Norman Gregg of R. H. Harry Stanger, Ltd., compounds and the principal phases in commercial
Hertfordshire, United Kingdom. Gregg reported that the cements. These authors systematically investigated approx-
paste represented several barrels of cement (made by imately 1000 combinations of lime, alumina, and silica
William Aspdin, son of Joseph Aspdin) that had been with fully 7000 heat treatments and microscopical exami-
aboard a ship that sank in the River Thames in 1848 near nations.
Sheerness, Kent, England. The story of these barrels of Using Tomebohms classification, Guttmann and Gille
cement and other early cements is told by Blezard (1984). in 1928 tabulated the basic optical properties of clinker
A polished thin section of the hardened paste (Photo phases and the common hydration products. In 1931,
graphs 1 through 4) was examined by the writer and found Guttmann and Gille summarized the 50-year controversy
to contain approximately 10 percent unhydrated portland over the nature of alite and demonstrated conclusively
cement clinker (UPC) particles. Although the UPCs are far that alite is CS.*
from identical to those of modem production, they clearly According to lnsley (1936) polished section examina-
contain, among other phases, the four principal phases tion of portland cement clinker was reported by Stem
typical of portland cement (alite, belite, aluminate, and (1908) and by Wetzel (1913); but, largely due to poor
ferrite). Glassy particles were also observed in the Aspdin technique, the metallographic method was abandoned
paste and appear similar to those described by ldom and until Tavascis very detailed paper in 1934 in which
Thaulow ( 1983) who described some of the microscopic reflected-light microscopy was combined with trans-
characteristics of a precast concrete wall placed in front mitted-light data.
of Portland Hall, Gravesend, Kent, England, in 1847. Tavasci (1934) believed that clinker was composed
The wall is said to have been built for William Aspdin. primarily of alite, belite (alpha and beta), and celite (a fine
Further discussion of this wall and the nature of the UPCs mixture of 3CaO * A120) and 4Ca0 * Al*O, . F~zO,), with
is given by Blezard (1981 and 1984) who shows photo- free lime as a frequent additional phase. With a series of
micrographs suggesting a coarsely crystalline clinker that etches, including nital, oxalic acid, hydrofluoric acid,
was slowly heated and slowly cooled. Cements similar to water, and others, Tavasci carefully described the various
this Aspdin cement may have comprised some of the effects of these solutions on clinker phases and other
samples studied by LeChatelier and other early workers in synthetic compounds. Tavasci presented rather meticu-
clinker microscopy. lous descriptions of the forms of belite, suggesting a
In 1897 Tomebohm, a Swedish investigator, possibly martensitetype separation in the transformation of alpha
realizing that because of compositional variation mineral to beta.
names might be better suited for clinker phases than Tavasci classified belite into three morphological types:
chemical formulas, clearly described the optical features I, II, and Ill. Belite I was said to show striations, sometimes
of the principal clinker phases in thin sections and powder like twinning, prevalently in two directions. The striae were
mounts and coined the terms alite, Mite, celite, felite, described as being relatively thick but not very fitte.
and also glassy residue. Tomebohm related microscopi- Upon etching with alcoholic nitric acid (nital) the striae
cal data to burning conditions, stating: were hollowed out with respect to the rest of the grain.
Belite II crystals were generally large, containing very
1. Well-burned clinkers are less porous and contain fitte striae, the dark striae showing relatively less attack
better-crystallized colorless alite and dirty-green to by alcoholic nitric acid than the bright striae. Belite Ill was
muddy belite. comparatively small and appeared to be an external zone
2. Brownish-orange celite functions as a flux, promot- over a core formed by belite I or II. Coarse striation did not
ing the development of the silicates. occur in belite Ill, but fine parallel striations were observed
3. Underbumed clinker disintegrates because of atmo like those in belite II. Belite Ill was said to contain a kind of
spheric moisture combining with residual lime. veining formed by inclusions which at high magnification
appear white and in strong relief.
Tomebohm also made notable contributions to the In 1936 lnsley (about whom much more is said later)
microscopical understanding of cement hydration, a clearly showed that (1) alite is tricalcium silicate (CS), (2)
topic that must be left for future discussion. two different habits of dicalcium silicate (CS) comprise
Richardson (1903-l 905) summarized theories on the belite and felite, and (3) celite is tetracalcium aluminofer-
chemistry of portland cement and demonstrated the use rite (CYF). Insleys descriptions and illustrations of clinker
of a polarized-light microscope in the prediction of cement phases remain the basis for much of succeeding publica-
quality from clinker examinations. Richardson stated: If tions by others.
the structure is coarser and the elements are more segre Among the many historically important contributors to
gated, the cement from such a clinker will be less reliable. the microscopy of portland cement clinker, Levi S.
Most of Richardsons work, however, was in the laboratory Brown deserves special recognition for his observational
where, with numerous sintering experiments, he made skills and interpretive acumen. Brown worked for Lone
frequent use of powder mounts and thin sections to study
the products. Richardson, undoubtedly, developed an
extensive and systematic body of knowledge that formed
a foundation for later work by others.
Rankin and Wright (1915) although they were not parti- *An abbreviated chemical symbolism in which C = CaO. S = S%
cularly concerned with the interpretation of burning con A = Alu203, F = FeO,, K = K20, and N = Na20.
Star Research Laboratory in Hudson, New York, in the in 1928a and b. Epezite was said to differ from portlandite
1930s and, in 1940, joined the research staff at the Port- in optical sign and refractive indices as follows:
land Cement Association, where he spent approximately
Epezite Portlandite
25 years in cement and concrete investigations. Most of
Uniaxial (+) Uniaxial (-)
his scientific efforts were dedicated to the microscopical
interpretation of clinker burning, cement hydration, and Epsilon = 1.55-l 56 Epsilon = 1.574
concrete deterioration. An unpublished report (1936) Omega = 1.54-l .55 Omega = 1.545
contains the following interesting observations: Epezite typically forms tiny popcomlike crystals. Port-
1. CA and C,S were discriminated in thin sections and landite crystallizes in pore spaces as tablets and platelets.
powders mounted in Hyrax,* a synthetic resin with The growth of epezite was thought to be responsible for
index of refraction** of approximately 1.710. clinker disintegration in open storage (even in supposedly
2. Differences in optical properties of C&S were defined tightly sealed containers on the laboratory shelf) due to
and birefringence and morphology were observed to the 97-percent volume change when free lime combines
show wide ranges; crystal zoning was not clearly with atmospheric moisture, hence the term air-slaked.
understood. Browns most widely known published work is his
3. Optical characteristics of CS, particularly the Microscopical Study ofClinkers ( 1948) in which 2 1 differ-
discrimination between polymorphic varieties (alpha, ent lots of clinkers were microscopically studied at the
beta, and gamma) were described. The better Portland Cement Association laboratories in order to
burned clinkers were said to contain relatively clear correlate mineral composition with what Brown termed
crystals. the degrees of burning in the cement kiln and concrete
durability. Although Browns description and interpreta-
4. Optical characteristics of CAF, especially the color
tion of what he termed the glass and dark prismatic
variations, were related to burning conditions, mag-
phase may be questionable in the light of recent research,
nesium oxide content, and a reducing environment,
his work in clinker and concrete microscopy was seminal.
the latter indicated by a honey-brown CdAFcolor and
Brown contributed significantly to the discussion of
weak pleochroism. The darkening and strong
clinker phases in a book by lnsley and Frechette (1955).
pleochroism of 6AF were thought to be due to incor-
Brown summarized his philosophy of microscopy in
poration of magnesium oxide.
1959 when he discussed the two primary modes of spec
5 . The morphologic and volumetric changes in the imen examination (transmitted and reflected light); the
transformation of calcite to lime in a portland cement phase rule in relation to the microscope; the nature of
raw mix were described. cement hydration and its effects on strength, water-
6 . Large crystals of periclase were described and ex- cement ratio, dimensional stability, durability, and other
plained as an effect of annealing of commercial concrete problems.
clinkers. Tavasci (1978) elaborated on the three forms of belite
7 . Gehlenite, found sparingly in practically all portland (I, II, Ill), relating them to C2S polymorphs (alpha, alpha
cement clinkers, was detected by examination of prime, beta, and gamma), and attempted to show the
floating particles that have a uniaxial character and analogy with the austenitemartensite conversion in high-
perfect basal cleavage in an oil of approximately 1.71 carbon, hardened steel. Belite I was said to contain alpha
refractive index. Gehlenite was said to be suggestive lamellae (etching relatively light colored in nital) and alpha
of underbuming. prime lamellae (narrow and etching dark in nital). Belite II
was said to contain alpha and beta; the alpha prime,
8 . Sulfate minerals in clinkers, observed as floating par- having originally formed from alpha, was transformed to
ticles in refractive index oil, were said to occur
beta upon further cooling. Alpha remained as an included
abundantly in underbumed clinker. Optical charac- phase. Belite Ill differed from belite II in having sharper and
teristics of clinker sulfates compared with sulfate less-regular separation of the alpha inclusions.
phases formed in the laboratory led to the conclusion Also among the many major historical contributions in
that the low-index mineral in clinker is an alkali sulfate clinker microscopy are the works of Parker and Nurse
with a variable but small amount of calcium sulfate (1939); Taylor (1943); Gille (1955); Kramer (1960);
held in solid solution.
Nurse, Midgley, and Welch ( 1961); Midgley (1964); Butt
9 . Free lime was seen to increase with raw feed particle and Timashev (1974); and others. Most of these authors
size and decrease with increasing burning time
are mentioned again in Chapter 7, Microscopical Inter-
(flame length).
pretation of Clinkers.
Three relatively recent publications of European origin
Brown and Swayze in 1938 published a paper describ
are considered required reading for cement microscopists:
ing the application of the microscope to autoclave prob
lems, namely, free lime and magnesia in portland cement
Three forms of free lime were defined: (a) light-burned
(quicklime), (b) hard-burned, and(c) air-slaked. The latter
type was described as a heretofore unidentified form of *Hyrax is briefly described in Chapter 4 under the heading
calcium hydroxide having optical properties different Techniques with Hyrax.
from normal calcium hydroxide (portlandite) and thought **Unless otherwise stated, the indices of refraction given in this book
to be the Epezit that was defined by Guttmann and Gille refer to sodium light.
1. Mikroskopie des Zementklinkers, Bilderatlas, F.
Gille, I. Dreizler, K. Grade, H. Kramer, and E. Woer-
mann ( 1965, Verein Deutscher Zementwerke),
2. Microstructure of Portland Cement Clinker,
Friedrich Hofmanner (1973, Holderbank), and
3. Microscopy of Cement Raw Mix and Clinker,
Erling Fundal (1980, F. L. Smidth).
As will be evident, this writer has drawn heavily on the
above three publications, plus several Japanese reports,
particularly the work of Yoshio Ono, whose detailed stud-
ies demonstrate the practicality of transmitted-light micros-
copy in the cement plant. Onos Method is discussed
in Chapter 6.
A commendable effort to bring cement and concrete
microscopists together for the purposes of sharing knowl-
edge and promoting the use of the microscope in the
construction industry is seen in the relatively recent found-
ing of the International Cement Microscopy Association
(ICMA) in 1980. Published proceedings of their annual
meetings have helped immeasurably in spreading knowl-
edge of various microscopical methods and have gener-
ally stimulated growth in cement quality control through
microscopy in North America.
Polarized-light microscopy and fluorescent microscopy
have been applied to the analysis of oil-well cement blends
containing pouolans, bentonite, potassium chloride, fric-
tion reducer, modified pouolan, fluid-loss addition, silica
flour, and other materials (Reeves, Bailey, and Caveny,
1983). Examination of cement polished sections has
shown a relationship of oil-well cement thickening times
and retardation rates (Caveny, Weigand, and Bailey,
1983).
Finally, it is clear that a large portion of the published
microscopical information about portland cement and
clinker is based on materials made in rotary kilns or small
electric laboratory furnaces. The products of vertical shaft
kilns in mini-cement plants, reported to be common in the
Republic of China and in India, have been only briefly
examined (Samuel, Rao, and Chopra, 1984).

9206 Coventry Lane, Duncanville, Texas 75137 USA.


Chapter 2
Sampling and Sample Storage
samawl by increasing the probability of studying particles repres-
enting most of the original clinker sizes. One should be
Taking the clinker sample for microscopical examination aware that different size fractions of crushed clinkers may
has, as yet, no formally accepted procedure and several have different phase abundances (some aliterich, others
techniques are currently used, largely dependent on the beliterich).
purpose of the investigation. Because of time constraints J. D. Dom (personal communication, 1985) stated that
during clinker production, the clinker sample must neces- clinkers less than approximately 25 mm are virtually the
sarily be small and, therefore, the conclusions must be same and that larger clinkers exhibit effects of different
cautiously drawn. A grab sample is preferable to compos- cooling rates. Dom recommended passing a quart of
ite samples for most investigations. clinker through a crusher, producing particles of approxi-
Hofmanner ( 1973) recommends the following sampling mately5-mm diameter, followed by riffling to a volume of 1
technique: cup and pulverizing to less than a No. 30 mesh (0.59 mm).
1. At intervals of five minutes or less take three 2-kg The No. 30- to 50-mesh (0.59. to 0.30-mm) fraction is used
samples, mix, and quarter down to 500 g. for a polished section.
2. Crush the 500-g sample to 5-mm-size particles. One problem with the crushing of clinker prior to exam
3. Quarter until a sufficient amount remains for encap ination is that microcracks seen in polished-section or
sulationwithresinina25mmdiametercup.Twoencap thin-section study are ambiguously interpreted. Micro
sulations are recommended to get a representative cracks that are not artifacts of sample preparation may, in
average of the random sample. some investigations, be related to strain caused by thermal
Ono (1981) recommends a grab sample every eight- stress (Homain and Regourd, 1980) crystal reorganiza-
hour shift during clinker production: hourly samples are tion, hydration, and expansion.
taken during kiln startup. If the clinker is extremely sandy or dusty, crushing prior
Hicks and Dom (1982) recommend the Ono test to sieving may not be necessary. A random spoonful taken
(except birefringence) once per day and every time a from a well-mixed sample will likely be adequate.
change is made in the burning process and, once per Other workers prefer to sieve the clinker sample, after
week, a polished-section examination of the No. 20- to which representative portions of arbitrarily defined coarse,
30-mesh (O&I- to 0.59-mm) granulated clinker. medium, and fine fractions are selected for analysis.
For determination of the phase content of clinker, Whole or crushed clinkers are encapsulated in epoxy and
Chromy (1983) utilized polished sections made from the polished sections are prepared. Powders for study in
quartered residue from 0.5 kg of clinker ground to a transmitted light can be made from representative por-
particle size passing a 1 .O-mm sieve. A 20-mm-diameter tions of the same sieve fractions.
polished section of particles embedded in epoxy was Long (1982a) stated that the sampling technique must
prepared. be dependent on the kind of problem under investigation.
One of the most popular methods involves crushing a A constant cement-quality problem might be studied with
random clinker sample of roughly a liter volume ( 1 to 2 kg) a clinker grab sample. However, for analysis of process
to approximately 2- to 4-mm-diameter particles, from variations of several days, for example, a combination of
which a few particles are randomly selected or riffled (1) several clinker samples to form a composite might pro
for encapsulation in epoxy for reflected-light examination vide an abundance of information, particularly if the
and (2) for further crushing to a powder for immersion in clinker shows variability. Hourly samples may also be
oil on a microscope slide for examination in transmitted studied as kiln modifications take place. Long recom-
polarized light. Several encapsulations can be made, there mends taking a 15-kg sample, crushing it to less than 6
mm, then riffling or quartering and separating the 2- to in 15-ml screwtop glass vials. Only the 44- to 75-c(m size
4-mm fraction for microscopical study. Dusty or sandy range (No. 200. to 325-mesh sieves) is retained. To help
clinker should be sieved into a coarse fraction (greater prevent hydration, the vials can be stored over Drierite or
than 2 mm) and a fine fraction (less than 2 mm). The similar hydrophilic material in a vacuum jar. Various types
coarse fraction is then crushed to supply the 2- to 4-mm- of plastic bags with sealable tops are available and may
size material for microscopical study as a companion to suffice for temporary storage. However, pinholes pro
the fine fraction. Whole clinker nodules can also be stud- duced by abrasion are not uncommon if the samples have
ied. These should proportionally represent the sizes of been subjected to jostling or other types of rough han-
the nodules in the grab sample and typically number 10 dling. Metal cans with tight-fitting lids (the type in which
to 12. paint is supplied) are also relatively satisfactory for sam-
The sampling method normally followed by the author ple storage.
is to restrict the microscopical investigation to clinkers Regardless of the type of clinker storage container, if a
from only a broadly defined modal-size class from which a significant quantity of free lime is present in the clinker,
number of clinker nodules are randomly selected, some disintegration of the clinker nodules will probably occur as
for encapsulation in epoxy and others for powder-mount a result of lime hydration (air slaking) forming calcium
preparation and X-ray diffraction (see Chapters 4 and 5). hydroxide. A dry (humidity-controlled) storage nxm or
The broadly defined modal class is presumed to represent cabinet is recommended.
that part of the clinker size population that volumetrically
supplies most of the cement and, therefore, has the domi-
nant influence on the cements hydraulic characteristics. Storage of Prepared Specimens
Thus, by neglecting the largest and smallest clinkers, one
studies the most common clinker sizes that perhaps more Polished sections and thin sections can be protected dur-
accurately reflect the burning conditions and the nature of ing storage by mounting the cover glass with a drop of
the raw mix. epoxy (without hardener) on the prepared section surface.
The sampling of cements appears to present no major A small dropper bottle containing epoxy resin (without
problems. Care should be taken, however, to avoid bias hardener) is kept at approximately 40C on the slide
from samples unduly rich in coarse or fine particles, or warmer for the purpose of mounting cover glasses. Keep
samples representing areas that might be affected by ing the resin at this temperature in the bottle seems to
moisture condensation-unless incipient hydration is the minimize the crystallization that may occur at room
object of the investigation. temperature. The cover glass can be easily removed for
In conclusion, sample volumes and sampling tech- several months, but even the epoxy (without hardener) will
niques appear to be largely the arbitrary choice of the eventually bond the cover glass to the section. Then the
microscopist, with objectivity and relevance to the aim of problem becomes one of trying to remove the cover slip
the investigation as the primary considerations. A stand- with a razor blade or by grinding. The polished surface can
ard practice for sampling and sample preparation is be protected with an acrylic spray, which can be removed
needed for routine microscopy. For certain studies, clinker by gentle rubbing with an acetone or xylenesoaked rag.
nodules can be halved, one half for microscopy, the other An acrylic spray eventually cracks, however, and does not
half for chemistry and X-ray diffraction (XRD). Only one prevent hydration of free lime exposed on the section
kiln should be represented in a single clinker or cement surface.
sample. A composite clinker sample can be somewhat Immersion of epoxy-encapsulated materials in polished
confusing due to the possible variety of burning conditions sections in an anhydrous lightweight oil (preferably odor-
represented. less) in a wide-mouth glass jar with a screwtop lid effec-
Systematic microscopical analyses of the clinker with its tively minimizes, but does not eliminate, hydration. If the
corresponding raw mix and cement are highly recom- specimen is reexamined microscopically, the oil appear-
mended. It is not uncommon for the writer to place a ing on the polished surface can be removed with a sonic
portion of the greater than 44.pm cement and raw mix in cleaner containing isopropyl alcohol, followed by a force
the same cup with the clinkers for epoxy impregnation and ful isopropyl alcohol spray. Dom and Adams (1983) use
polished thin-section examination. Freon in a sonic cleaner to remove residual oil on
polished-section surfaces.

Sample Storage
Preventing atmospheric hydration and carbonation of
cement and clinker is a difficult but, for most microscopi-
cal studies, not insurmountable problem. Sample contact
with water, atmospheric or otherwise, should be mini-
mized. For long-term storage, glass jars or vials with corks
or screwtops that have been sealed with molten wax
appear to be moderately effective. During routine exami-
nations, the author stores cement or crushed clinker sieve
fractions (after wet sieving with an isopropyl alcohol spray)
Chapter 3
Stains and Etches
The techniques of imparting color to various crystalline in a 1:l ethyl alcohol-water solution followed by a
phases preferentially are well known in geology (see wash in isopropyl alcohol, and buff for approximately
Carver, 1971, and Hutchison, 1974). Stain differentiation 15 seconds on Microcloth* wetted with isopropyl
between plagioclase and potash feldspars and between alcohol. Wash with isopropyl alcohol. C,A turns
various carbonate minerals is commonplace, using parti- blue.
cles, thin sections, and polished slabs. Stains are those B. Sodium hydroxide-ethyl alcohol solution is pre
liquids or vapors that, when applied to the polished cross pared with 2.5 g of sodium hydroxide plus 40 mL of
section of a clinker or to a sample of portland cement, water plus 10 mL of ethyl alcohol. If the contact of the
preferentially color certain phases observed in reflected or polished surface with the solution is more than
transmitted light. Etches are used to bring out microstruc- roughly 20 seconds, a deposit from a reaction
tural details of individual crystals. Both stains and etches between hydroxide and aluminate forms that buffing
can be related to the relative reactivities of various clinker will not remove. CA turns blue. If determination of
phases. Photographs 5 through 10 illustrate some of the alkali sulfates is desired, stain only one time for
effects of a few stains and etches. approximately 10 seconds, washing with 1 :l ethyl
Perhaps the most thorough treatment of the subject of alcohol-water solution, followed by isopropyl alto
stains and etches is the work of Ellson and Weymouth of hol. Do not buff. This treatment will darken alkali
Australia (1988). Their paper lists approximately 43 re- sulfates slightly and with prolonged treatment (as
agent solutions and their effects on portland cement and for GA) will dissolve the alkali sulfate, producing a
blast furnace slag phases in terms of (a) reaction type dark void.
(stain or structural etch), (b) time required for the desired
C. Potassim hydr0* solution (0.1 molar aqueous)
effect, (c) recommended temperatures, and (d) con-
can be applied in single drop fashion or in a small
centrations. puddle on a polished surface for 30 seconds. Rinse
Much of the information given here was extracted from
with an isopropyl alcohol spray and dry with forced
the work of John Marlin of the Oklahoma Cement Corps-
warm air. GA stains blue, alkali sulfate darkens, and
ration (now a subsidiary of Lone Star Cement Company, free lime turns brown.
Greenwich, Connecticut). Many of his recipes and results
( 1978 and 1979) are reproduced in this chapter with only D. Boiling sodium hydroxide solution (10% by mass)
slight modification but only a few have been tried by this will turn calcium aluminate blue or brown in 20 sec-
writer. Marlin recommends making fresh solutions every onds in a high-alumina cement. Etching 30 seconds
two months for most of these stains and etches. Most of with a 1% borax solution turns &A7 gray (Long,
the solutions described in the following pages have simul- 1983).
taneous staining and etching effects, and, unless stated
otherwise, the tests are carried out at room temperature. It
will be obvious that the effects of various etches and stains
silicates
are also functions of time and clinker phase composition. A. Dilute salicylic acid stain is mixed as follows: 0.2 g
salicylic acid plus 25 mL of ethyl alcohol plus 25 mL
of water. After a 20- to 30second immersion, fol-
AhmimtesandFreeLime lowed by an alcohol spray wash, alite and belite are
A. Potassium hydroxide-etkyl alcohol solution
(5%) is placed in contact with the polished section for *Microcloth is a tough, feltlike, rayon polishing cloth with a low nap
no more than 20 seconds. Wash the section surface marketed by Buehler Ltd., of Lake Bluff, Illinois.
blue-green. A modification of this stain is 0.2 g of Effects of this stain are very similar to those of
salicylic acid plus 25 mL of isopropyl alcohol plus 25 NH,NOI except the NH,CI stain is approximately25%
mL of water, which, after 20 to 30 seconds, reveals that faster. Alite turns brown in 10 to 20 seconds; belite is
alite stains 50 percent faster than belite and which, unaffected. This stain can be used directly as a belite
therefore, can be used to distinguish the two phases. indicator by extending the submersion time to 30 to
A precise immersion time for a series of samples aids 45 seconds. Alite turns yellow to yellowish green and
in their comparison. belite to brown. The effects of this NH,CI solution are
B. Salicylic acid etchant is made by dissolving 0.5 g not as clear for belite lamellae as NH,NO, following
of salicylic acid in 50 mL of methyl alcohol. After a salicylic acid.
45second etch the alite and belite are clearly seen, I. Ammonium nitrate solution is comoosed of the
the latter showing its lamellar structure. Longer following ingredients:
contact with the solution degrades belite lamellae. 1 g NH,NOj + 20 mL Hz0
Alite is more strongly etched than belite. This etchant + 20 mL ethyl alcohol + 10 ml acetone
can be used prior to ammonium nitrate for alite-belite + 150 mL isopropyl alcohol
differentiation with very little effect on the matrix Alite is colored in 25 to 30 seconds. With increas-
phases. Reaction of salicylic acid in ethyl alcohol is 50 ing treatment time, the colors on the silicates progres
percent that of methyl alcohol and attacks alite about sively range from light brown to brown to purplish
twice as fast as belite. With isopropyl alcohol, how brown to blue to blue-green to green to yellow-green.
ever, the reaction is less than 25 percent that of Normally, when alite is stained yellow-green, belite
methyl alcohol, and alite is intensely and rapidly will be brown. This solution can be applied following
attacked, with belite almost nonreactive. the salicylic acid stain to show alite and belite with an
C. Nital is perhaps the most common etchant and approximately 30second submersion time.
stain for silicates and improves with age. Nital is 1.5 J. Hydrofluoric acid (HF) vapor, used to etch and
mL of nitric acid (HN03) in 100 mL of ethyl, methyl, stain a polished clinker, has been a very informative
isopropyl, or amyl alcohol. The author routinely technique (Long, 1982a). Almost all the clinker
uses a solution of 1 mL of HN03 and 99 mL of
phases can be differentiated with an HF vapor etch.
anhydrous isopropyl alcohol. The solution quickly The HF is kept at a temperature of 20C to 22C. A
reacts in 6 to 10 seconds with alite and belite. At a finely polished surface is held for 5 to 10 seconds in
0.05% dilution the reaction time is 20 to 40 seconds. HF vapor and, after waiting a minute or two for the
Depending on the relative reactivity of silicates, alite excess HF fumes to leave the polished surface, the
normallytums blue to green, belite is brown to blue- section is examined in reflected light. Belite turns
both silicates showing details of internal structure.
blue and alite is brown. With practice at varying the
Nital superimposed on a 20second potassium hy etch times one can develop reliable HF-vapor etch
droxide etch turns C,A light brown. criteria for other phases such as the alkali sulfates.
D. Acetone-water solution (in a 1 :l proportion) can Prout reported (personal communication, 1984) that
be used as a rinse because it reacts slowly on silicates. a temperature differential between fume and speci-
A 120second stain time reveals well-stained alite and men enhances etching. The specimen can be cooled
belite. GA is also visible. or the HF warmed. GAS (melilite) is colored with HF
E. isopropyl alcohol solution (10%) is an easily vapor and occurs in high-alumina cement (Long,
made stain (10 mL of isopropyl alcohol plus 90 mL of 1983).
water) that reacts strongly with alite and weakly with fYOTE: Care must be taken to avoid damaging the
belite in 30 seconds to 2 minutes. CA exhibits a weak microscope objective lens with HF vapors emanating
reaction. from a freshly etched polished section. Waiting a few
F. Maleic acid attacks alite and belite at about equal minutes before examination is recommended. Be
rates and a little faster than salicylic acid. When cause of the extreme danger in skin contact with HF,
followed by NHINOj, it does not give color dis- suitable precautions with gloves and ventilated hood
tinction to alite and belite. are strongly suggested.
Ci. Ammonium chloride (saturated, aqueous) colors a K. Distilled water was described by Brown ( 1948) as
hexagonal section of alite (perpendicular to the an etch that enabled one to discriminate nine clinker
threefold axis) light yellow. The slender hexagonal phases after a relief polish. With the use of present-
section of alite (parallel to the c axis) is colored blue. day materials and equipment, Browns procedure is
Zoned crystals in the slender hexagonal section show as follows: ( 1) Final polish on Microcloth or nylon with
light-blue cores and dark-blue rims. Ono recom- 0.05-pm alumina. (2) A removal etch, using distilled
mends an etch time of one-half to one second (letter, water at pH 6.8 to 7.0, is developed by holding the
1976) but this writer has found that three to four polished surface with moderate pressure on a rotat-
seconds produces satisfactory results. ing saturated Microcloth for two to three seconds
H. Ammonium chloridestain is made as follows: while the distilled water is Poured onto theMicrocloth.
1 g NH,CI + 20 mL Hz0 (3) Wash quickly with isopropyl alcohol and dry with
+ 20 mL ethyl alcohol + 10 mL acetone forced warm air. Periclase remains topographically
+ 150 mL isopropyl alcohol high due to its relative hardness. Free lime etches
dark to iridescent green and blue. CA turns dark B. Potassium hydroxide is used for detection of
blue. What Brown called dark prismatic (actually, fluoroaluminate. The section surface should be re
alkali aluminate) and ragged dark interstitial material polished after the water etch. The freshly polished
turn faint blue. Alite becomes brown, and belite is clinker surface is then exposed to O.l-molar potas-
recognized morphologically. Alkali sulfates are dark sium hydroxide solution for 30 seconds. The fluoro-
L. Dimethyl ammonium citrate (DAC) solution is aluminate compound is identified by the definitive
prepared by dissolving 192.6 g of citric acid in 1 L of brownish purple interference color that is deeper in
warm water. The solution is cooled and brought to hue and sharper in outline than the one that, as
mentioned, is sometimes visible after the 30second
2 L by adding 891 mL of aqueous dimethyl ammo-
distilled water etch.
nium solution (33 percent). A 5- to 1 O-second
application of DAC on a polished surface structurally The 30second period of etching with the potassium
etches alite strongly and belite slightly. An optional hydroxide solution apparently is not critical since similar
preparatory etch with water for five seconds will aid in results have been obtained with etch periods of 25 to 35
the identification of aluminate. seconds or longer. Any reaction product of CA with
potassium hydroxide, if present, will not interfere. CA is
M. Borax solution is used for etching pleochroite more reactive in basic solutions than the fluoroaluminate,
(approximately Cz2AIjF&). This mineral occurs in and the 30second reaction time will produce a relatively
some high-alumina cements and characteristically thick and very irregular orange-colored reaction product
has a bladelike habit. It is etched by boiling in a on the CA. This reaction product does not have a uniform
1 -percent borax solution (Long, 1983). interference color; much of the reflected light is irregularly
N. Cyclohexanediaminetetraacetic acid disodium scattered to produce a generally nondescript area of both
salt (CDTA) solution is mixed as follows: 5 g CDTA positive and negative relief, often giving the appearance of
in 100 mL distilled pure water plus 100 mL denatured a void in the clinker.
ethyl alcohol. The polished section is covered with Experimental work on the microscopical staining
the etchant and two drops of etchant are added every method also reveals that fluorine-modified alite could be
10 seconds until 60 seconds have elapsed. The identified with the 30second potassium hydroxide etch. In
surface is rinsed with ethyl alcohol. Alite is blue, that case, the characteristic pseudohexagonal outlines of
green, pastels, and other colors; belite is not highly individual alite crystals would become ragged and indefi-
colored; ferrite remains brightly reflecting; aluminate nite and the crystals would assume a faint brownish purple
appears as gray flecks or spots; free lime is highly hue similar to that seen on the ternary compound after the
colored (Caveny and Weigand, 1985). Dom ( 1985) 3second distilled-water etch. In all cases thus far, little or
stated that lime-rich alite with an EDTA-type etchant no fluoroaluminate compound has been seen when the
(30 seconds) quickly turns blue: an average lime-rich fluorinemodified alite was present.
belitetums bluish gray. Blue, relatively limerich belite It should be pointed out that the potassium hydroxide
crystals occur on the periphery of some belite nests. method should be applied to materials representing only
the compositional field where the usual portland cement
phases and fluoroaluminate can occur, as identification
does not rely on unique optical properties of the various
phases.
Calcium Fluoroaluminate
Examination of Stained Powders
A staining procedure for calcium fluoroaluminate has
been developed by microscopists at the PCA laboratories
and is based on the slightly different activities of CA and A stain technique proposed by Poole and Thomas ( 1975)
CllA7CaF2. A polished surface of clinker, etched for 3 has been modified and found to be quite appropriate for
seconds in distilled water with a pH of 6.5 to 7.0, reveals gypsum, plaster, and anhydrite in portland cement and, to
GA as a bluish color. The surface is then given a second some extent, alkali sulfates in clinker. The 6% stain solution
polish and a 30-second etch with a 0.1 -molar potassium is made from an aqueous mixture of BaClz and KMn04 in
hydroxide solution that reveals CIIACaF~ as a deep a 2:l ratio.
brownish-purple hue. Comments on each of these etches A few milligrams of cement or crushed clinker are
follow. immersed in a puddle of the stain solution in a small
A. Wateret&(&tiRerdwat&inthepHrangeof6.5to beaker for 1 minute, after which the mixture is washed with
7.0 reacts rapidly with CA to form an interference isopropyl alcohol into a No. 325 (44-pm) sieve, and finally
film on the CsA that produces a bluish color when into a watch glass. Excess alcohol in the watch glass can
viewed through a reflected-light microscope. The be drawn off with a paper towel. The residue is slowly dried
procedure must be followed closely because other in the watch glass at a temperature of approximately40C,
colors may appear with shorter etch times or slightly under a heat lamp or on the slide warmer, and examined
different acidities. Although the fluoroaluminate com- with oblique or transmitted light on the stage of a
pound sometimes also reacts to produce a faintly polarized-light microscope. Oblique light illuminates the
visible brownish purple hue, this particular reaction is particles from a point beside the microscope objective.
not used for positive identification. Sulfate minerals retain a prominent pink to red color. A

10
white paper background accentuates the color contrast skimmed aside for study in a powder mount; anhydrite
while viewing the stained particles with oblique lighting. may sink in the liquid.
Refractiveindex oils as mounting media can be used with Certain minerals in cement raw materials examined in
transmitted light; however, the alteration of some sulfates thin sections or sieved powders can be selectively stained
during the staining may interfere with refractiveindex with a wide variety of liquids (Carver, 1971; Hutchison,
determinations. 1974) and studied with a stereomicroscope and a petro-
The following easy method for concentrating some of graphic microscope. The stains are normally used to
the sulfates in cement or crushed clinker for microscopical augment data from ordinary optical microscopy. Stain
examination has been developed. ( 1) Place a small portion procedures to distinguish the following minerals may be
of sample into a watch glass and flood with isopropyl helpful in raw material investigations: calcite, dolomite,
alcohol. Swirl the mixture in the watch glass for a few ferroan calcite, ferroan dolomite, aragonite, magnesian
seconds to concentrate the whit&o-clear sulfate particles calcite, gypsum, anhydrite, alkali feldspar, plagioclase
in the center. (2) Draw the liquid off with a paper towel and feldspar, feldspathoids, cordierite, quarts, anorthoclase,
dry the remaining powder in the watch glass under a heat paragonite, muscovite, and others.
lamp or on the slide warmer (no hotter than 40C). (3) Observations of minerals and rocks in transmitted
Using a thin metal spatula, scrape off the top-central area polarized light, utilizing the principles of optical mineralogy
of the residue in the watch glass and place it on a micro- combined with stain techniques, yield a wide variety of
scope slide for examination in oil with a selected index of important analytical data readily applicable in cement
refraction (n). manufacture. Mineral characteristics in transmitted and
Although the mount is impure, in an oil with a refractive reflected light are clearly described in standard optical
index of 1.54, gypsum (n = 1.52 to 1.53) and plaster (n = mineralogy texts (Heinrich, 1965; Kerr, 1977). The optical
1.55 to 1.57) can be distinguished. Gypsum has inclined properties of almost all known minerals, with a concise
extinction, but the extinction of plaster is straight (Lea, description of optical theory and technique, are given by
1970). Anhydrite (n = 1.57 to 1.61) also shows straight Fleischer, Wilcox, and Matzko (1984) who emphasize
extinction, cleavages at right angles, and relatively high particle-mount analysis. An excellent book by MacKenzie
birefringence. Extinction angles to differentiate gypsum and Guilford (1981) emphasizes color photomicrographs
from plaster, however, are difficult to apply due to the very of the common rock-forming minerals as seen in thin
finely microcrystalline structure common in gypsum and section. A similar, highly recommended, book by Mac-
plaster particles. This microstructure appears to be a pro Kenzie, Donaldson, and Guilford (1982) covers igneous
duct of recrystallization due to relatively high temperature, rocks and textures. Sedimentary rocks are depicted in a
grinding stress, or both, which convert the previously book by Adams, MacKenzie, and Ciuilford (1984). Rock
continuous atomic structure into a myriad of minute and mineral sets, particle mounts, and thin sections with
polygonal crystalline units. Dom (personal communica- descriptions are commercially available and, to a great
tion, 1985) reported that sulfates such as gypsum and extent, can serve as microscopical standards.
plaster float in refractive-index oil (n = 1.71) and can be

Photomicrographs of Effects of Stains and Etches


Photograph 5 Coarsely uystalline clinker from
coarse seashell feed. Angular subhedral to euhedral
Mue alite, round tan-to-brown belite with wide
lamellae, and matrix of dark aluminate &A) and
brightly reflecting ferfite (C,AF). Coal- and coke-
fired, semidry process kiln, 1850 tons/day. High
maximum temperature, long burning time, slow
heating rate, quick to moderately quick cooling,
8390 psi (44.1 MPa).

Polished section
Nital on KOH etch
FD = 0.21x0.21 mm
Photomicrographs of Effects of Stab and Etches (continued)
Photograph 6 Blue coloration on alite with an
otherwise uniform tan color on alite crystals. Possi-
ble expkmations include differences in uystallo-
graphic orientation, chemical composition, st~ctu-
ral state (for example, monoclinic versus Mclinic),
or perhaps combinations of these.

Polished section
Nital etch
FD =0.21x0.21 mm

Photograph 7 Differential colomtion by nital etch


on angular alite and round belite. Coarsely uystal-
line clinker from coarse raw feed. Coal- and coke-
fired, semidry process kiln, 1850 tons/day. High
maximum temperature, long buming time, slow
heating rate, quick to moderately quick cooling,
8390 psi (44.1 MPa).

Polished section
FD = 021x0.21 mm

Photograph 8 Aqueous NH Cl etch (3 to 4 sec-


onds). Sections perpwrdicu 4ar to the c crystallo-
graphic (three-fold axis) of alite are brown. Sections
parallel to c are blue.

Polished section
FD = 0.12x0.12 mm
Photograph 9 Large, round, slightly raggedy be
Ike; blue subhedral to anhedral alite; and matrix of
aluminate (C arrow) and fenite. Superimposed
nital over KOi?pruxluces increased clarity in mati
phase definition.

Polished section
Reflected light with stop
m = 0.21xo.21 mm

Photograph 10 Wekiifferentiated matrix of ahuni-


nate (C$) and fenite (C4AF) in nit&etched pol-
ished section.

Oil immemion
Reflected light
FD = 0.1oxo.10 mm
Chapter 4
Preparation of Polished Sections, Thin Sections,
and Particle Mounts
Methods of sample preparation (Figure 1) for the micro
scopical investigation of clinker and cement are essentially
the classic geologic techniques of optical mineralogy and
petrography, with minor variations. In this chapter the use
of diamond-rimmed cutoff saws and various grinding and
polishing equipment is given principal emphasis in the
production of polished sections, thin sections, and pol-
ished thin sections. The chapter summarizes sample
preparation procedures for clinker and cement studies
using the so-called petrographic microscope with trans-
mitted polarized light, the so-called metallographic micro
scope with reflected light, and the scanning electron
microscope (SEM).
The importance of a well-prepared surface should not
be underestimated. The author strongly believes that
efforts to produce a high-quality polished section or thin
section are rewarded by the relative lack of artifacts that
can possibly lead the investigator to incorrect interpreta-
tions. Phase identifications free of doubt are worth the 5 7 8
extra few minutes of preparation time.
6
Methods making use of epoxy resins, resulting in pol-
ished sections in only a few minutes, are discussed first,
followed by details of impregnation and encapsulation.
Equipment and techniques for grinding and polishing, Figure 1 Modes of sample preparation: (1) single
including thin-section procedures, are described. The use clinker, impregnated with epoxy resin, cut, and
of Hyrax, a synthetic resin with an index of refraction of polished; (2) <rushed clinker fragments, encapsulated
1.71, is discussed, followed by a description of a recom- and impregnated with epoxy, cut, and polished; (3)
whole clinkers impregnated with epoxy and mounted on
mended method for refractiveindex determination of par- a thin film of epoxy on a glass microscope slide, cut,
ticles mounted on a thin film of epoxy. and polished; (4) millimetersize crushed clinkers,
NOTE: Many of the chemicals used in sample preparation embedded in epoxy, ground, and polished; (5) cement,
and examination are toxic and adequate ventilation is an size graded by sedimentation in an alcohol-mhmrai
absolute requirement, as are other common laboratory spirits mixture in a glass vial, dried, impregnated with
safety precautions. epoxy, cut, and polished; (6) drilled holes in an epoxy
plug, filled individually with cement (a) extracted wlth a
potassium hydroxide-sugar solution, (b) extracted wfth
maleic acid, and (c) unextracted-the plug has been cut
Basic Steps for Rapid Polished and pollshed; (7) thin section of whole cllnkers; section
Section Preparation thickness is approximately 22 @; (8) crushed clinker,
No. 200- to 325.mesh fraction, ln Hyrax, for
The procedure described here is an outline of recom- determination of the kiln parameters with the Ono
mended steps in the production of polished sections of Method. Scale dhdsions in mm.
whole clinkers or a sieved fraction of crushed clinkers. The
recommended procedure involves the use of epoxy resin,
the Ecomet* (a rotating-wheel grinder and polisher), and
the Isomet* (a tabletop saw). These instruments are illus-
trated in Figures 2 and 3. An elapsed time of less than 30
minutes is typical for the proposed procedure by which a
virtually flawless polished section is produced. Following
are the basic recommended steps, using the Ecomet
and Isomet:
1. Vacuum impregnate the clinker fragments or whole
clinkers with epoxy resin.
a. Encapsulate in labeled polyethylene cups, or
b. Mount small whole clinkers (or a selected sieved
fraction of crushed clinkers) on a cleaned, labeled,
glass microscope slide (46x24 mm), see Fig. 1.
2. Cure in an oven or slide warmer at approximately
75C.
3. Cut with the lsomet saw.
4. Grind the sawcut surface with the Ecomet, using No.
320 adhesive-backed, silicon-carbide paper for
approximately two to three minutes.
5. Grind on No. 600, adhesive-backed, silicon-carbide
paper for approximately two to three minutes.
6. Grind the mount on a glass plate with 5-pm alumina
for approximately two minutes.
7. Polish on Texmet* (a low-nap chemotextile polishing
cloth) with 0.3.pm alumina for roughly three minutes
with the Ecomet. Examine the section microscop
ically and repolish if grinding pits are observed.
8 . Polish onTexmet* or Microcloth* with 0.05km alumina
for three minutes; this step is considered optional. Figure 2 The Isomet (upper instrument) and the
Minimet (lower instnanent). The Isomet blade moves
9. Clean the polished section with a forceful isopropyl through a container of propylene glycol as the specimen
alcohol spray and dry with forced warm air (an elec- is lowered by gravity onto the cutting edge. The Minimet
tric hair dryer). arm fits into a hole in the epoxy encapsulation and
Propylene glycol is used as the grinding and polishing moves the sample in an irregular manner on the
liquid in all steps. Pressure on the section surface is two to polishing cloth attached to a glass platen in the bowl.
four pounds (0.91 to 1.81 kg). Care should be taken not to
allow drying of the polished surface prior to the last step
because grinding and polishing debris is difficult to
remove, even with a sonic cleaner. Contamination of a
polishing cloth can quickly ruin a polished section, requir-
ing the worker to return to the grinding steps. Therefore,
between each of the grinding and polishing steps, the
section is washed with isopropyl alcohol and the workers
hands washed with soap and water.

Encapsulation, Impregnation, and


Particle Mounting
Many materials (clinkers, metals, rocks, minerals, and so
on) require impregnation or encapsulation or both in
order to prepare them properly for sectioning. If they are Figure 3 The Ecomet, a grinder and polisher with a
friable, or even slightly crumbly, impregnation is manda- removable rotating wheel on which adhesive-backed
tory to produce a high-quality section. Several resins are papers, bearing various grit sizes of silicon carbide or
suitable for both impregnation and encapsulation (see polishing cloths of several types, can be placed.
Table 4 in Chapter 10).
The epoxy-resin procedures described here are intended
for single polished sections and polished thin sections of Buehler Ltd.
selected sieve fractions of whole or fragmented clinkers, 3. Epoxy hardening time ranges from 10 minutes (Epo-
rocks, bricks, ceramics, concrete, and many other mate- Kwick at 105C) to several hours (Araldite and Epofuc
rials. The desirable properties of an epoxy-encapsulating at room temperature). Araldite and Epofuc harden in
and -impregnating medium are approximately 1 to 1 YZ hours on the electric slide
1. Insolubility of the hardened epoxy in acetone, xylene, warmer set at 40C to 50C. Temperatures above
alcohol, or other similar solvents. 75C or several hours on the slide warmer cause
significant strain birefringence in the epoxy, thereby
2. Hardness sufficient to promote the development of a
reducing its optical usefulness in transmitted light
relatively flat surface during grinding and to minimize
Strain is minimized by curing at room temperature.
the development of panicle relief during polishing.
For polished sections, epoxy strain is normally not
3. Quick setting, within a few hours at most, with neither important. Waiting time for the epoxy to harden is
inordinate heat generation nor excessive shrinkage. almost never a problem at PCA because, normally,
Some epoxies and other cements, such as cyanoacry- several clinker projects are concurrently underway
late ester (Super Glue), which harden in only a few and in various stages of completion.
minutes, are recommended in circumstances where
quick answers are needed. Prout (letter, 1984) recommends the use of Quick-
mount (see Table 4) which hardens in 25 to 30 minutes.
4. Low viscosity for maximum penetration of the speci- Clinkers are placed in bottomless brass cups on a glass
mens. Xylene and toluene can be used as a thinner at plate covered with a petroleum jelly, such asvaseline, and
a concentration of not more than 25 percent by weight
the Quickmount is added.
of resin. Filling as many of the pores as possible with
epoxy is desirable in order to reduce retention of
grinding and polishing debris and of cleaning liquids Sawing,Grinding,andPolishing
that can interfere with stains and etches. Low
viscosity resin is a suitable medium for producing a The wide variety of available sawing, grinding, and polish-
size-graded cement or raw feed sample, using a ing equipment, and the necessity for economically pro
centrifuge to effect the particle separation in a glass ducing a high-quality polished section, result in several
or polystyrene test tube (Campbell, 1986). options in building a compact, relatively maintenancefree
5. Wetting characteristics that produce a tight bond on and inexpensive system for sample preparation. At PCA
the particles, improving edge retention of the par- three instruments are given daily use in the preparation of
ticles during grinding and polishing. polished sections: the lsomet and Minimet (Fig. 2) and the
Ecomet (Fig. 3).

Encapsulationandimpregnadon Isomet and Minimet method


The procedure utilizing epoxy resins (Araldite, Epo-Kwick, Preparation of high-quality polished sections or polished
and Epofuc*) at PCA to encapsulate and impregnate a wide thin sections requires expertise and patience. A tabletop
range of materials in the petrographic laboratory is as saw (the Isomet) and a small polishing device (the
follows: Minimet) have greatly improved the polishing of encapsu-
lated clinkers and single thin sections. The method of
1. Immerse the whole clinker or a sieved fraction repre- preparing polished sections and polished thin sections
senting several clinkers in the freshly mixed epoxy plus described here is relatively quick and, in the long run,
hardener in a small, labeled polyethylene cup (approxi- economical, especially if several sections are examined in
mately IO-mL capacity and 25-mm diameter), or the course of microscopical investigations. The method
other suitable labeled container, coated with a thin has been used for 12 years by the writer for routine
film of silicone mold release. A small file-card label, microscopy of cement raw materials, clinker, paste, and
inscribed with India ink, can be placed on the inside of concrete. Although not as fast as grinding and polishing
the cup before the sample and epoxy are added. If a with the Ecomet, the major advantage of the Isomet-
thin section is to be made and determination of its Minimet method is that the instruments are busy cutting,
thickness is necessary, quartz grains (50 to 100 grinding, and polishing while the microscopist is else
mesh) with a known constant birefringence of 0.009 where, returning frequently to keep the project progress-
may be added to the mix in this step. Thin-section ing. In addition, theMinimet is useful in polished section-
thickness can, therefore, be calculated. The inclusion electron microprobe studies. The IsometMinimet proce-
of quartz increases the time required for sawing, dure is as follows:
grinding, and polishing due to the minerals hardness 1. The sample is impregnated and encapsulated with
(7 on Mohs scale). epoxy resin as previously described.
2. Place the polyethylene container with its contents in a 2. The encapsulation is placed in the proper chuck at-
vacuum bell jar and evacuate for a few minutes. tached to the lsomet saw, which slowly cuts the sam-
Epoxy will bubble under vacuum and, if the container ple as it is lowered by gravity onto a slowly moving,
is too full, will overflow. Periodically breaking the thin, diamond-rimmed blade. The blade edge passes
vacuum will reduce the bubbling tendency. Slowly
release the vacuum, allowing atmospheric pressure
to force the resin into the sample. *See addresses in Table 5, Chapter 10.

16
through propylene glycol in the coolant container. quently, with a single Ecomet and several interchangeable
Sawing time normally takes 5 to 10 minutes, after wheels, the entire grinding and polishing process can be
which the saw automatically stops. A 127-mm-di- accomplished. Or, as is found at PCA, three Ecomets
ameter blade with 45-mm flanges is recommended. are used with several interchangeable wheels: one Ecomet
3. At this Point, the Minimet is used for grinding and for coarse grinding, another for fine grinding, and a third
polishing. A4.75-mm-diameter hole is drilled into the (with variable speed) only for polishing. Interchangeable
center of the top of the encapsulation into which the wheels on which polishing cloths and polishing com-
arm of the Minimet is placed. Prout (letter, 1984) pounds have been placed are kept in large zip-lock plastic
recommends the use of a carbide-tipped bit. The bags between periods of use in order to minimize contam-
bottom of this hole must be 5.6 to 6.4 mm from the ination. This is particularly important when diamond is
surface to be polished. A sample alignment fucture used as the polishing compound. Having more than one
(also supplied by Buehler Ltd.) aids in drilling the hole Ecomet lessens the chances for contamination by decreas-
to the standard depth. Using a moderate load of one ing the handling of wheels. A section can be routinely
to two pounds (0.45 to 0.91 kg) on the encapsulation, ground, Polished, and sonically cleaned in approximately
the freshly cut surface is ground successively with 10 minutes.
propylene glycol on No. 320 and No. 600, adhesive Assuming that the sample has been impregnated and
backed, silicon-carbide papers mounted on glass encapsulated in epoxy resin as previously described and
platens within plastic bowls placed on the Minimet. A that the mount has been cut with the lsomet or other
setting of 7 for the Minimet arm speed is used. suitable saw, the encapsulation is ready for grinding and
Approximately 6 to 10 minutes for each paper is polishing with the Ecomet as follows:
normally sufficient, after which the sample is thor-
1. Grind the saw-cut surface by hand for at least three
oughly cleaned with isopropyl alcohol in a sonic
minutes on a rotating Ecomet wheel with an adhesive-
cleaner or with a spray bottle. Using a figure-eight backed, No. 320-grit, silicon-carbide paper. Wheels
motion, the sample is finely ground by hand on
and discs with embedded diamonds are also avail-
a glass plate with 5-pm alumina in isopropyl alcohol
able and highly recommended because they sig
or propylene glycol for approximately three minutes. nificantly shorten the grinding steps. Propylene glycol
Again, the sample is thoroughly cleaned in alcohol.
or isopropyl alcohol are used as vehicles in all
4. At a speed setting of 7 and a load of 2 pounds grinding and polishing.
(0.91 kg), an adequate polish is produced in approx- While the encapsulation is in contact with the
imately 6 to 10 minutes as the sample moves in an grinding paper, move the mount clockwise (opposite
irregular manner on the adhesive-backed Texmet on the direction of the revolution of the wheel). Periodi-
which a few drops of propylene glycol and 0.3-pm cally rotate the encapsulation by hand to promote
alumina have been placed. The sample is removed uniform abrasion. The wheel rotates at approximately
and thoroughly cleaned as described. If, after micro- 350 revolutions per minute. Use relatively heavy
scopical inspection, the polished surface still shows pressure on the wheel during grinding and polishing.
grinding pits, repeat the polishing step.
2. After cleaning the fresh, coarsely ground surface with
5. The final polish (optional) is produced in approxi- a forceful isopropyl alcohol spray, apply a No. 600-
mately 6 to 10 minutes with the Minimet, using liberal grit, silicon-carbide, adhesivebacked paper to the
amounts of 0.05-pm alumina on Texmet with a few grinding wheel and grind the specimen surface for at
drops of propylene glycol or alcohol, again using a least three minutes using isopropyl alcohol or pro
speed setting of 7 and a load of 2 Pounds (0.91 kg). pylene glycol as the vehicle.
Care must be taken if using isopropyl alcohol not to
3. After thorough cleaning, grind the sample for at least
let the cloth dry out during polishing. For easy recog
nition of periclase, relief is enhanced by using two minutes on a clean glass plate to which 5-pm
alumina grit has been applied, using a figureeight
Microcloth and 0.05-pm alumina. Diamond grinding
motion. Be certain to clean the encapsulation and
and polishing compounds quickly produce a superb
hands thoroughly between the grinding steps. Con
surface and are advisable especially when use of the
microprobe is anticipated. tamination can quickly ruin all previous work and is
quite probable with a less than careful technique. A
6. After thoroughly cleaning the specimen with an alcohol forceful alcohol spray is moderately successful for
spray and drying with forced warm air, the polished cleaning, but a sonic cleaner followed by the iso-
section can be examined in reflected light. An etched propyl alcohol spray appears best.
surface is normally necessary for study with a scan If the clinker is hard and dense, encapsulation,
ning electron microscope and microprobe. impregnation, and sawing are not absolutely neces-
sary. A flat surface can be produced by applying the
clinker to a coarse grinding paper (No. 240 grit or
Use of the Ecomet coarser) on a rotating wheel, followed by the required
The versatility of the Ecomet is clear from the fact that its grinding and polishing steps.
rotating wheel is removable and interchangeable with 4. Polishing the saw-cut encapsulated clinker (or a
other wheels on which a variety of adhesive-backed grind- single bare clinker) by hand requires diligence,
ing papers and polishing cloths can be attached. Conse patience, and practice to produce a high-quality fin-

17
ish, but it can be done in only a few minutes. The edge scribed by Roy Hams (1984) of the Monarch Cement Com-
of the section surface should be beveled (rounded) pany, Humboldt, Kansas. With Harriss method the -30 to
by abrading it against a fine steel file or a coarse +200 mesh clinker fraction is polished on a glass micro
abrasive paper attached to a rotary wheel to remove scope slide, the entire procedure typically requiring less
sharp corners or edges that might tear the polishing than 20 minutes. Harriss technique, designed for rapid
cloth. analysis, is as follows:
Using a thick slurry of 0.3-pm alumina on Texmet 1. On a cleaned, labeled, petrographic glass slide sprin-
with alcohol or propylene glycol as a vehicle, polish kle a liberal amount of crushed clinker and add a few
the sample on the rotating Ecomet wheel. A moder- drops of Super Glue.
ate to heavy pressure on the sample against the 2. Place the slide on the slide warmer for 5 minutes at
Texmet with a circular motion opposite to the rota 105F.
tion of the wheel facilitates the production of a mirror
3. With a slide holder designed for use with theMinimet,
finish in approximately two to three minutes.
the mounted material is ground by hand with 5.0-pm
5. The final polishes (optional) are accomplished in alumina on a glass plate. Isopropyl alcohol is used as
roughly two minutes with 0.05-pm alumina on the vehicle.
Texmet, followed for one minute on Microcloth,
4. After cleaning the slide, slide holder, and hands, the
which, because of the slight nap of the latter, will
final polish is accomplished with the Minimet with
produce a minor relief and can be helpful in identi-
0.3-pm alumina and propylene glycol on Texmet.
tying periclase.
This writer has had excellent results using techniques
After cleaning the polished surface with isopropyl alco- somewhat similar to those of Harris (1984) for producing
hol in the sonic cleaner, the section is dried with forced polished sections of small whole clinkers (pea size) or
warm air and is ready for study in reflected light. Effects of
crushed clinkers (-4 to +8 mesh). Because of the chance
stains and etches can be removed by repolishing the
of sample bias due to crushing and sieving, the writer
section with 0.05-pm alumina and Texmet. Suitably pol- favors polished-section examination of whole clinkers,
ished and etched surfaces can be examined with a scan-
where possible. The technique, using epoxy instead of
ning electron microscope. Super Glue, is as follows:
Drafting linen, washed to remove the starch, can be
successfully used as a polishing cloth with SnOz or other
1 . Place 15 to 20 small clinkers in freshly mixed epoxy
polishing compounds. Diamond pastes or aerosol sprays
resin with hardener and vacuum impregnate.
are applicable in the polishing steps and are highly
recommended. In addition, wrapping paper with 0.25-pm 2. Remove the clinkers from epoxy with forceps and
diamond paste on the Ecomet produces an excellent place them on a paper towel for approximately one
low-relief surface. minute so that the excess epoxy can be absorbed into
Prout (letter, 1984) recommends the following proce the towel.
dure for preparation of polished sections for routine rapid 3. Place the clinkers on a clean, labeled, petrographic
examination: glass slide and put the slide in an oven (or on a slide
1. Encapsulate clinker halves (previously cut with the warmer) set at 70C. The epoxy that flows from the
Isomet) in Quickmount. clinkers during heating is sufficient for bonding the
clinkers to the glass. Buehler Epo-Kwick hardens in
2. Grind the encapsulation for a short time with No. 240
approximately 10 minutes.
silicon-carbide paper on a rotating wheel to expose
the clinkers. Denatured alcohol (99 parts ethyl alco- 4. Withdraw the slide from the oven and allow the slide
hol plus 1 part benzene) is used for grinding and to cool for a minute or two. If any epoxy has hardened
polishing. on the bottomside of the glass, scrape it off with a
single-edged razor blade. The slide, with clinkers
3. Subsequent grinding steps are (a) 90 seconds with
firmly mounted, is now ready for cutting on the
No.1 200 alumina on a glass plate and (b) 90 seconds
Isomet, after which full cross sections of the clinkers
with No. 3200 alumina on a glass plate.
will be exposed. Cutting time is approximately three
4. The section is polished in 45 to 60 seconds with 1 -pm minutes. Grind the saw-cut surface with No. 320 and
alumina on drafting linen. 600 silicon-carbide papers on the Ecomet. Using the
Resin-bonded diamond discs placed on a flat tabletop slide holder, grind the sample on a glass plate with
function quite well for rapid hand grinding of a saw-cut 5-pm alumina.
surface of epoxy-encapsulated clinkers preparatory to pol- 5 . Polishing the mounted clinkers can be accomplished
ishing with the Minimet or Ecomet (Hoodmaker, personal in as short a time as three minutes on the Ecomet or
communication, 1985). A few drops of propylene glycol four to eight minutes with theMinimet, using 0.3-pm
are used as the grinding and polishing liquid. The dia- alumina on Texmet and isopropyl alcohol. The writer
mond discs are cleaned with soap and water and rinsed prefers to use propylene glycol with the Minimet
with a forceful alcohol spray. because evaporation is slow and the Minimet can be
left unattended.
Harriss technique Between grinding and polishing steps, the mount
A quick, recently developed technique using Duro Super and slide holder should be cleaned with a forceful
Glue (containing a cyanoacrylate ester) has been de isopropyl alcohol spray. The hands may be washed
with soap and water. Before examination, the pol- 3. The wafer is then slowly and gently reduced to
ished section should be cleaned in a sonic cleaner approximately 30 pm on the diamond cup wheel of
with isopropyl alcohol, followed by a brief rinse with the Ingram thin-section grinder or other similar
an alcohol spray. equipment. Grinding time is approximately five min-
utes. If a mechanical thin-section grinder is not avail-
able and time is not a problem, the wafer thickness
can be reduced by hand, using a Buehler thin-section
Thin Sections holder (Buehler catalog No. 30-8005) and a sequence
of coarseto-fine, adhesivebacked, silicon-carbide
Routine clinker investigations normally do not involve pol- papers or, preferably, diamond discs on a horizontal
ished thin sections. However, for some aspects of clinker
rotating wheel. Propylene glycol as the vehicle and a
research and for many raw material studies, thin sections
speed of approximately 200 to 350 revolutions per
are invaluable. minute are recommended. Rather than using the
A clinker thin section at PCA is always made from the
Ingram grinder for the entire grinding step, less dam
polished epoxy encapsulation after the latter has been
age to the thin section results when thickness reduc-
studied in reflected light and mounted on a glass micro tion from 30 to 20 pm is accomplished with silicon-
scope slide with epoxy resin. The thin-section top surface is
carbide papers on the Ecomet wheel, or with loose
also polished and, therefore, the section can be studied No. 600 grit silicon-carbide powder on a glass plate.
with both transmitted and reflected light, each of which Finally, gentle hand grinding with a 5-pm alumina for
has distinct advantages. Thin sections on the order of 15-
a few minutes with alcohol or propylene glycol on a
to 20-pm thick can be easily made, using a diamond-
glass plate brings the section to the proper thickness,
rimmed cutoff saw, diamond grinding equipment, a glass which for portland cement clinker is approximately
plate, and polishing wheels. At a thickness of approxi-
15 to 20 pm.
mately 15 pm the problem of crystal overlap is minimal.
Examination in transmitted light allows measurement of 4. Using Texmet with liberal amounts of 0.3.pm alum
optical properties, such as birefringence, and observation ina, a few drops of alcohol or propylene glycol, and a
of pleochroism; reflected-light examination at higher slide holder, the thin section is polished on the
magnification (particularly with oil immersion) permits rotating wheel of the Ecomet at a medium speed and
study of the interstitial materials and hardness relief. moderate pressure. Circular movement of the slide
Doubtful phase identifications with reflected light may be opposite to the direction of rotation of the polishing
resolved with transmitted light. Selected size fractions of wheel is recommended. This polishing step requires
the clinker, cement, and raw feed can be combined in a approximately three to fnre minutes. Although this
single encapsulation. The procedure at PC4 for making step is not intended to reduce thickness, with extended
thin sections, requiring a worktime of approximately 15 to application some reduction in thickness does occur.
30 minutes. is as follows: The Minimet can also be used to polish thin sections.
With the speed set at 7 and a moderate load, and
1. The previously ground (or polished) surface of the using 0.3.pm alumina, Texmet, and propylene glycol,
encapsulation is mounted on a cleaned, labeled, the Minimet can be left largely unattended during the
petrographic slide (standard size, 46x24 mm) with a polishing. Clean the slide thoroughly.
small amount of epoxy. The writer has found that by 5. An optional final polish is accomplished with 0.05.
smearing and striking off a few successive droplets of pm alumina on Microcloth in three to five minutes on
epoxy with the glass microscope slide, the epoxy fills the Ecomet or Minimet (same settings as described
virtually all the voids on the section surface and there in step 4.) Diamond paste is recommended for thin
by promotes a firm bond. Curing time is two hours sections that are to be studied with the scanning
with Epofrx and fnre to six hours with Araldite. A electron microscope and the microprobe.. The sec-
weight of approximately 100 grams, such as a lead tion should be an optimum thickness of approxi-
fishing sinker or a I-in.-diameter (25.4-mm) hex- mately 15 to 20 pm, at which the interference colors
agonal steel nut, can be placed on top of the mount in cross-polarized light are low first-order gray for
during hardening of the epoxy to maintain a uniform quartz and alite and first-order whitish gray to yellowish
epoxy thickness between the polished surface and white for belite. At thicknesses less than 20 pm,
the glass slide. The top surface of the slide warmer damage to the quartz becomes progressively more
should be protected from epoxy with aluminum foil significant. However, significant clinker damage with
and a silicone grease or mold release. Epoxy that these techniques does not occur in most cases until a
overflows the slide and hardens on the bottom of the thickness of approximately 10 pm is reached. For
slide must be carefully removed with a single-edged many crystals the damage occurs in the form of
razor blade after hardening. cleavage cracks.
2. After the epoxy has hardened, the excess mount is 6. The thin section is then cleaned with isopropyl
removed by sawing on the Ingram thin-section cutoff alcohol in a sonic cleaner, followed by a forceful spray
saw or similar device (for example, the Buehler of isopropyl alcohol, then dried with warm air. The
PETRO-THIN) so that a wafer with a thickness of section is ready for staining, etching, and examina-
approximately 0.5 mm remains on the glass slide. tion in reflected light. For work in transmitted light,
The lsomet can also be used. the cover glass is loosemounted temporarily with

19
refractiveindex oil (n = 1.71). Thus, the cover glass 2. Place a drop of Hyrax (nom-rally shipped diluted with
can be removed and the slide cleaned with isopropyl toluene or xylene) on the petrographic slide and add
alcohol when necessary to examine the section again a few grains of the clinker or cement (44- to 75-pm
in reflected light. Effects of most stains and etches fraction, for example).
can be removed by repolishing the section with 0.3-pm 3. Stir the particles briefly with a clean needle to pro
alumina on Texmet, but occasionally one has to duce a uniform dispersion and allow the mixture to
regrind the surface to ensure against misinterpreta- heat until it stops bubbling (evaporation of toluene).
tions promoted by superimposed effects of some The heating time may take up to 20 minutes.
etches. 4 . Using broad-tipped forceps, place the cover glass on the
The writer has found that by extending the time of the molten resin by first resting one edge of the cover
final grinding step (5-pm alumina on a glass plate), an glass on the slide and slowly lowering the cover glass
intentionally wedged section that thins to zero thickness into position. The excess resin, if present, can be
on one side and is approximately 20 pm on the other side squeezed out by gentle pressurewith a pencil eraser.
can be produced. Although subsequent polishing thins 5. Using broad-tipped forceps, remove the mount to a
the section somewhat, it usually is not detrimental. A flat, cool surface and allow the resin to harden
wedged polished thin section is actually advantageous for (approximately 10 minutes).
( 1) determination of phase birefringence on the thick side
The procedure for making thin sections is similar to that
and (2) examination of interstitial microstructure in trans-
using epoxy, except considerably more heat is involved
mitted light on the relatively thin side. Ultrathin sections for
light microscopy and SEM-EDXA work can be made by and the technique is generally much faster. Methods de
scribed below are for whole clinkers with 25 mm diameters
using an epoxy disc that has been polished on both sides
or slightly larger. If the clinker is not friable, then, using
instead of a glass microscope slide. An epoxy-encapsulated
coarse grinding equipment or the lsomet saw, a flat sur-
and polished section of clinker is attached to the disc with
face on the clinker nodule can be produced which will
epoxy. A wafer is cut, followed by grinding and polishing to
subsequently be polished in the normal manner with var-
a thickness of approximately 10 pm.
ious cloths, polishing compounds, and handheld tech-
A light application of an acrylic spray protects the thin
niques. For friable clinkers the procedure for making pol-
section during storage and can be removed with xylene,
ished sections and thin sections is as follows:
trichlorethylene, or isopropyl alcohol. Preferably, a cover
glass will be mounted in epoxy resin (without hardener). 1. Impregnation is mandatory. Place the clinker in a
The cover glass can be removed by sliding it off with the small watchglass mounted on the triangle on an
fingers. The residual liquid resin is readily removed by a electric hotplate at approximately 90C under a venti-
stream of toluene or acetone. lating hood.
Polished mounts and polished thin sections are pre 2. Slowly add Hyrax in droplets to the warmed clinker in
pared commercially by several companies (Table 6). the watchglass until the clinker rests in a small
Some companies will stain raw feed thin sections for puddle. Allow the Hyrax to bubble and penetrate the
feldspar and carbonate mineral identification. Waiting specimen. Viscosity at this stage is quite low and
time may range from a few days to several weeks. For impregnation is virtually thorough. Heat until bub
clinker thin sections, the microscopist must speoify the bling stops, which for some specimens may require
required thickness and that nonaqueous media must be 20 minutes or more. Remove and cool the specimen
used in cutting, grinding, polishing, and cleaning. on aluminum foil at rmrn temperature.
-3. Using the Isomet, or similar saw, with propylene glycol
as the blade coolant and lubricant, cut the impreg-
TechniqueswithHyrax nated clinker at roughly the clinker midsection.
Because the clinker is relatively soft, cutting time is
Properly cured Hyrax has an index of refraction of approx-
only a few minutes. The resulting specimen is ready
imately 1.71, which is very close to most clinker phases.
for grinding, polishing, and, if desired, reflected light
Therefore, when used as a mounting medium for a clinker
examination.
thin section and its cover glass, or for whole particle
mounts as in the Ono Method, the high quality of the 4 . The polished surface of the impregnated specimen is
preparation becomes a permanent feature, changed only placed in a puddle of hot, bubblefree Hyrax on a
by remelting the resin. The procedures for using Hyrax as a cleaned petrographic microscope slide on a level
powder-mounting medium are described below, followed triangle, sitting on the hotplate under a hood at
by a technique for thin sections using the Isomet, Minimet, approximately 90C. As the Hyrax in the clinker melts,
and other equipment. it flows out of the specimen and serves as a bonding
medium to the glass slide. If bubbles form, the mount
1. Place a clay-covered, iron-wire triangle on a small, should be heated until bubbling ceases, after which
level, electric hotplate under a ventilating hood. Place the mount is removed from the hotplate to a flat,
separately on two comers of the level triangle a room-temperature surface for cooling. With forceps,
cleaned, labeled glass microscope slide (petro- gently press the clinker to the glass slide to ensure
graphic type, 46x24 mm) and a cleaned cover glass. an even thickness of Hyrax beneath the specimen.
Bring the temperature of the glass slide and cover After cooling, check the bond for bubbles with a
glass to approximately 90C. stereomicroscope. If the remaining bubbles are

20
thought to be excessive, reheat the mount and attempt with various refractive-index (RI) liquids and for the appli-
to work the bubbles out by moving the clinker cation of various stains as in raw feed analysis. The tech-
around on the slide with forceps. nique for making epoxy film-grain mounts is as follows:
5. Use an lsomet or similar saw, cooled and lubricated 1 . Cover a clean, labeled, glass microscope slide (46x24
with propylene glycol, to cut away the excess mount, mm) with a puddle of epoxy resin plus hardener.
leaving a thin clinker wafer (0.5 mm thick) on the 2. With the edge of another glass slide, strike off the
glass slide. Sawing time is approximately two minutes. excess epoxy, leaving only a thin film.
6. With an Ingram thin-section grinder, or other similar 3. Sprinkle the mineral grains over the epoxy film,
equipment, slowly reduce the wafer to a thickness of making sure by stereomicroscope or hand-lens exam
approximately 30 pm, at which thickness the belite ination that only the bottom side of the particles is in
exhibits a first-order yellow interference color in cross contact with the epoxy substrate. Particles ranging
polarized light. An oil coolant and lubricant in the from approximately 74 to 149 pm are recommended
thin-section grinder does not appear to be unsatisfac- for this type of preparation.
tory. This step takes about three to five minutes. 4. Cure the mount on the slide warmer at a temperature
7. Using No. 320- and 600-grit, adhesivebacked, silicon- no higher than 45C.
carbide papers or diamond-impregnated discs on the 5. After the epoxy has hardened, a cover glass can be
Ecomet, the section is quickly reduced to a final placed on top of the mount. Liquid of known RI
thickness of approximately 20 pm. A Buehler thin- applied to the edge of the cover glass will move under
section holder is recommended for grinding and the cover by capillary action and immerse the
polishing. Excessive pressure on the section will exposed particles. Some of the nontoxic RI liquids
cause cracks and limit its usefulness. Clean the sam- are clove oil (n = 1.537 to 1.544) cedarwood oil
ple with a forceful isopropyl alcohol spray between (R = 1.515), and cinnamon oil (R = 1.605 to 1.619).
grinding steps.
6. Using the Becke line (or other comparative refractive
8. Polishing on the rotating wheels or with the Minimet index techniques) determine whether the particle has
can be done with the following successive materials: an index higher or lower than the RI of the liquid.
(a) 5-pm alumina on adhesivebacked nylon and (b) Wash off the liquid and cover glass with a gentle
0.25-pm diamond or 0.3-pm alumina on adhesive stream of xylene over a container that can be sealed
backed Texmet. Use propylene glycol, with an occa- for safe storage and disposal.
sional shot of isopropyl alcohol, as polishing vehicles 7. Use of a mechanical stage, which allows measured
in all grinding and polishing steps. Clean the section movements of the slide in mutually perpendicular
with a sonic cleaner, followed by a forceful isopropyl
directions, enables one to relocate the same particle
alcohol spray. The polished top surface of the thin
examined previously, but now in a different RI liquid.
section can be examined in reflected light at this point Repeated examination with different liquids finally
or the cover glass can be placed.
identifies one or more of the refractive indices of the
9. Heat the cover glass to approximately 90C on a level particle. For most minerals, additional optical proper-
triangle on a hotplate under a hood. Place a drop of ties (such as color, pleochroism, twinning, cleavage,
Hyrax on the cover glass and heat until bubbling fracture, and so on) will be helpful in making the
ceases. Heat the slide bearing the clinker thin section mineral identification. With these data, the tables of
on the triangle until the Hyrax is just barely molten optical properties given in many standard optical
(normally about two minutes, or less). With forceps, mineralogy texts may be consulted, especially those
pick up the cover glass and tilt it over the thin section in Fleischer, Wilcox, and Matzko (1984) and Winchell
so that the droplet of Hyrax falls on the section and Winchell (1964), who emphasize identification
surface. Lower the cover glass slowly onto the by particle methods instead of thin-section techniques.
section. Excess Hyrax can be gently squeezed out
with a pencil eraser. Hyrax at the slide edge should
not be removed with a razor blade because of possi-
ble damage to the section. Use only the minimum
amount of Hyrax necessary to mount the cover glass.
Excess pressure in squeezing out the extra Hyrax
could distintegrate the section, especially if clinker
porosity is high. The thin section should now be
ready for examination in transmitted light.

Particle Mounts on Thin


Epoxy Fh
Particle mounts in which the particles are attached to a thin
film of substrate epoxy on a glass microscope slide are
quite useful for repeated examination of the same grain

21
Chapter 5
Microscopic Characteristics of Clinker Phases
Understanding what one observes in powder mount, Therefore, any cross section of typical clinker displays
polished section, or thin section requires an appreciation (1) the more or less loosely tied framework of alite crystals,
of not only the cement manufacturing process but also the (2) belite that occurs as single crystals and as concentra-
varied effects of light as it passes through or is reflected tions, and (3) a matrix of aluminate and ferrite formed as
from crystals and amorphous materials. Formal training the molten liquid cools and crystallizes. The matrix corn
or extensive experience in microscopy is required. For monly contains secondary belite and shows effects of
example, when viewing crushed clinker in cross-polarized reaction with alite. Voids remain in areas not filled by the
light in refractive-index oil on a microscope slide or a thin liquid, forming sites for crystallization of alkali sulfates on
section, one must be aware that what one observes is the cavity walls. Thus, the typical clinker is a somewhat
dependent mainly on four factors: porous mass of interlocking crystals, a truly crystalline
1. The natural color of the phase. mosaic. Recent studies of the sequence of crystal devel-
opment in the production of portland cement clinker can
2. The thickness of the phase.
be found in papers by lmlach and Hofmanner (1974)
3. The birefringence of the phase, if it is anisotropic. Moore (1976) Ono (1981) Chromy (1974, 1982) and
Birefringence is the difference in the reciprocals of Maki (1982).
the light velocities of the fast and slow rays; in other Much of the descriptive information regarding clinker
words, the difference in indices of refraction of the phases is based on early work by Le Chatelier (1883)
fast and slow rays.
Tornebohm (1897), and Rankin and Wright (1915), each
4. The crystallographic orientation of the crystal with of which is summarized in Bogues classic text of 1947,
respect to the planes of polarized light produced by The Chemistry ofPortland Cement The following optical
the analyzer and polarizer of the microscope. descriptions of clinker phases have been taken for the
Changes in any of these factors produce changes in what most part from publications by lnsley (1936); Taylor
one observes on a polarized-light microscope stage. (1964); Glle, and others (1965). Relatively recent pub
When examining a polished section or thin section, the lished descriptions of clinker phases are found in the
viewer must constantly think in three dimensions, not works of Ono, Kawamura, and Soda (1968); Hofmanner
merely in terms of the nearly two-dimensional view seen in (1973); Sansoni and Zybell (1974); Chromy and Carin
the microscope. Dendritic periclase, therefore, should be (1980/81); Maki (1973,1974,1982); and Maki and Kato
considered as a three-dimensional, branching, treelike or (1982).
skeletal crystal, typically growing within a liquid matrix, the
surface of the section revealing only part of the tree. Alite,
the most abundant phase in portland cement clinker,
tends to form a somewhat discontinuous, open, three-
dimensional framework of linked and stacked crystals, Alite is a solid-solution series of trigonal, monoclinic, and
outside of which most of the other phases, including triclinic modifications of impure tricalcium silicate, which
pores, are developed. Belite crystals, developed by resorp- is generally termed C,S in the cement industry. Substitu-
tion of alite and attached thereto, are typically described tion of magnesium and aluminum for silicon causes tri-
two dimensionally as fringes, the term suggesting that, clinic pseudotrigonal forms to change to monoclinic pseu-
in three dimensions, the alite crystal actually has a coating dotrigonal forms; other substitutions may involve iron and
of secondary belite. Belite crystals generally do not sodium. Alite may include up to approximately 4 percent
develop assemblages of attached crystals like alite, except impurity (Ghosh, 1983). It comprises 40 to 70 percent of
in a tightly packed nest, and even in such nests a small normal portland cement clinker. Its density is 3.13 to 3.22
amount of liquid phase almost always divides the crystals. Mg/m3.

22
Crystals are idiomorphous, vitreous, compact, lath, parallel to c are pseudopolysynthetic twins formed in
tabletlike, or equant, usually six-sided in cross section monoclinic to triclinic inversion; basal pinacoid twins are
depending on the angle of cut, commonly perfect hexa- observed in discontinuous bands.
gons. Crystal forms are typically combinations of two Some of the optical characteristics of alite polymorphs
rhombohedra (Ono, Kawamura, and Soda, 1968) or and their correlative changes with differential thermal
pyramids (Maki, Haba, and Takahashi, 1983) terminated analysis (DTA) and X-ray diffraction (Xf?D) analysis have
by basal pinacoids. Normal crystal sizes range from 25 to been the subjects of reports by Maki and Kato ( 1982) and
65 pm. Alite hardness is approximately 5 on Mohs scale. Chromy and Car-in (1980/81).
Alite crystallizes between 1200C and 1450C from the Maki, Morikoshi, and Takahashi (1985) and Maki
melt. Its refractive indices are 1.716 to 1.720 for nx and ( 1984) have described two modes of alite growth, unsta-
1.722 to 1.724 for nZ, and birefringence is 0.005, ranging ble and stable. Unstable growth is indicated by relatively
from 0.002 to 0.010 as a function of ionic substitution large amounts of entrapped interstitial crystals, gases, free
(Ono, Kawamura, and Soda, 1968). Boikova (1980) indi- lime, and belite, and by morphological irregularity. Stable
cated that alite birefringence ranges from 0.005 to 0.008 growth is indicated by a scarcity of entrapped materials
and that pure tricalcium silicate birefringence is 0.003. and a trend toward crystal faceting. The monoclinic MI
Average birefringence in thin section is bimodal, 0.0044 alite variety was thought to be a primary type (formed by
and 0.0022 (Fundal, 1982). Crystals are colorless to nucleation from the melt) with or without inclusions; the
slightly colored in transmitted light; interference color in monoclinicMj variety was said to be a product of recrystal-
grains or thin sections of 20- to 30-pm thickness is low, lization, the rate of which being dependent on crystal size
first-order gray; the phase is length slow. Alite crystals and temperature. Combined in the highly variable clinker-
reflect gray but etch brown-blue-red-green-yellow with ing environment, the stable and unstable growth modes
nital (1% nitric acid in isopropyl alcohol). Nital etch color produce a wide variety of crystalline textures of alite. Prep
is, to some extent, a function of length of etch time, tem- aration of the raw mix, the minor chemical components,
perature, and reactivity of the crystal. Sections parallel precalcination, the heating rate, and the maximum firing
to c show least the effect of etch (Ono, 1980d). temperature were suggested as the controlling factors in
In transmitted cross-polarized light, alite crystals show alite nucleation and growth from the liquid matrix (Maki,
wavy to straight extinction. X, the direction of the acute 1986).
bisectrix, is perpendicular to the horizontal section that
shows a regular hexagon, threefold symmetry, and low
interference colors; Xis parallel to the length of the section Belite
showing an elongate hexagonal shape. The negative 2V is Belite is a solid-solution series of trigonal, orthorhombic,
20 to 60. Alite crystals rarely show polysynthetic twin and monoclinic varieties of impure dicalcium silicate,
ning. Twinning is 5 to 10 percent on rhombohedral faces normally termed C2S in the cement industry. Polymorphs
and up to 50 percent on the basal pinacoid faces (Ono, of dicalcium silicate are called alpha, alpha prime, beta,
1980d). Alite commonly exhibits poor basal cleavage or and gamma, of which the alpha-prime and beta forms are
parting (perpendicular to the threefold symmetry axis). said to compose approximately 10 to 30 percent of most
Crystals may contain round belite inclusions and exhibit portland cement clinker. Substitutions may be magna-
belite coatings, the latter as a product of alite resorption sium, potassium, sodium, barium, chromium, aluminum,
into the matrix. Crystal zonation is common. manganese, phosphorus, iron, or sulfur. Impurities may
The high-temperature polymorph is ditrigonal scale approximate as much as 6 percent (Ghosh, 1983). Belite
nohedral, uniaxial negative, with a 2V of 0 to 20; X is grains are idiomorphous, vitreous, and normally rounded,
parallel to c. Birefringence may reach 0.010 in clinkers with a marked multidirectional lamellar structure, in part
rich in sodium, potassium, sulfur, and magnesium. Sim- due to twinning (Yamaguchi and Takagi, 1968). Hardness
ple twins are common on basal pinacoid (0001) and is 4 to 5 on Mohs scale. Belite is colorless, pale yellow,
rhombohedron (0112); twinning on (0001) is evident in yellow, amber, or shades of green. The crystal shows poor
cross-polarized light afterfiversion of alite to triclinic poly- prismatic cleavage (parallel to the threefold symmetry
morph. Twinning on (0112) appears as a hexagonal axis). Belite crystals reflect gray on an unetched polished
cross section with a diagonal twin plane that, when surface. The interference color in a thin section of 25-pm
inclined to plane of section, results in undulatory thickness is first-order whitish yellow. Birefringence in thin
extinction. section is 0.0153 (Fundal, 1982). Belite size is 1 to 4 pm
The medium-temperature polymorph is monoclinic below 1300C but recrystallizes to 20 to 40 pm with
and biaxial negative;X is parallel to c(trigonal), Y is parallel treatment at high temperature (approximately 1500C).
to a (trigonal), and Z is perpendicular to a (trigonal), with Etch colors are brown to blue in nital, dependent on time
the latter two relationships less firmly established. The 2V in the etchant, temperature, and reactivity of the crystal.
is 20 to 60. In horizontal sections, alite may show irregu- Insleys classification of belite, most of which was pro
lar patches of threefold cyclic twins formed in the trigonal posed in 1936, has become a standard for the industry:
to monoclinic inversion; uniform extinction occurs in ver-
tical sections. Type1 -two or more sets of intersecting lamellae
Type la -characterized by discrete particles along traces
Triclinic alite, the low-temperature polymorph, is biaxial
negative. The 2Vranges from 20 to 60, withxinclined to of intersecting lamellae (lnsley and others, 1938)
c (trigonal) at an angle ranging from 0 to 15. Obscure Type II -one set of parallel lamellae
extinction occurs in horizontal sections. Indistinct bands Type Ill -no lamellae; overgrowth on Type I

23
Type I belite, according to Yamaguchi and Ono ( 1962) is monoclinic, stabilized by sodium and phosphorus.
normally forms rounded grains with indistinct crystal Alpha prime &S is orthorhombic. Some alpha prime
faces and shows two or more sets of lamellae (alpha and C2S grains show striations of beta phase. Colors range
beta) crossing at 60. Minute polysynthetic twins in the from black brown, yellow, green to colorless. Density is
lamellae with high birefringence have twin planes parallel 3.31 Mg/m3. According to Boikova (1980) nx is 1.719,
to Z. Lamellae are skeletal, being formed during the alpha and n, is 1.732, with one, two, or three directions of
to alpha prime inversion. Polysynthetic twins within lamel- lamellae.
lae are produced during the alpha prime to beta inversion. Beta dicalcium silicate is metastable below 670C and
Variable extinction ranges from uniforrn to extremely monoclinic, with an nx of 1.717, an n, of 1.722, and n,
patchy and diffuse. Type la was said by lnsley to exhibit the of 1.736 and parallel to b; birefringence is 0.019. The
effects of unmixing (phase separation) during cooling. (+)2V is 64 to 69, with the axial plane (010). The beta
Type II belites are irregular grains with one set of distinct form exhibits very close polysynthetic twinning (Chromy,
parallel striations (lamellae). Minute polysynthetic twins, 1970). It comprises most of belite in clinker. Cleavage is
(101) lamellae, and parting occur on (100) and (010) with poor on (100) and (010). Colors range from colorless to
a lo- to 20-degree difference in extinction angle. X is yellow or brown. Density is 3.28 Mg/m3. Boikova (1980)
parallel to a (approximately), Y is parallel to b (approxi- reported a typical yellow color and spotty surface (not
mately), Z is parallel to c. Z makes an angle of 10 degrees striated).
with a, and the acute bisectrix is c, the threefold axis. Type Gamma dicalcium silicate forms at 830C and is
II belite is not a common variety in normal clinker but is orthorhombic with an nx of 1.642 and parallel to a, an n,
abundant in kiln coatings (DeLisle, 1979) and low- of 1.645 and parallel to c, and an n, of 1.654 and parallel
temperature kiln flushes (Dorn, 1985, personal to b; birefringence is 0.012. The (-)2Vis 60 with the axial
communication). plane (001). Cleavage is parallel to (010). Faint yellow to
Type Ill belite, the nonlamellar form, is uncommon in colorless crystals are common. Crystals are prismatic and
norrnal plant clinkers and is merely a single crystal with a may be polysyntheticallytwinned (Wieja and Wieja, 1980).
uniform internal microstructure. Density is 2.97 Mg/m3.
Belite crystals with an internal microstructure of lamel- The polymorphous transformation of beta to gamma
lae arranged in a concentric hexagonal pattern are rare. belite that accompanies the phenomenon of self-pulver-
Belite with significant amounts of alkalies has indices of ization at 500C as well as detailed techniques for using
refraction as follows: R, is 1.694 and nz is 1.702, with the microscope for analysis of the gamma form, were
a birefringence of 0.008. The 2V is 20. Alkali belite has presented by Wieja and Wieja ( 1980). These authors state
been said to show one set of evenly spaced parallel lamel- that gamma calcium orthosilicate with 10 percent FeSi04
lae in polished and nital-etched section but published in solid solution has n, equal to 1.653 and n, equal to
confirmatory microprobe data are scarce. According to 1.677. Optical properties of aluminates in self-pulverizing
Ono (letter, 1977) alkali belite in normal clinker can be materials, as well as ferrites, were also described in detail.
recognized by (1) large crystal size, (2) lack of color, (3) a
birefringence of 0.012 to 0.015, (4) sharp, clear striations,
(5) coarse sandwich structure of alpha and beta forms,
and (6) a surface free of ferrite phases. Alkali belite,
KC&2, according to Gutt and Osborne (1970) has a Commentsonbeliteclassificationand
doubtful existence, being merely a point on the KCS-CS polymo~hic varieties
join in a phase diagram. Type I belite crystals according to lnsley (1936) were
Alpha dicalcium silicate forms at approximately 1425C generally considered characteristic of alpha dicalcium
and melts at 2130C. It is ditrigonal dipyramidal with an nx silicate. lnsley also observed that twinning in dicalcium
of 1.702, nz of 1.712, and a birefringence of 0.010. The silicate is indicated by interpenetrating sets of parallel
2V is 0. Density is 3.07 Mg/m3. Alpha dicalcium silicate, bands with extinction inclined in opposite directions in
rich in sodium oxide, is isotropic (Soda, Mizukami, and adjacent bands. Type II crystals were described as having
Shirasaka, 1968). Coarse alpha belite, crystalliied from a a single set of polysynthetically twinned bands that are
feldspar melt reacting with calcium oxide, is colorless and clearly depicted in his Fig. 10 (Insley, 1936). Type Ill
alkali-rich (Ono, 198Oc). In contrast, Chromy (1970) crystals are untwinned, irregular grains, sometimes as
stated that the alpha form is generally not twinned and has overgrowths on Types I or II and commonly with veinlets
a weak birefringence (0.003). Boikova (1980) reported or cracks. Insleys Fig. 12 shows belite grains that appear
indices of refraction of 1.717 for nx and 1.720 for nr. The to be internally divided so as to produce relatively large
alpha form can occur between lamellae of beta dicalcium areas of untwinned individuals.
silicate (Regourd and Guinier, 1974). Ono (1975) stated that the structure of Type I belite is
Alpha prime dicalcium silicate is derived from alpha by skeletal instead of polysynthetically twinned. Thus, confu-
phase transformation and crystallizes between 830C and sion, and perhaps some disagreement, in the literature
1447C; nx is 1.7 18 and is parallel to b; n, is 1.7 17 and is exists as to the description and origin of the microstmc-
parallel to a; nz is 1.732 and is parallel to c; birefringence ture of Types I and II belites. Onos argument (1975) in
is 0.019; and (+)2V is 30. Alpha prime, according to support of a largely skeletal interpretation of belite and a
Chromy (1970) has a birefringence of 0.013. Alpha brief statement on polyrnorph origins are reproduced
prime LCzS is orthorhombic and can be stabilized by below almost verbatim with only slight editorial change to
potassium, sodium, and phosphorus. Alpha prime &S put the statement into clear English.

24
Ono (letter, 1985) stated that the facial indices of skele
tal I_amellae in the alpha_ to alpha-prime in_versio_ are
(1012) and equivalent (1102) (0112) (0112) (1012),
(1102) of the alpha hexagonal lattice which are (011) and
( 112) of the alpha-primeorthorhombic lattice. The angle
bekeen (011) and (011) and also between (112) and
Inversion Texture of Type I Be&e (112) is about 73 degrees.
Skeleton Stmchue Manufacturing aspects of belite doped with barium sul-
The cross striations of the Type I belite have been called fate (BaSOJ, calcium tribasic phosphate [Cas(P04)30H],
polysynthetic twinning. However, this structure is not poly- or vanadium oxide (VzOz) as energy conservation mea-
synthetic twinning but a skeleton structure, consisting of sures are discussed by Matkovic, and others (1981). This
beta and alpha forms of belite. paper includes well-illustrated microscopical descriptions
In the clinker-burning process, at the low temperatures of polymorphic belite transformations by Chromy who,
of about 1100C to 14ooC, beliie is a minute crystal of using a hot stage on the microscope, observed the belite
alpha prime form, and through the alpha prime to alpha changes as they occurred during heating and cooling.
inversion, belite recrystalliies into a big crystal of alpha, These data were correlated with results from DTA, XFZD,
absorbing impurities from the melt. The alpha form is a and scanning electron microscope examinations and
round and plain crystal without striations. Through the generally indicate a sequence of polymorphs similar to
cooling process, thin lamellae of alpha prime appear in
that described by Ono (1975).
the round crystal of alpha. Gradually the lamellae increase
and extend all over the crystal, and finally the belite crystal Groves (1982) demonstrated optically resolvable twins
is cooled to room temperature. If the clinker is cooled in alpha prime dicalcium silicate, which, upon transforma-
quickly, plenty of alpha remains in the spaces between the tion to beta, developed a single set of planes. Alpha dical-
lamellae. The lamellae of alpha prime usually invert to cium silicate, formed at a somewhat higher temperature,
beta, keeping the outer shape of the earlier lamellae. With had twin lamellae with widths on the order of 2000 ang
an electron microscope, a fine polysynthetic twinning cor- stroms (beyond the range of resolution by light micros-
responding to the alpha prime to beta inversion can be copy) visible only with the transmission electron micro
observed. However, the inversion texture is usually too fine scope; however, the groups of twin lamellae, termed
to be observed by optical microscope. domains, were observed with a light microscope.
Color of Type I Belite This brief study of some of the published material on
belite microstructure has led this writer to the conclusion
The alpha form contains plenty of impurities at high
temperatures. The solubility of elements into the alpha- that commonly occurring belite grains can be
prime form in solid solution is very small, less than 1 1. Simple continuous structures (nontwinned)
percent. Therefore, through the alpha to alpha-prime 2. Uniformly twinned (apparently polysynthetically)
inversion in cooling, the impurities separate into a colloi-
dal state in the grain of belite, and belite changes color 3. Multidirectional lamellar skeletons with twinning
from light yellow to amber, according to the cooling rate. If within individual lamellae
the clinker is cooled quickly, belite is colorless or light 4. Combinations of the foregoing types.
yellow. If the clinker is cooled extremely slowly, belite is Application of modem microscopical equipment, such
amber, and minute dispersions can be observed. as the transmission electron microscope, to the problem
Biretiingence of Type I Belite of belite microstructure appears to be a promising field of
research and may, as Groves ( 1982) stated, provide data
If the lamellar structure is coarse, and the lamellae stand
on belite twinning types relating to the temperature at
perpendicular to the plane of the section, the lamellae of
beta and alpha can be observed distinctlywithout overlap, which the belite formed.
and their birefringence can be measured separately. Usu- lnsleys ( 1936) morphological classification of belite
ally the two phases are overlapped and light passes into Types I, II, and Ill is particularly valuable because it is
through both of them, thus the birefringence is measured not confused with genetic or polymorphic restrictions.
as the sum of the retardations. The birefringence of alpha Even though lnsley discussed polymorphic, composi-
is very weak and in proportion to the content of beta. tional, and temperature variations, the morphological
classification was apparently meant to be primarily obser-
herskm Texha of Type II Belite
vational with interpretation as a derivative. With progress
If clinker is burned below the temperature of alpha prime in defining the relationships between polymorphic varie-
to alpha inversion, and beliie is cooled from the tempera-
ture region of alpha prime, belite has only the alpha prime ties of belite (alpha, alpha prime, and so on) and their
to beta inversion texture. This texture is observed as one common forms, we may eventually understand the rather
set of parallel striations, which is polysynthetic twinning complex genesis of the phases. For now, in the authors
and parting on ( 100) and (010) after the crystal axes of the opinion, the nomenclature should remain descriptive.
alpha prime. Rarely occurring are polysynthetic twins on Microscopical appearances of belite polymorphs (al-
(iio),(iio),(oii), and(oil). pha, alpha prime, beta, and gamma) have been described
by Chromy and Carin (1980/81). These authors illus-
trated nonlamellar, alpha belite and stated that the trans-
formation of alpha to alpha-prime dicalcium silicate is
manifested by the growth of six sets of alpha-prime lamel-
lae, the speed and completeness of the transformation

25
being a function of the alkali concentration in the melt in cross-polarized light, colorless (in white cement) to tan
The recognition and abundance of alpha belite, how and brown in transmitted light, with an index of refraction
ever, has been given a major importance in the strength of 1.710. It reflects gray on unetched polished surfaces
gain of mortar, particularly by Japanese investigators, and and etches blue to blue-gray in distilled water (preferably
alpha belite, therefore, warrants additional discussion. warmed to 40C) and potassium hydroxide. Tricalcium
Relatively high mortar-cube strengths at 28 days have aluminate may be a solid solution with iron, magnesium,
been correlated with alpha-belite percentage, according silicon, sodium, and potassium. Impurities may approx-
to Soda, Mizukami, and Shirasaka (1968). Tomita, Haya- imate up to 10 percent (Ghosh, 1983). It typically fills
shi, and Nagase (1970) have shown that the percentage of interstices between crystals of C,AF and CS. Density is
alpha belite and the temperature at which quenching 3.04 Mg/m3. The existence of monoclinic tricalcium
occurred have a strong effect on 28-day mortar strength. aluminate in commercial clinker has been questioned by
Certain alkali contents and the abundance of alpha belite Regourd and Guinier (1974).
(which was shown to be stabilized by potassium oxide,
sodium oxide, or both) were correlated with relatively high
mortar strengths by Ono, Hidaka, and Shirasaka in 1969.
Onos method of concentration of belite for XRD and AlkaliAluminate
estimation of alpha content is as follows (letter, 1981):
1. Wash 300 grams of clinker or cement with alcohol by Alkali aluminate is an orthorhombic and monoclinic solid
suspension and decantation techniques. Several solution series of NaCaoA130s, NCsA3, and possibly CA,
suspensions and decantations are necessary in with partial substitution of sodium by potassium. It occurs
as idiomorphous tablets, laths, and stavelike prismatic
order to concentrate the 20- to 60-pm particles.
forms. It is biaxial with R, equal to 1.702, nL equal to
2. Pass the dried sample through a magnetic separator 1.710, and a birefringence of 0.008. The (-)2Vis 0 to 35.
with a forward inclination of lo to 20 and a side tilt Alkali aluminate is length slow, colorless to dark in thin
of *5 in order to separate ferrite from belite. Repeat section, and, in polished section, turns blue with water and
four to five times. potassium hydroxide, as C3A does. Orthorhombic (low
3. Methylene iodide and benzene are mixed to a density sodium oxide) experimental phases may be twinned on
of 3.20Mg/m3, combined with the fraction produced (1 lo), (010) (100) and (001) with oblique extinction. An
in Step 2, and centrifuged three to four times. After experimental monoclinic form (high sodium oxide) shows
each centrifuging the floating material is taken away. crossed grids of fine lamellar twins on (100) and (010)
A 0.2- to 0.3-g separation of belite can be obtained. wavy extinction, and a 2Vof 64 to 67 (Maki, 1973). Alkali
4. XRD of the heavy concentrate shows strong peaks aluminate may also show microgranular (nonprismatic)
for beta belite and weak peaks for alpha. The alpha habit with isotropic cores surrounded by twinned forms
percentage is estimated from the intensity of 32.95 with higher birefringence.
to 33.00 28, Cu-kalpha radiation. Alpha prime gives a
strong peak at 33.26 to 33.28 28.
Takashima (1972) describes progressive dissolution of
alite and beta belite with an accompanying ease of detec-
tion of alpha by XRD using methyl-ethyl-ketone (MEK) and Fefiite
salicylic acid. Alpha belite was most easily detected by
XRD when a 1.0-g cement sample was combined with 3.0 An orthorhombic solid solution series of Ca4Fe4010 to
g of salicylic acid and 100 mLMEK. Details of the test are Ca4FeA13010,~ferrite is prismatic and pleochroic with an n,
given in his article. of 1.98 (olive green), an n,of 2.05 (olive green), and an nz
Also using XRD techniques, Regourd ( 1979) stated that of 2.08 (almost opaque). The birefringence is 0.010 and
in slowly cooled industrial clinker alpha belite was not (-)2V is moderate. X equals b, Y equals c, and Z equals
detected, but in rapidly cooled, air-quenched clinker, a. Crystal color is nom-rally brown to yellow; elongation is
alpha belite amounted to 3.0 percent positive and the phase is pleochroic with the Z direction
showing the strongest brown absorption. Ferrite reflects
dull to bright on polished surfaces. It displays a distinct
cleavage on (101) and can show twinning with (101) as
the composition plane. Crystals are commonly tabular on
TricalciumAl~te (010) but can be idiomorphous interstitial filling; ferrite
Isometric, orthorhombic, tetragonal, and monoclinic can also be prismatic, dendritic, or massive to fibrous.
forms of tricalcium aluminate (Ca&06) with a melting Ferrite may comprise almost all the matrix in sulfate-
point of approximately 1542C are termed C3A in the resisting and oil-well cement clinkers. Polishing hardness
cement industry. Tricalcium aluminate normally consists is greater than alite and belite but less than periclase. Its
of uniform, small, xenomorphous to rectangular crystals index of refraction is lowered by 0.02 by magnesium oxide
(1 to 60 pm) in low-alkali or alkali-free clinker. GA may in solid solution. Impurities can reach 13 percent (Ghosh,
comprise as much as 18 percent in ordinary clinker, 1983). Slowly cooled crystals have a blade form, crystals
forming between ferrite crystals. Crystals show poor formed under a moderate cooling rate are prismatic,
cleavage parallel to (OOl), conchoidal fracture, and a quickly cooled crystals are dendritic, and very fast cooling
hardness of 6. Tricalcium aluminate is normally isotropic possibly produces glass. Density is 3.77 Mg/m3.
Free Lime (Poole and Thomas, 1975) has been found moderately
successful for detection of alkali sulfates in clinker powder
Free lime, isometric calcium oxide (calcia), occurs as (see Examination of Stained Powders in Chapter 3).
colorless, rounded, idiomorphous grains, singly, in clus- For most studies, XRD remains a dependable and rapid
ters, or as inclusions in aluminates or alite. Its index of mode of analysis for establishing the varieties of sulfate
refraction is 1.833 and hardness is 3 to 4. Free CaO phases. However, their locations, crystal sizes, and, to
comprises approximately 1 .O percent in ordinary portland some extent, their abundances are best described by
cement. Free lime has perfect cubic cleavage: reflects microscopy. Some of the alkali-sulfate phases are listed
brightly with light yellow to cream color, tarnishes to irri- below:
descent calcium hydroxide in room humidity; and etches Arcanite (KzSO,) is orthorhombic with an nx of 1.49,
rapidly with water. Its density is 3.32 Mg/m3. Free lime is an R, of 1.49, and an nz of 1.50; colorless; void-filling or
indicated by Whites test (Lea, 1970): to a finely powdered rarely dendritic; and has a density of 2.67 Mg/m3. It inverts
cement or clinker on a microscope slide, add a drop of to a uniaxial phase at roughly 650C.
solution mixed with 5 g phenol in 5 mL nitrobenzene, to
Calcium langbeinite (K2S04 - 2CaSO3 has an no
which two drops of water are added. If free lime is present,
of 1.52, an ne of 1.53, and a birefringence of 0.010. It
long radiating needles of calcium phenate form in less
undergoes a phase change in KzS04 leading to character-
than 10 minutes, and calcium hydroxide forms in 20
istic cracking (Bye, 1983). Calcium langbeinite is biaxial
minutes or longer. In clinkers and cements, expansive
and relatively dark in reflected light. It is said to control
hydration of free lime produces popcorn or cauliflowerlike
setting in mineralized high-alite cement (Moir, 1982).
crystals of calcium hydroxide, called epezite, surrounding
the original particle of free lime (see Brown and Swayze, Aphthitalite [ (Kz Na)2SOI] is hexagonal with tabular
1938). Formation of epezite via air slaking normally crystals showing marked trigonal development. Crys&ls
causes clinker disintegration. can form bladed aggregates. Cleavages are fair (1010)
and poor (0001). Hardness is 3 and density is 2.7 Mg/m3.
Crystals are uniaxial positive with an no of 1.491, an ne
of 1.499, and a birefringence of 0.008 for K: Na = 2.46:1;
Periclase no is 1.487, ne is 1.492, and the birefringence is 0.005
Periclase is isometric magnesium oxide (magnesia) occur for K: Na = 1:1.5. The birefringence increases slightly
ring as small, colorless, triangular, octahedral, rectangu- with increase in the tenor of potassium. Continuity from
lar, or round grains with diameters up to 30 pm or as NazK&S04)s to KzS04 is improbable (Winchell and Win-
dendritic crystals. Periclase can be interstitial or intragran- chell, 1964). Aphthitalite can have a small optic angle and
ular; crystal clusters are common. Periclase abundance is colorless unless stained by iron oxide.
may range up to 6 to 7 percent in some clinkers. The index Syngenite [ K&a(SO& * Hz01 is monoclinic with
of refraction is 1.736. Crystals show cubic cleavage and a beta of 1045. Crystals typically develop as (100) tablets
have a hardness of 5.5 to 6, resulting in a high relief on or prisms. Twinning is common on (100). Syngenite
polished surfaces. Periclase is colorless and reflects shows perfect (110) and (100) and distinct (010) cleav-
brightly with pinkish light gray. It is not affected by usual ages. Hardness is 2.5 and density is 2.6 Mg/m3. The
etch media. Density is 3.58 Mg/m3. angle of Xwith c is -217, Z = b, (-)2V= 2818, r < u
is very strong; n, is 1.5010, n, is 1.5166, n, is 1.5176,
and the birefringence is 0.0166. Crystals are colorless or
Alkali Sulfates white. Syngenite occurs in silo-stored portland cement
and is reported to be responsible for pack set and some
Sodium and potassium sulfates occur in various crys- problems of flowability.
tal forms of the hexagonal and otthorhombic systems.
These phases typically are found as spotty void fillings and
deposits on alite crystals and void surfaces in clinker, even IWiscellaneous Phases
in cracks in alite crystals (Gouda, 1980). Alkali sulfates
make up only a few percent in clinker but have important Calcite (CaCOs) is a hexagonal mineral with perfect
effects. Alkali sulfates in polished sections have low reflec- rhombohedral cleavage (three directions not at right
tivity, are dissolved by most etching media, and turn dark angles); parting and rhombohedral twinning are com-
with hydrofluoric acid; some alkali sulfates are said to be mon; hardness is 3. Crystals are uniaxial negative with an
characteristically surrounded by a halo of unetched n, of 1.654, n, of 1.485, and a birefringence of 0.169.
clinker (Pollitt and Brown, 1968). Alkali sulfates can be Calcite is normally colorless and has many forms and
observed in a powder mount beneath a cover glass as habits (anhedral to euhedral crystals, columnar, coarse to
floating particles in oil with an RI of 1.715. In thin section very finely microcrystalline, sugary, layered, and so on).
and transmitted light, alkali sulfate varieties can rarely be Density is 2.71 Mg/m3. Calcite can occur in clinker as a
distinguished, occurring in many cases as transparent, carbonated hydration product. Calcite can be identified
irregular, multiphase masses of intergrown crystals that with certain stains and thereby distinguished from dolo-
can be more easily seen on a very finely polished section. mite [(Ca,Mg)(C03)2], a very similar mineral.
Optical properties determined on small particles in refrac- Gypsum (CaSO, . 2Hz0) is monoclinic with one per-
tive-index oils will help to identify the phases. A potassium fect cleavage and two good cleavages, the latter intersect-
permanganate and barium chloride stain for sulfates ing at 66. Hardness is 2. Gypsum is biaxial positive; n, is

27
1.521, R, is 1.523, nz is 1.530, and birefringence is 0.009. with an no of 1.542, an ne of 1.551, and a birefringence
Gypsum is white to colorless. It loses three-fourths of its of 0.009. Its density is 2.65 Mg/m3.
water at about 120C resulting in an no of 1.50 and an ne Fly ash is composed of tiny spherical and ellipsoidal
of 1.56. Gypsum recrystallizes by directed stress or tem- beads and bubbles of glass, typically containing other
peratures above approximately 100C but may retain its phases. Other common constituents are irregular carbon
original outward form of the particle. Gypsum may be particles, hematite, magnetite, tridymite, cristobalite,
fibrous, platy, or massive. Particles in cement typically quartz, mullite, and spinel. It may contain small amounts
show a complex internal microcrystalline character. of belite, aluminate, and free lime. The RI of the glass is
Density is 2.32 Mg/m3. Gypsum has a blue dispersion 1.50 to 1.63.
stain when mounted in oil with an RI of 1.528 (Green, Glass of variable composition fills voids in extremely
1984). Application of distilled water at 40C to a polished rapidly cooled clinker. It forms equant to highly irregular
section imparts a dark coloration to gypsum particles in masses and is normally isotropic unless strained. Glass
cement samples. may comprise up to 20 percent of abnormal portland
Plaster (2CaSOr l Ha) is hexagonal with needlelike cement clinker. Regourd and Guinier (1974) state that
crystals exhibiting six-sided prisms. It is uniaxial positive; glass may form a few percent in clinker. Glass may
no is 1.558, ne is 1.586, and birefringence is 0.028. Plas- occur as a dark-green variety, developed as a uniform
ter is colorless and the density is 2.7 Mg/m3. Other phases groundmass between large belite crystals, and has been
with this composition exhibit slightly different optical called gehlenite glass with a composition of approximately
properties (see Winchell and Winchell, 1964). Plaster also CAS. Gehlenite glass has an n of 1.638 and a density of
occurs pseudomorphically after gypsum, retaining the 2.884 Mg/m. Glass has never been identified by the writer
internal microcrystalline character of gypsum as des- in normal portland cement clinker.
cribed here. Green (1984) reports a variable RI, usually Coke (C) forms irregular to round particles of medium
approximately . . . 1.54, and a relatively high porosity, thus reflectivity with a yellowish hue and marked reflection
.
making invrsrbrlrty difficult in refractiveindex oils. pleochroism of yellowish white to dark gray.
Anhydrite (CaSO,) is orthorhombic with crystals Potassium iron sulfide (KFeS,) is very soft and
showing a varied habit: equant grains or tablets developed shows a bright reflection pleochroism of gray-yellow,
on (010) (100) or (001) or elongated parallel to a or c. greenish gray, and copper red.
Cleavages are perfect on (010) very good on (100) and Calcium sulfide (CaS) is isometric but resembles
distinct on (001). Polysynthetic twinning is common and
ferrite. It commonly forms colorless spherical or dendritic
may be in two directions. Hardness is 3 to 3.5: density is
crystals, is strongly reflecting, and rapidly etches with
2.98 Mg/m3. Anhydrite is soluble in hydrochloric acid. dimethyl ammonium citrate. It has an RI of 2.137 and
The melting point is 1450C. X is parallel to b, Z is par- perfect cubic cleavage. Hardness is 4 and density is 2.6
allel to c, and the (+)2Vis 43. Dispersion is r < u (weak).
Mg/m3.
The nx is 1.5698, ny is 1.5754, n, is 1.6136, and the
birefnngence is 0.0438. Crystals are biaxial positive. Anhy- Wustite (FeO) is isometric, black and nearly opaque
drite is generally colorless in transmitted light; thick crys- at an Fe0 content of 80 percent. Wustite is opaque (bottle
tals may be bluish or violet with Xcolorless to pale yellow green) with an n of 2.12 at 78 percent FeO, with the
or rose, Y pale violet or rose, and Zviolet. remainder MgO. Wustite reflects gray-white with a tint of
Calcium sulfate inverts at 1195C to alpha anhydrite, brown, with brighter reflectivity than ferrite. It is dendritic,
which is monoclinic with lamellar twinning like plagio- has poor cleavage, and its density is 5.5 Mg/m3.
clase and has an n, of 1.50, n, of 1.56, and birefringence Graphite (C) is hexagonal; it is black and opaque with a
of 0.060. Beta anhydrite is obtained by heating anhydrite moderately bright, strongly pleochroic reflectance. Cleav
above 170C. It is stable to 500C. It is probably ortho- age is parallel to (0001) and perfect, forming thin basal
rhombic and is pseudohexagonal; density is 2.85 Mg/m3. lamellae. Hardness is 1 to 2; stalk to strip-shape. Density
Z is c, (+)2E is approximately 45, nx is 1.562 ? 0.003, nr is 2.1 to 2.3 Mg/m.
is 1.595, and birefringence is 0.013. A third phase Gehlenite (2Ca0 . Al203 SiOz) is tetragonal; cays-
l

(gamma anhydnte) has been called soluble anhydrite tals are uniaxial negative with an ne of 1.658 and no of
srnce rt is much more soluble in water than ordinary 1.669. It has short prisms or tablets, often with a square
anhydrite. It is made by dehydrating CaS04 . lhH20 at outline and distinct basal cleavage (Insley and Frechette,
about 30C. Crystals are hexagonal basal plates. Density is 1955). Extinction is parallel to crystal edges. Crystals are
2.55 to 2.61 Mg/m3. It is uniaxial positive with noof 1.56, n, colorless and may be zoned and twinned. Gehlenite is
of 1.50, and birefringence of 0.060. This phase takes up revealed in high alumina cement clinker with 2% ammo
water readily in contact with moist air. It varies markedly in nium chloride plus a 2% dibasic sodium orthophosphate
properties with variations in temperature; for example, at solution with an etch time of three to five minutes at
100C it has an nx of 1.547 and n,of 1.570; at 150C it has 100C. Hardness is 5 to 6 and density is 3.07 Mg/m3.
an nx of 1.499, n, of 1.544; and at 450C to 550C it is Spunite (2CazSiOd * CaCOs) is possibly mono
isotropic with an n of 1.500 (Winchell and Winchell, 1964). clinic, with distinct (001) and poor (110) cleavages at 79
Quartz (SiOJ is trigonal trapezohedral, typically seen and multiple twinning. Hardness is 5. It is uniaxial negative
as equant to somewhat shardlike particles with a con with an nx of 1.64, n, of 1.674, n, of 1.679 and birefrin-
choidal fracture and virtually no cleavage. It is colorless to gence of 0.039. The 2V is 40. Density is 3.014 Mg/m3
cloudy, with a hardness of 7. Quartz is uniaxial positive, (Amafuji and Tsumagari, 1968).

28
Double salt (3Ca2Si04 l 2CaSO3 has an R, of
1.628, a ne of 1.636, a birefringence of 0.008, and a large
2V (One, Amafuji, and Okumura, 1966).
Metallic iron (Fe) is isometric and occurs as steel-gray
to iron-black masses normally in droplet form with a
strong white reflectance. It has distinct cubic cleavage,
with a hardness of 4 and a density of 7.87 Mg/m3.
Calcium sulfosilicate (2CazSi04 CaSO4) is orthor-
l

hombic, with irregular to prismatic crystals; nx is 1.630


and R, is 1.640 (Sundius and Peterson, 1960), or R, is
1.632, R, is 1.638, and n, is 1.640, with a (-)2V of 60,
according to Pryce (1972). The material is made from
calcite and silica and has RI of 1.635 and a low birefrin-
gence according to Gutt and Smith (1966). Trojer and
Warbenowa (1977) reported RIs for the solid-solution
series 2CazSi04 * CaS04 - 2CazSi04 * CaCrOl, indicat-
ing an increase in RIs and birefringence with chromium
content. The mineral etches similar to belite in HF vapor,
showing elongated prisms with cusp-shape ends, typically
set in a groundmass of calcium sulfate or calcium lang-
lxinite, or both.

29
Chapter 6
Onos Method-History, Explanation, and Practice

History of 01~08 Theories of Kiln and crystal morphology as functions of raw material fine-
Control Through Microscopy ness, mixing, and heating rate. He concluded with a pro-
phetic statement that the microscopical information
Yoshio Onos major contribution to cement production might be useful in the control of clinker manufacture.
technology has been largely through the use of trans- In 1962 Yamaguchi and Ono published a detailed
mitted, polarized-light microscopy as one of the methods microscopical and XRD analysis of belite, describing and
of quality control. Ono brought transmitted, polarized-light defining the crystallographic orientations of various lamel-
microscopy from the research laboratory virtually onto the lar structures. The structures were said to be a result of
kiln floor where, in combination with data from other tests three sets of skeleton crystals and six sets of lamellae, the
and instruments, the kiln could be controlled and the combination of these forming a pseudohexagonal,
cement quality enhanced. This brief history of Onos work orthorhombic crystal. Twinning produced during the
in clinker and cement microscopy clearly illustrates the alpha prime to beta inversion was observed with a scan-
applicability of both reflected- and transmitted-light micros ning electron microscope. Yamaguchi and Ono stated
copy to day-today cement production. that (1) during polymorphic inversions from alpha to
Naito and Ono in 1953 reported the relationships alpha prime to beta, the crystal axes remain parallel and
between three size fractions of raw feed (greater than 30 (2) the typical multidirectional lamellar structure is formed
pm, 20 to 30 km, and 10 to 20 pm) and their bumabilities, during the alpha to alpha prime inversion. A belite grain
concluding that (1) coarse quartz increased the difficulty with only one set of striations (Insleys Type II belite) was
of burning and (2) a few percent alkalies and magnesia as reported to show cleavage parallel to one set of conjugate
mineralizers greatly improved sintering. Microscopically it planes of polysynthetic twins.
was shown that with the same raw mix burned for 20 Onos doctoral thesis (1963) the most exhaustive study
minutes, Type II belite with a single set of parallel lamel- of alite and belite known to the present writer, was con
lae characterized a clinker burned at 1380C and Type I cemed with many of the microscopic aspects of phase
belite with several sets of multidirectional lamellae formed transformation during production of portland cement
at a temperature of 1430C. clinker. Among his findings was the fact that alite grows
Ono described the polymorphs of dicalcium silicate larger with increasing particle size of quartz in the raw feed.
with transmitted-light microscopy and X-ray diffraction Ono, Kawamura, and Fujimura in 1964 described the
(XRD) in 1953, demonstrating the occurrence of alpha- sequence of reactions that occur between powders of
prime, beta, and gamma forms. calcite, clay, siliceous rock and copper slag (an iron
In 1954 Ono discussed changes in the specific gravities bearing glass) through chemistry, XRD, and transmitted-
of C2S and C,S as functions of magnesium, potassium, light microscopy.
and sodium oxides and pointed out the inhomogeneity of Research results on the effects of alpha-belite on mortar
CS, saying that the grain consisted of minute, highly strength, published by Yamaguchi, Ono, Kawamura, and
birefringent laminae and isotropic substances in a skel- Soda in 1963, led to a definitive paper in 1965 (Ono and
eton structure. Ono stated that the specific gravity and Soda) correlating the crystallographic relationships of
refractive index of the birefringent laminae in belite alite and belite with the strength of mortar. In the latter
seemed to be higher than those of the isotropic sub- paper, polymorphic varieties of belite and morphologic
stances (later said to be the alpha polymorph). changes in alite were related precisely to the following
A major contribution came when Ono (1957) pub- parameters of the burning condition: rate of heating, max-
lished a microscopical study of the formation of portland imum temperature, length of time at high temperature,
cement clinker, tracing the changes of phase chemistry and rate of cooling. These parameters, empirically stud-

30
ied, resulted in an equation giving a prediction of 28-day powder-mount microscopy. The dissemination of Onos
mortar-cube strength. Ono and Soda showed, with micros- technique to the Western world was largely due to this
copy and XRD of selected magnetic and density separa seminar. Since that time Onos theories and method of
tions of clinker powders, that the highest mortar-cube clinker interpretation have been subjects of research in
strengths were achieved with clinkers enriched in rela- laboratories of many North American cement companies,
tively clear, alpha belite. the Portland Cement Association, and in Europe. Mau
Also in 1965, Ono, Uno, and Kanai reported data on fwe (1979) reported on the routine application of the Ono
laboratory-made polymorphs of tricalcium silicate that technique in Hawaii and strongly supported Onos Method
persisted at room temperature. These authors described and theories, stressing their use to control burning
monoclinic, triclinic, and rhombohedral forms of alite. temperature.
Ono and Soda (1967) demonstrated that, when a finely At the 1980 meeting of the International Cement
ground raw mix is burned for a long time in the tempera. Microscopy Association (ICMA) in Dallas, Texas, U.S.A.,
ture range of 1200C to 1300C coarse granules of 1 OO- and at the General Technical Committee meeting of the
to 200-pm sizes are produced in a powdery, porous Portland Cement Association (PCA) at about the same
clinker. In addition, the mineralogic changes in raw mate time in Skokie, Illinois, USA., Ono presented a paper
rial were observed as it progressed from white (unburned) (1980d) summarizing relationships between crystal size
to pink, yellow, brown, and gray, with the temperature of alite and heating rate, showing that large alite can be
increasing to 1500C. produced by slow heating and not by burning at high
Ferrite microscopy was the subject of a paper in 1967 temperature for long periods. In addition, Ono stated that,
by Ono and Shimota. Various crystallographic and optical as a substitute for alite birefringence to determine maxi-
properties of ferrite were described as a function of the mum burning temperature, one could use the etching
aluminum to (aluminum + iron) ratio, the alumina modu- degree of alite, by which he meant the rapidity of color
lus, in laboratory-produced clinkers. change of alite crystals on an etched, polished surface. As
In 1968 Ono and Shimota published a paper concern a substitute for belite color to estimate the cooling rate,
ing the microscopic textures of ferrite in the systems Ono recommended observation of lxlite crystal surface
GA2F-GA and C2F-C&F-MgO with laboratory-made roughness in etched polished section.
clinkers.They related ferrite crystal morphology and optics On0 presented the following multilinear regressive
to cooling rates, showing that in slowly cooled clinker, equation (among several other similar equations), which
ferrite occurs as femlike crystals and in quickly cooled gives a prediction of 28day mortar-cube strength:
clinker the crystals resemble bamboo leaves. 28day mortar-cube = 415 + 1163(HM) - 205(FL)
Perhaps the most influential paper by Ono was co strength in Ibs/in. - 0.005 (BL) + 0.375 (7d)
authored with Kawamura and Soda in 1968 and pre + 89(AS) + 2OO(AB) + 74(BS)
sented at the Fifth International Symposium on Chemistry + 237(BC) (Eq. 1)
of Cement in Tokyo. This contribution summarized opti- where
cal properties of polymorphic varieties of alite and belite, HM = hydraulic modulus
showing the correlations between transmitted-light micros- FL = free lime percent
copy of these phases and burning conditions. Emphasis BL = Blaine specific surface in cm2/gram
was placed on cooling rates to get optimum hydration 7d = 7day mortar-cube strength in kg/cm2
characteristics from belite. For ordinary and rapid-hard- AS = alite size
ening portland cement, a cooling rate of 17C to 20C per AB = alite birefringence
minute to a temperature of 1200C was considered opti- BS = belite size
mum. This paper, probably more than any previous BC = belite color.
paper, brought international attention to Japanese
methods and theories of kiln control through transmitted- The microscopical parameters (AS, AB, BS, and BC) are
light microscopy. given numerical values with an arbitrary scale of: excellent
The effects of sodium, potassium, and magnesium (4), good (3), average (2), and poor (1) as seen in Table 1.
oxides on the strength of mortar were investigated by This paper was also published in the Onoda Cement
Ono, Hidaka, and Shirasaka (1969) and optimum percen- Company Journal of Research (Ono, 1980b).
tages were established. These authors concluded that Ono (198Oc) indicated that differences in cements with
mortar compressive strength was related to abundances Blaines of 300,330,360, and 400 m2/kg could be easily
of alpha and alpha-prime belite. detected by microscopical examination. Free-lime abun-
Alite crystal chemistry was discussed in a paper by Ono dances of 0.5,0.7, 1 .O, and 1.5 percent were also said to
(1974) in which he described changes in the atomic be microscopically discernible, as well as hydration films
structure of alite in response to such variables as solid on cement particles and flower petal or cauliflowerlike
solution, exsolution, thermal vibration, states of disorder, crystals of calcium hydroxide. Ono microscopically de
inversion, and partial decomposition. scribed the progressive sequence of clinker particle char-
Onos method and theory of kiln control were intro acteristics resulting from repeated grinding of clinker in a
duced to the Western world by Mau (1975). In that same porcelain mortar and pestle, sieving with a 150.mesh
year Ono conducted a seminar for North American sieve, and related these data to clinker grindability. This
cement-company personnel in Hawaii, at which he taught paper also gives a brief history of Onos professional
the details of his theories and method of kiln control with career upon graduation from Tokyo University in 1950.

31
In 1981 Ono published an article tracing the micro
scopic changes of raw feed constituents along the length
of a cement kiln, describing the phase changes in terms of Onos method of cement kiln evaluation is based on
temperature and raw feed position in the kiln. In addition, observations of clinker or cement powder mounted in a
Ono described the characteristics of clinkers in response liquid medium on a glass microscope slide. A polarized-
to different flame lengths and burning conditions. He light microscope (the so-called petrographic micro
presented the following multiregressional equations for scope) is an absolute necessity, and magnifications at
the prediction of 28.day mortar-cube strength from approximately 400X are recommended. The principal
microscopical data: value of Onos technique is that it can be employed by a
competent, trained microscopist on a small sample of
28-day strength in kg/cm* = 253 + 6.4(AS) + 21.9(AB)
+ 4.O(BS) + 21.5(BC) clinker during production. The rapidly performed test
permits a virtually immediate modification of some kiln
0%. 2)
conditions, thus quickly optimizing some of the most
in Ibs/in* = 3422 + 86(AS) + 296(AB) important energy intensive variables that comprise the
+ 54(BS) + 290(BC) manufacturing process. The economic value of the tech-
0%. 3) nique is obvious.
where AS = alite size, AB = alite birefringence, BS = be The principal kiln conditions and microscopical pa-
lite size, and BC = belite color, stated in the arbitrary rameters evaluated by Onos technique are
numerical scale given previously. A standard deviation of 1. Rate of heating (alite size, AS)
230 psi (1.69 MPa) was indicated for this strength predic- 2. Burning time at high temperature @elite size, BS)
tion in Onos presentation at the PCA and ICMA ( 1980d). 3. Maximum temperature (alite birefringence, AB)
Additional testing is recommended.
4. Rate of cooling @elite color, BC)
The crystal lattice constants of alite (a, b, c) and unit cell
volume(V), determined by XRD, were studied in relation to The above list indicates sole emphasis on silicate char-
alite double refraction (Ono, 1984). Alite with high double acteristics observed in powder mounts. However, as Ono
refraction was characterized by long a and short band c, a recommends, data from other microscopical techniques,
decreased V, and large (a/b)*. Laboratory-prepared alite, such as polished sectjon and thin section, can be routinely
burned at high temperature for a long time, had a small V, used in a corroborative manner. A schematic tempera-
large (a/b)*, and a high double refraction.Therefore, XRD ture-time curve and the relationships between the silicates
can be used in much the same way as the microscope in and burning conditions are given in Figure 4 and Table 1,
the quality control of clinker. respectively.

Table 1. Burning Condition and Microscopical


Character of Alite and Belite (Ono, 1981)
Burning condition Hydraulic activity
C
maximum temperature
Excellent (+) Good (4 Average (v) P o o r (-) 1500 ) t
burning time
heating - - - - - - - - - - - - - - - cooling
Heating Rate Quick Slow 1400
rate / \ mtr=
Fiz;f alite 15-20 20-30 (25) 30-40 40-60 (120)
1300

Maxlmum
Temperature High
Birefringence 0.010-0.008 0.007-0.006 0.006-0.005 o.OO,TOO2
of alite
Burning Time Short
Size of belite (20) %?I (60) (15)%-25 (lO)G-20 5-10 0 10 20 30 min.
b-4
Figure 4 Schematic temperature-time relation of
Coolln Rate Quick - - Slow
C o l o r 0P belite Clear Faint yellow Yellow Amber clinker buming (Ono,198Oc).
(C) c-1 WI (A)
Birefringence of 0.012 0.015 0.017 0.018
belite

Content of alpha 1 Abundant (40%) Medium (20%) Few (10%) Nil (0%)

Note: If MgO in clinker is higher than 1.8%. birefringence of alite in the table is plus 0.001. If MgO is
less than 1.2%. birefringence is minus 0.001.

32
Onos method as used at PCA may not be precisely typical of poor burning in a 4000.tons per day kiln (One,
the technique used or taught by Ono. Where significant 198Oc).
deviations occur, a brief explanation is presented in the
section entitled Comments on the Ono Method. The
technique is as follows: Alitebirefdngence(AB)
A representative sample of clinker, say approximately The term birefringence refers to the difference in in-
0.5 kg, is crushed to cement fineness, and a small portion dices of refraction ( nZ - nl ) of relatively fast and slow light
is placed on a glass microscope slide with a spatula. rays as they pass through an optically anisotropic mate-
Alternatively, wet sieving approximately 5 g of the crushed rial, which divides the incoming light into two refracted
clinker (or cement) with isopropyl alcohol to separate the rays traveling in slightly different directions at different
greater than No. 325-mesh (44.pm) and the less than No. velocities. The birefringence (B) of an anisotropic sub-
200-mesh (75.pm) material produces a clean, relatively stance is a constant and dependent on the velocities of
uniformly sized powder mount. After placing the cover light vibrating along certain crystallographic directions.
glass on the powder, a few drops of oil of known RI (1.715 Therefore, if the observed light is not vibrating along these
to 1.720) placed at the edge of the cover glass, are drawn specified directions, the maximum value of I3 will not be
inward by capillary action, thereby immersing the clinker measured.
particles. Hyrax (RI = 1.71) may be used as a permanent Retardation (delta) is the distance that the slow light ray
medium (see Chapter 4). Using a standard petrographic lags behind the fast ray and is directly related to crystal
microscope slide (46x24 mm) and cover glasses (of birefnngence and thickness. In other words,
approximately 10x10 mm), up to four powder mounts
Retardation, A = (Birefringence, B) X (thickness, t)
can be prepared on one slide, thus facilitating compari-
or A = (B)(t) = (nz - nl)(t)
sons of hourly samples.
A standard polarized-light microscope equipped with a and, therefore, B = A/t @I. 4)
Senarmont compensator, having magnifications up to Thus the problem, in practice, becomes the measure
400X, and a rotatable analyzer with a graduated scale are ment of A and t. Delta can be measured with the use of a
used at PCA. All the observations are made with the use of Senarmont compensator. The Senamront compensator
the upper element of the substage condensing lens on the is a crystallographically oriented, thin mica plate designed
microscope. to produce light path differences of more or less than a
quarter wavelength. The fast and slow light velocity direc-
Awe size (As) tions in the Senarmont compensator are parallel to those
of the analyzer and polarizer of the microscope. It is com-
Alite size in the Ono method refers to average alite crystal monly used for determination of retardations of materials
length. After scanning the powder mount for clinker par- of low birefringence such as alite. With the Senarmont
ticles containing whole or nearly whole alite crystals, one compensator inserted in the accessory slot over an alite
measures the lengths of the most commonly occurring crystal viewed in cross-polarized light, linearly polarized
crystal sizes, using a calibrated eyepiece scale. An average light is produced just below the analyzer. The phase differ-
of measurements on approximately 10 crystals is recom- ence (delta) of this light can be reduced to zero by a
mended. Crystal length, width, and thickness can be meas- measured rotation (theta) of the analyrer. Monochromatic
ured by crystal rolling in a high-viscosity refractive-index light is required and, therefore, a green filter (wavelength =
oil, but the procedure is tedious. Alite crystals can also be 546 nanometers) is used.
measured in reflected light, using a finely polished, suit- To measure alite birefringence using a Senarmont
ably etched, cross section of clinker or cement. Clinker compensator and the upper element of the substage
polished sections, in this writers opinion, give a better condenser, Ono recommends the following steps:
measure of average crystal length because an abundance 1. Select a relatively bright alite crystal (appearing white
of clearly cross-sectioned crystals is presented to the to yellowish white to bright gray in cross-polarized
viewer for examination. Crystals chosen for size meas- light), having length to width dimensions of roughly
urement in powder mounts and thin sections are gener- 2:l and, preferably, attached to other clinker phases
ally not those chosen for birefnngence determination.
on at least three sides so that a whole crystal can be
Alite size (according to Ono) depends on burning rate examined (Photographs 11 and 12).
and crystallization rate. Quick-burning by a short flame
produces small crystals formed (a) at low temperature by 2. Measure and record the crystal width (W) in pm using
the calibrated, graduated eyepiece scale.
direct contact of CaO and C2S, and (b) at high tempera-
ture; both developments are relatively rapid. Slow-burning 3. In cross-polarized light, rotate the stage 45 from
in a long flame produces large alite crystals; the rate of crystal extinction (darkness) as illustrated in Photo-
crystallization is generally slow, except during the initial graph 12. For crystals that exhibit a strongly wavy
stages. Crystal enlargement by cannibalism is also slow (undulatory) extinction, birefringence data may be
and negligible in slow-burning. questionable. Therefore, crystals with uniform or
Burning too near the discharge end of the kiln, where nearly uniform extinction are sought.
the temperature change is 1100C to 145oC, also pro 4. Place a green filter in the path of the incoming light
duces small alite, and the clinker is usually poorly burned. and insert the Senarmont compensator, properly
Alite sizes of less than 15 pm in a 1 OOO-tons Per day kiln oriented so that the darkness of the background
can be indicative of poor burning; a 20.pm alite size is results in cross-polarized light. The green filter facili-

33
Photomicrographs Illustrating Onos Method
Photograph 11 Ones method for apparent hire-
Mngence of alite in powder mount. Crystal length-
to-width ratio = approximately 2% On0 measures
particle width. Other observers, the present writer
included, measure uystal width.

Transmitted, plantpolarized light


FD = 0.21xo.21 mm

Photograph 12 Same as Photograph 11 but in


crossed polars and45 from the extinction position.

Photograph 13 Crushed clinker in relkctiw-index


oil showing large, clear to pale yellow, round belite
(amow) with typical internal crossed lamelk. Mod-
erate@ high maximum temperature, long burning
time, slow heating rate, quickly cooled. Dry-process
Mln with flash caldner, 5000 tons/day.

Transmitted, plane-polarized light


m = 021xo21 mm
Photograph 14 Clear to faint yellow, round belie
cq&als in powder mount (44. to 75-pm fraction).
Fast to moderately fast cooling. Coal- and coke-
fired, dry-process kiln, 6500 psi (45 MPa).

Transmitted, plane-polarized light


FD = 0.21xO.21 mm

Photograph 15 Amber Mite uystals in 44. to 75-


pm fraction of crushed clinker. Low maximum tem-
pelature, long burning time, slow heating rate,
moderately slow to slow cooling. Coal-fired, wet-
process kiln.

Powder mount
Transmitted, plane-polarized light
FD = 0.21xO.21 mm
tates obsenmtion of the alite crystal compensation tive of the microscope and is comprised of two precisely
point determined in the next step. cut, crystallographically oriented wedges of quartz. A cays-
5. Rotate the analyzer (upper polarizing element) to tal is set 45 from extinction in cross-polarized light and
crystal darkness (compensation); read the angle of the 546-nanometer filter is placed on the light source. As
rotation, theta (6), indicated on the graduated ana- the sliding portion of the compensator is slipped into the
lyzer scale; and record. If the crystal darkens from optical path, the crystal being examined will slowly darken
edge to center (inward movement), the light interfer- as light compensation occurs. If the crystal is in the sub-
ence is said to be subtractive. If the crystal darkens tractive position, the thinnest part will darken first, followed
from center to edge (outward movement), the light by darkening of the center. The compensator reading lens
interference is said to be additive. In the latter case, is inserted, focussed, and a scale, observed on the cross-
the angle of rotation is subtracted from 180 to give hairs, is read and recorded as X
8. The calculation of birefringence, using I?, is as The formula for calculating retardation, A, with the
follows: Cabinet compensator is:
Retardation (A) is a direct function of theta (0) and A = aAM (X-b) 0%. 9)
the light wavelength lambda (X) passing through the
filter and is expressed where a and b are constants determined by the
he compensator manufacturer and normally given in
A=i% (Es. 5) two wavelengths (h): 546.1 or 589.3 nanometers.
The thickness, X, is determined by rolling the crystal, or
where h = wavelength in pm it can be approximated by other techniques as previously
8 = angle of analyzer rotation. described. Aiite birefringence is calculated as follows:
As previously seen,
Birefringence, B = A/ t( 100) (Eq. 10)
B=A/t
and consequently, A third method of determining alite birefringence
requires a refined appreciation for the various colors of
B = &i/t 0%. 6) alite as seen in cross-polarized light and also the use of a
third-order red accessory plate (gypsum). The Michel
Assuming that the interference is subtractive, the L&y Color Chart, which is a required part of this tech-
following equation is used to calculate birefringence: nique, can be found in almost all optical mineralogy text-
books and is included in the back of the present
A (6) 546 publication. The Chart graphically displays the relation-
0%. 7) ships between interference color, retardation, thickness,
B=T= 180(0.75)(W)lOOO
and birefringence. The procedure utilizing alite interfer-
where 8 = angle of analyzer rotation ence color, a gypsum accessory plate, and the Michel
546 = wavelength of green filter in nanome- L&y Color Chart is as follows:
ters, which is divided by 1000 to convert
to micrometers 1. Select a bright alite crystal (one that exhibits the
and W = crystal width in micrometers. maximum interference color in cross-polarized light)
The equation, therefore, reduces to: and rotate the microscope stage so that the crystal is
at its extinction position (dark).
B = 6 (o.~@d) (Eq. 8) 2. Insert the gypsum accessory plate (wavelength =
530 nanometers). The interference color of the alite
crystal will be first-order red (530 nanometers), as
This formula has been found at PCA to produce an seen on the Chart.
apparent birefringence which, more often than not, easily 3. Rotate the stage 45 to the left, and match the yellow
fits with what is thought to be the correct interpretation of interference color of the crystal observed in the
kiln conditions. However, Ono has stated that 0.75 times microscope to the same shade of yellow on the
the particle width (instead of crystal width) is the best Chart. Mark the position of color identity on the
measurement (Ono, 1981). This topic will be discussed Chart. Rotate the stage 45 to the right of extinction,
later in this section. observe the blue-green crystal color, find it on the
If true crystal thickness is required, the crystal may be Chart, and mark the location.
rolled in refractive-index oil to the proper measurable 4. Measure the distance between the color identity
position by tapping the cover glass with a pencil point points on the Chart and divide by 2.
while observing the particle motion. A high-viscosity liquid
such as marine varnish (n = 1.63) facilitates the technique 5. Measure the crystal thickness (pm) by rolling the
of crystal rolling and measurement. crystal, or estimate the thickness by determining the
The Babinet compensator, rather than the Senannont, crystal width and multiplying by 0.75.
is preferred by some microscopists. The Babinet com- 6. On the side of the Chart labeled Thickness, find
pensator fits into a specifically built slot above the objec- the line corresponding to the value determined in

36
Step 5. From the left end of the line, measure the The observer should not be unduly influenced by extremes
distance finally determined in Step 4. project a line in the range of colors observed. Examination of true
diagonally to the upper right and read the graphically color and crystal surfaces of silicates is facilitated by a
determined birefringence at the top of the chart. study of samples from which the matrix phases have been
One of the principal problems with this method of extracted with a potassium hydroxide and sugar solution
determining birefringence is the variance in color interpre- (Hawkins, 1982). Belite colors are illustrated in photo
tation between workers and even within a single observer. graphs 13,14, and 15.
With practice, however, this technique is quite fast and Belite in the alpha form can contain up to 2 percent
correlates well with methods using other accessory plates. alumina, 2 percent iron oxide, and 3 percent sodium
One can easily distinguish relatively high and low bire- oxide, but only traces of these oxides in the alpha-prime
fringences in powder mount without charts or calculations form. The amounts of these impurities, therefore, are
after becoming familiar with the optical characteristics of functions of the cooling rate. As cooling and exsolution
alite. Obviously this requires frequent practice and an occur, belite changes from clear to faint yellow, to yellow
unbiased observation, as does all reliable microscopy. and amber, depending on the rate of temperature decline.
Alite birefringence observed in clinker is a function of Very slow cooling results in dispersed dotlike impurities in
burning temperature and crystal modifications. High otherwise clear belite. Belite colors observed in transmit-
temperature, trigonal (R) alite has a birefringence of 0.007 ted light have been generally correlated with data from
to 0.010. The disordered monoclinic variety (MI), retain- reflected-light examination of polished sections (Ono,
ing some of the R form, and the M3 form (Maki and 1981).
Chromy, 1978) have birefringences of 0.005 to 0.007. An
ordered MI form has a birefringence of 0.004 to 0.005. Use of Ono*s tables to interpret kiln
The triclinic form (T2) has a birefringence less than 0.004. condltlons and predict 28&y
The birefringence of alite is also a function of where it mortar-cube strength
forms in a clinker nodule. Small alite crystals near a nest of
After listing the powder-mount data, one records the
free lime have low birefringence. Large or medium crys interpretations taken from Onos table showing the rela-
tals near a belite nest have high birefringence. Isolated tionships of the parameters to various burning conditions
crystals blown around in the high-temperature burning (Table 1). For example, assuming the data given below,
zone have very high birefringence (Ono, 198Oc). the interpretations are as follows:

Bellte size (B8) Assumed


HYYF
parameter data Interpretation and symbol
This parameter is the average of the longest diameters of
approximately 10 crystals. Typical belite crystals are seen Alite birefringence Low maximum Poor (-)
= 0.004 temperature
in Photographs 13 through 15. In selecting the crystals for
measurement one should look for crystals representing Belite size Long burning Excellent (+)
the most commonly occurring crystal size. Belite size, in = 35 microns time
the writers opinion, is best determined with polished, Alite size Moderately slow Average ( v )
etched sections or thin sections. = 38 microns burning rate
At a temperature of approximately 1100C to 1200C Belite color Moderately quick Good (4
alpha-prime belite forms as small crystals; at about = Faint yellow cooling rate
1400C the crystals change to alpha and exhibit consider-
able growth. Crystal size of belite, therefore, is primarily To predict the 28-day mortar-cube strength using
dependent on the time maintained above 1400C~the Onos table (Table 2) one successively locates each of the
burning time. interpretive symbols corresponding to the four kiln condi-
tions (maximum temperature, burning time, rate of heat-
ing, and rate of cooling) in the order listed and thereby
Bellte color (BC) reaches a predicted value for mortar strength. For the
Perhaps the most important of the four parameters, belite given example, Onos table of 28-day mortar-cube strength
color is estimated using an arbitrary numerical (Table 2) gives a predicted strength of 370 kg/cm2 (5261
scale: Amber (1) Yellow (2) Pale Yellow (3), and Clear psi). Table 2, presented at the Paris Congress on the
(4). One should examine approximately 10 belite crystals Chemistry of Cement (198Oc), utilizes data from kilns with
which are not coated with interstitial phases, noting the quite different daily productions: 500 to 700 tons per day
most commonly occurring color with the arbitrary scale and 3000 to 8000 tons per day. Free-lime contents of 1 to
and calculating an average and standard deviation. Rowe 2 percent may result in 28.day mortar strengths less than
(letter, 1985) recommends observation of belite color in a the table value (Ono, 198Oc). In addition, Ono states that
powder mount made with the minus loo-mesh (0.149 the alite birefringence value should be increased by 0.001
mm) fraction. in the table if the magnesium oxide content of the clinker
As in the estimation of alite birefringence, one should is greater than 1.8 percent: the table value should be
eliminate the extremely large and the very small crystals. A decreased by 0.001 if the magnesium oxide is less than
thin section is particularly advantageous in estimating 1.2 percent. A negative correction factor of 0.001 is also
belite color because the observed belite crystal is a cross recommended by Ono if the sulfate (s03) content is
section and, therefore, uncomplicated by attached ferrite. greater than 1.25 percent.

37
Table 2. Effect of Burning Condition on 28-Day Strength, /cm
+: excellent vv: good, v: average, -: poor, referTfb Table 1 (One, 198Oc)

Max. Temp. + vv V

Burn Time + v v V + v v V + v v V + vv v -

Rate of
Bum Cool
+ + 470 465 460 455 445 440
- 440 435 425 420 415 410 405 400 395 390
vv 445 445' 440. 435 425 420' 415. 415 405 400 395 390 380 375 375 370
425 420 415 415 405 400 395 390 380375 375 370 360 355 350 350
405 400 395 390 3Bo 3Bo 375 370 360 355 350 350 340 335 330 325

vv + 460 460 455 450 440 435 430 430 420 415 410 405 395 390 390 385
vv 440 435' 430* 430 420 m 410. 405 395 395 390' 385 375 370 365 365
V 420 415 410 405 395 395 390 385 375370 365 365 355 350 345 340
395 395 390 385 375 370 365 365 355 350 345 340 330 330 325 320

V + 455 450 445 445 435 430 425 420 410 410 405 400 390 385 380 380
vv ZT 430' 425 20 410 m 405' 400 3903m38038c& 370 365 360 355
V 410 410. 405 400 390 385' 385' 380 j7J m 360, 345 345 340 335
390 385 385 380 370 365360 355 345 345
- 340 335 325320315 315
+ 450. 445 440 435 425 425 420 415 405 400 395 395 385 380 375 370
vv 430* 425' 420 415 405. 400 400 395 385 38q 375 370 360 360 355 350
V 405 400 400 395 375 370 360 360 ! 355 350 340 335 330 330
385 380 375 375 355 350 340 335
- 1 335 330 320 315 310 305

Note: Underline: Japanese cements in 1962-l 963. 500-700 t/d kilns.


Asterisk (): Japanese cements in 19751979,30X!-WOO t/d kilns. (kg/cm) (0.09807) = MPa

Ono stated (letter, 1977) that an alite birefringence 1. Alite-crystal size, optics, zoning, fringing, habit,
slightly higher than 0.007 could be written 0.007 and crystal form;
ranked as good; a birefringence slightly lower than 2. Belite-crystal size;optics, morphology and texture,
0.008 may be written as 0.008- and ranked as excellent. recrystallization, gelappster, exclusion of impurity;
Ono readily admits that the powder-mount parameters
3. Interstitial-crystal size and optics.
used to interpret burning conditions are merely expedients
and that they provide data in which variations reflect rela- Kiln variables with which some of the phase characteris-
tive changes in kiln conditions. Herein lies, perhaps, the tics are correlated are kiln speed, coating of burning zone,
salient point of the On0 method: If the method can be used burning zone temperature, flame length, burning zone
to determine correctly the relative changes in the individ- length, temperature gradient, cooling rate, and atmo-
ual variables (maximum temperature, burning time, rate sphere.
of heating, and rate of cooling), then the use of the method The Ono parameters were found to be the dominant
can be rewarding because immediate changes in some of variables (above chemical composition, including the
the major energy-related production processes can be normal moduli and porosity) in an experiment to explain
made. That the parameters are somewhat imprecise or problems of grindability (Kawamura, and others, 1982).
that their application is not as rigorous as one might want These authors gave the following equation to predict the
should not detract from the essential purpose of the Blaine surface area (BL) with the Ono method:
method: detecting relative changes in kiln conditions. BL=1513+171AS+167AB+417BS-153BC(Eq.11)
Successful application of Onos theories and tech- correlation coefficient = 0.840
niques in routine clinker production and in kiln start-up standard deviation = 97 cm/g
operations is recorded by Prout (1979) with powder
mounts and polished sections providing essential data. n = 30
Prout strongly asserts that application of the Ono tech- where: AS = alite size
nique should be more qualitative than quantitative and AB = alite birefringence
that the data should be interpreted relatively for optimum BS = belite size
benefit (Prout, oral communication, 1984). BC = belite color
An interesting paper by Takagi and Kawashima (1980)
shows the effects of various kiln conditions on alite, belite, Large belite nests were shown to be indicative of poor
and interstitial phases. These authors present a clinker grindability, even though the same clinker may have rela-
Character Index, a collection of parameters which, when tively high porosity. Clusters of belite crystals remained
plotted against compressive strength at 28 days, forms a undivided even at the final grinding stage.
sigmoidal curve. The Ono parameters figure significantly Using alite birefringence and belite size, Ueda and
in the formulation of the Character Index, as seen in the Suzuki (1985) were able to monitor the variable calorific
following list of phase characteristics: value of coals and make adjustments in the kiln condi-

38
tions to maintain clinker quality. made. Powder-mount determinations of birefringences,
The results of microscopy by the Ono method are using Equation 8 and clinkers from the same sample
considered an important part of the data base in a compu- studied in thin section, resulted in an average birefrin-
terized multivariate analysis conducted routinely for gence of 0.0078, standard deviation of 0.0016, and maxi-
cement quality control in plants of the Onoda Cement mum and minimum values of 0.0104 and 0.0034,
Company in Japan (Aizawa, 1985). Microscopical data respectively.
are said to be helpful in making frequent adjustments in It is clear that the Ono formula (Eq. 7) gives an appar-
kiln parameters, clinker silo operation, and adjustment of ent birefringence and, perhaps, should be indicated B*
cement fineness. The continually updated analysis (read B star). Ono is in agreement with this suggestion
involves the following process variables: burning zone (1981). Nevertheless, even though one does not deter-
temperature, kiln outlet clinker temperature, secondary mine the true birefringence with Onos method, the data
air temperature, extraction air temperature, kiln rotation can be validly interpreted to indicate relative changes in
torque, nitrous oxide, percent clinker passing the 5-mm maximum burning temperature, interpretations which can
screen, and liter weight. be corroborated by other microscopical data. The inter-
Application of the Ono Method to the evaluation of kiln pretive value of apparent birefnngence for maximum
conditions in relation to cement hydration processes and temperature is being used by many microscopists in
types of added sulfate (natural gypsum, beta hemihydrate, Oriental and North American cement plants.
and anhydrite II) is the subject of a recent paper by Uchi- In this connection, Ono stated (1980d) that the etch-
kawa and others, ( 1984). These authors showed that the ing degree of alite could also be used instead of alite
burning degree, defined as an exponential mathemati- birefringence to interpret maximum temperature. Dorn
cal function of maximum temperature (T), critical temper- and Adams (1983) have described the various etch rates
ature T, = 1250C and the retention time (time required to of alite and belite in relation to hydraulic activity. A blue
keep the clinker above T,), corresponds closely to the color on alite after a 15second nital etch was said to
amount of free lime, liter weight, and microscopal data. represent an active alite.
The highest 28-day mortar-cube compressive strength One of the principal difficulties in the determination of
(43.1 MPa) was obtained with cement made from the apparent birefnngence by powder mount is finding proper
well-burned clinker and gypsum. Well-burned and poorly crystals, those with relatively bright interference colors
burned clinker were characterized by the following factors: and length to width ratios of approximately 2. Extreme
Well burned Puody burned
difficulty in satisfying the ratio requirement may, in itself,
Liter weight (kg/L) 1.25 1.10 be indicative of burning conditions such that the desired
Free lime (W) 0.17 1.64 crystal development was inhibited.
The problem of measurement of crystal thickness (t)
Alite size (pm) 40 20
for the determination of alite birefnngence in powder
Alite birefringence 0.007 0.004 mounts has been the subject of much discussion. Prout
Belite size (pm) 30 10 (oral communication, 1984) finds that the thickness can
Belite birefringence 0.012 0.018 be approximated by the equation (length + width)/2, giv-
ing a reasonable apparent birefringence.
The factor of 0.75 in the denominator of Eq. 7 for alite
birefnngence was statistically derived to account for devia-
Comments on the On0 Method tions between true and observed birefringences of an alite
crystal in which the X vibration direction is not exactly
Alitebirefringence parallel to the microscope stage and the Y and Z
According to Ono, Kawamura, and Soda (1968) alite directions are not precisely known. In order to minimize
birefringence is a function of maximum temperature in the this deviation, which lessens the birefringence, a crystal-
kiln load: the higher the temperature, the larger the bire- thickness-to-particle-width ratio of % is assumed (Ono,
fringence. Birefringence in Onos method is measured on letter, 1978). The clinker particle, in this case, was illus-
alite crystals in clinker particles mounted in RI oil and trated to contain only part of an alite crystal.
observed in transmitted, polarized light. Preliminary data from optical techniques with powder
To date, more than 1500 alite birefringences have been mounts to determine apparent maximum and minimum
determined on crystals in thin section by the present writer, indices of refraction of alite, using an RI oil of 1.72 and its
using clinkers embedded with quartz in epoxy resin. Some dispersion curves, were discussed by Stark (unpublished
of these results have been presented in a microscopical PCA analysis, 1980). Stark found a birefringence range of
comparison of North American and foreign clinkers 0.0030 to 0.0065 with the above technique, compared to a
(Campbell, 1979). The known birefringence of quartz range of 0.0030 to 0.010 by the standard Ono proce
(0.009) was used to calculate the thickness of the section. dure in which the factor 0.75W is used; One-method
No correction was made for differential hardness relief on values for birefringence were consistently higher.
the thin-section surfaces. Average alite birefringence A different interpretation of alite has been given by
determined by the thin-section method is 0.0044, with a Fundal (1982), who stated that alite crystals are twinned
standard deviation of 0.00099. Maximum and minimum individuals of a lower symmetry which imitate a higher
values are approximately00083 and 0.0022, respectively. symmetry (a mimetic relationship). The monoclinic form
A discrimination among and within zoned crystals was not of alite was said to have an index of refraction of 1.72 and a

39
birefringence of approximately 0.0050. Triclinic alite was a maximum in a shorter time when the burning tempera-
reported to be polysynthetically twinned in a fused clinker ture is higher and the raw mix finer, (2) alite impurities
and have a birefringence of 0.0020. Alite birefringence, decrease with an increase in the maximum temperature,
however, exhibits two average values in Fundals Table 1 and (3) correlations between alite birefringence and mag-
(1982): 0.0043 ( monoclinic) and 0.0023 (trigonal and nesium oxide content do not exist and a high content of
possibly triclinic). In fused clinker the monoclinic form was impurities is not essential for making M3 stable at ambient
observed zonally in thin section on the interior triclinic temperature.
form. The zoning relationship was not revealed by pol- Asakura, Uda, and Kawabata (1984) classified alite into
ished section etches with HF-vapor or 4 percent HNO3 in four varieties according to birefringence and texture
ethanol.Trigonal alite was seen associated with void de determined by microscopical examination of plant clink-
posits of alkali sulfate. ers: (1) coarsely crystalline alite (M, variety) with a bire-
Consequently, Fundal (1982) reports results contradic- fringence of 0.003, possibly formed in slow burning; (2)
tory to Onos theory of kiln interpretation, namely, that: zoned crystals with round, dusty M, cores that have low
birefringence (0.003) and Mj rims characterized by fine
1. Determination of alite birefringence in powder mount
inclusions and relatively high birefringence (0.005) the
is subject to an error of approximately 0.0006 and
round M, cores thought to exhibit the effects of possible
that a petrographers rule of crystal width being
remelting with M3 precipitating from the melt on the origi-
equal to 4/3 crystal thickness is not valid as a short
nal crystal; (3) dusty Mj alite, with a birefringence of 0.004
cut
to 0.005, interpreted to result from the second variety
2. Alite birefringence determined jn thin section, using (described above) by successive addition of heat; and (4)
quartz as an internal thickness standard, is a suitable euhedral, prismatic crystals with a birefringence of 0.006
method. However, a correlation with burning tern and without fine inclusions, said to be a possible result of
perature was not evident. rapid heating,
Fundal ( 1982) measured crystal length (L) as an approxi-
mation of thickness (t). Fundals alite birefringences are, A l l t e size
therefore, quite similar to true birefringence because the Alite crystal size, according to Fundal (1982) is primarily a
denominator (L) in the birefringence equation is relatively function of raw mix coarseness: Large raw mix particles
large. Fundal (F. L. Smidth report, Jan. 2,1978) stated that promote crystallization of large alite crystals because of
the variations in D/L, where D = crystal thickness, account relatively large compositional gradients developed during
for thevariations in alite birefringence by Onos technique, burning. Crystal size, therefore, increases with the increas-
and that small, flat crystals give high birefringences using ing temperature normally necessary to sinter the hard-to
the Ono formula. A form factor was said to represent the bum coarse raw feeds. Crystal volume measurements
birefringence determined by Onos method. Statistically (rr/GxLW) where L and W represent crystal length and
treated data concerning crystal dimensions and birefrin- width, respectively, are best for crystal size distribution
gence are greatly needed. determinations. Fundal found that the larger the crystal
In response to Fundal (1982) Lee ( 1983) pointed out volume, the poorer the bumability.
the bimodality of alite birefringence determined by Maki Lee (1983) stated that kiln variables such as feed
and Kato (1982) who demonstrated relationships with granulometry, feed composition, fuel characteristics, and
magnesium oxide content in the crystal. Lee restated the alkali sulfur circulation are more or less futed in a normal
conclusion by Maki and Kato that the MI (monoclinic) kiln. Therefore, alite size reflects the heating rate, as Ono
phase appears pseudotrigonal in an X-ray powder- has maintained in many papers.
diffraction pattern. Lee believed that Fundals comparison
of alite compositional and optical data with a tectosilicate Bellte color
solid-solution series, such as plagioclase feldspar, or with a The color of belite crystals, according to Ono, is depend-
nesosilicate series, such as olivine and monticellite, did not ent on their contained impurities and the degree to which
suffice to explain the variation in alite birefringence. the impurities are exsolved as the crystal cools. Slow cool-
Chen, Conjeaud, and Lehoux (1985) estimated burning ing permits time for exsolution to occur and a relatively
zone temperatures with three techniques: by bumability dark (amber-colored) crystal results. In a cement, one
studies of the raw mix, by electron-microprobe analysis of commonly observes a wide range of belite colors, extend-
alite in clinker, and by birefringence of alite. The latter ing from clear to amber and probably representing a range
method was said to be the least accurate, due possibly to of cooling rates or crystal compositions (and other kiln
clinker magnesium oxide and sulfate contents, kinetics of variations). Therefore, a modal color, that is, one repre
alite crystallization from a melt, raw mix particle size, and senting the most frequently occurring color, is given princi-
variable calcination rates. pal importance. If belite clusters (nests) comprise a large
Nagashima, Asakura, and Uda (1983) have shown with portion of the observed belite, then their color is given the
laboratory experiments that the MI variety of alite precipi- most weight in a determination of cooling rate. As dis-
tated from the melt is always observed at the maximum cussed later, abundant large belite nests are detrimental to
burning temperature but it is converted to M3 with longer clinker quality and their effect may lessen that of an excel-
holding time. Slow burning results in the M3 variety even lent cooling rate. It is not unusual to find a wide range of
though the holding time is long (up to two hours). These belite color in different belite nests in a thin section of a
authors also suggested that (1) alite birefringence reaches single clinker nodule, the color differences being due to

40
local micro variations in raw feed chemistry (Ono, letter,
1980). Belite color has been said to be the most important
of the Ono parameters (Dom, oral communication, 1980).
Fundal (1982) also presented a different interpretation
of belite stating that, like alite, belite seems to be mimetic,
occurring in the trigonal system and transforming during
cooling to an orthorhombic (alpha-prime form), twinned
symmetrically and pseudohexagonally around the gamma
optical vector. Index of refraction was said to vary little
from 1.72, with a birefringence of 0.015 for both synthetic
(laboratory) and industrial clinker. Fundal pointed out the
common occurrence of different belite crystal colors in
the same nest and, using the ratio of clear to brown
crystals, concluded that the method based on color was
useless for kiln control. The ratio was said to be possibly
influenced by decrepitation and rebuilding of nodules
during burning and by different types of raw mix. Clear
crystals were thought to be produced by crystallization
from the melt, and nests were produced from quartz,
feldspar, low-lime marl, schist, diopside, hornblende, and
other types of particles.
Colorless belite, according to Lee (1983) can occur as
very small inclusions in alite and contains very little impur-
ity. Large-crystal, ringlike belite nests (from coarse alkali
feldspar) are also colorless because of iron-oxide defi-
ciency. These occurrences of belite, therefore, do not
reflect the cooling rate. Consequently, Ono ( 1978) recom-
mends color observation of roughly 20-pm belite crystals
in order to judge the cooling rate.
If the cement or clinker contains belite only as fringes
(coatings) on alite crystals, then the use of belite color and
size in Onos method appears virtually impossible because
of the scarcity of observable belite in powder mount. The
other parameters, alite size and birefringence, however,
remain and can be utilized.

41
Chapter 7
Microscopical Interpretation of Clinkers
Alite and belite, which comprise most of portland cement tory experiments and in cement plants. The author of each
clinker, have a close genetic relationship and are not easily observation and interpretation is indicated, although
separated for microscopical discussion. Alite crystals, for it is very difficult in many cases to establish historical
the most part quickly nucleate and grow within the melt, originality. The reader should be aware that such a listing
exhibiting dissolution, recrystallization, and decomposi- of observations and interpretations taken out of context
tion, the latter to belite (Maki, 1982, and Maki, Morikoshi, from the referenced publications can be misleading,
and Takahashi, 1985). Belite can form during the heating and that general application of the interpretation could
stage as well as in the cooling stage of the burning proc- be risky.
ess. Thus, the microstructures that one may observe in Unfortunately, some interpretations stated by different
the silicates reflect a rather complex genetic history. The authors in the table are contradictory and the reader is left
matrix is an intimate, finely microcrystalline intergrowth of to his or her experience to determine the correct state
aluminate and ferrite which formed during the very early ment. Additionally, some observations may have more
cooling stage above 1300C (Bye, 1983). than one correct interpretation, that is, multiple causes.
Consequently, instead of a text organization based Furthermore, some of the referenced work appears less
primarily on genetic sequence (see Hofmanner, 1973; than systematic. Such problems point out the need for
Chromy, 1974; Butt and Timashev, 1974; Ono, 1981; and research, and, indeed, it is hoped that the contents of this
Chromy, 1982) the observations and interpretations in this publication serve to stimulate scientific cement research,
chapter are listed first with some of the relatively large- particularly quantitative microscopy with a statistical
scale features of clinkers and then, for the most part, approach, using techniques that group and characterize
according to phase abundance. Rather than in a lengthy the sets of observations and genetic conditions.
narrative survey of interpretive details of clinker phases, The photographs in this section are illustrations of
stated by various authors in many published papers, the clinkers examined and interpreted by this writer, with
information is communicated in tabular form. Table 3 emphasis on the use of Onos interpretive table (Table 1).
presents, in a double column, a list of (a) clearly recorded It is important to note that individual photographs may not
observations and (b) verbatim published interpretations, depict all the microscopic features normally associated
associations, or correlations. This survey is not a critical with the stated interpretation of kiln conditions, the inter-
review. pretation having been drawn from the results of several
Seldom does a single observation of a particular techniques of examination and study of several clinkers in
microscopic feature provide sufficient evidence to warrant the sample. Designations such as 6200 psi (42.8 MPa)
a widely applicable interpretation. Most interpretations in the photomicrograph captions indicate reported 28-day
given herein represent conclusions drawn from reported mortar-cube strength.
observations of clinkers made by many authors in labora-

Table 3. Microscopical Interpretation of Clinkers


General Features of Clinkers
OblElVdOIM lnteqm%ations
Evenly distributed phases; idiomorphic alite; rounded belite; Optimized manufacturing conditions: correct chemical com-
finely differentiated matrix; scarce, small, free-lime crystals position of raw feed, well mixed, no particles too coarse, satisfac-
tory maintenance of sintering and cooling temperatures (Hof-
manner. 1973)
Even distribution of silicates Ideal clinker structure, good production conditions (Fundal,
1980)

42
General Features of Clinkers (continued)
Obsewations Interpretations
Increase in alite content and crystal size, increasing difficulty in Relative increase in lime saturation factor, LSF (Long, 1982b)
burning, reduction in cement strength
Increase in silicate abundance, decrease in liquid, higher tem- Relatively higher silica ratio, S.R. (Long, 1982b)
perature required for combination of feed ingredients, decrease
in alite size
Very heterogeneous clinkers as seen in degree of burning, size, Wet process, introduction of precipitator dust after chain sys
and distribution of minerals tern (Hawthorne, Richey, and Demoulian, 1981)
Clinker shape: (a) single grains, (b) lumpy (a) rotary kiln, (b) shaft kiln (Ciille, and others, 1965)
Edges of alite damaged, notched and pitted belite, dark inter- Typical clinker from large kilns (5xl85m) (Kolenova, 1974)
mediate material with low reflectivity
Prismatic alite; round belite; light-colored, highly reflective Typical clinker from small kiln (4.5x170m) (Kolenova, 1974)
intermediate material; dark prismatic aluminate
Nodule size greater than 25mm diameter Requires longer burning time or higher burning temperature
(Heilmann, 1952)
Increasing clinker size Higher burning temperatures and larger amount of liquid phase;
more time for nodulation (Eby, 1985)
Chains of silicates Bridging reaction between constituents, and between burning
zone and cooler inlet; easily eroded, producing dust (Fundal,
1980)
Large pores, wide bridges, and large solid areas Dry process (Kramer, 1960)
Numerous small pores, narrow bridges, crescent-shaped voids Pellet&d raw mix (Kramer, 1960)
Pores with wide range of sizes, shape, and distribution; abrupt Wet process (Kramer, 1960)
size changes in adjacent pores; small bridges
Increasing roundness of pores, decrease in porosity; higher fer- Increasing MnO content (Knbfel, Strunge, and Bambauer,
rite and belite content at expense of aluminate and alite; de 1983)
crease in melt viscositv. increase in arindina time
Extremely dense structure, large alite Kiln wall (Fundal, 1980)
Dense clinker structure, closed pore system Densification at temperature below melt formation (Fundal,
1980)
High clinker porosity Low degree of burning (Gille, and others, 1965)
Highly porous clinker, open pores, 5090 Mm alite Sandy raw meal (Fundal, 1980)
Compact clinker with spherical, closed pores; 1 O-20 pm alite Marl-type raw mix (Fundal, 1980)
Large pores, nontwinned belite, large alites High !30J (Tsuboi and Ogawa, 1972)
Rough pore surfaces Low temperature burning (Tsuboi and Ogawa, 1972)
Very porous clinker consisting of small bright grains with Under-burned clinker (Tornebohm, 1897)
rounded edges
Porous, aliterich, lumpy clinker, some with dense centers; Excessive hard burning (Long, 1982a)
dusty clinker, ring and stalagmite formation in kiln and cooler;
large alite crystals; sparkling luster of clinker; lowered cement
strength
Friable clinkers surrounded by a deposit of alite crystals alone Very hard burning of high silica ratio materials (Pollii, 1980)
Clinker nodules of varying composition Inadequate blending of feed or segregation in kiln (Long,
1982a)
Clinker inhomogeneity Lower reactivity of ash, too short retention time at clinkering
temperature, high ash content, lump coal for precalcining
carbon-rich fly ash as a raw material, waste-derived fuels
containing graphite (Sprung, 1985)
Nests Excessive particle size in raw mix (greater than 0.1 mm) (Gille,
and others, 1965)
Streaks and spots in clinker Nonhomogeneity of raw mix, segregation of dust in air ducts,
during transfer to silo or in kiln (Gille, and others, 1965)

43
General Features of Clinkers (continued)
Ob!XWiltiOnS Interpretations
Spots in clinker Local increase of individual components of raw material; low
burning degree (temperature too low or burning time too short);
low lime content (Gille, and others, 1965)
Overall crystal size Function of temperature, time, and chemical composition of
surrounding material; absorbed nests and prior nonhomoge
neities (Gille, and others, 1965)
Large crystals High temperature, long burning time, surrounding material is
low lime (belite) (Gille. and others. 1965)
Large crystal cements Unsatisfied charges on broken crystal surfaces resulting in ag-
glomerations, abnormal setting characteristics, and increased
grinding time (Hansen, 1977)
Large crystal size and narrow crystal size range Unfavorable grindability (Tachihata, Kotani, and Jyo, 1981)
Overall increase in crystal size; alite more than belite, which Lowering of feed to speed ratio, thinning clinker bed depth as
tends toward yellow color burning zone moves uphill (Rader, 1985)
Coarsely crystalline clinker High early strengths, abnormal setting problems (Hansen,
1980)
Coarsely crystalline clinker with a high degree of hydration per High compressive strengths (Entin, Nekhoroshev, and Soroch-
unit specific surface kin, 1980)
Hard, dense clinker, with large alite, plus soft, porous clinker with Variable burning, flushing (passage of charge too rapidly
low alite content through kiln), or excessive feed (Long, 1982a)
Small, poorly formed phases; very high porosity; uneven phase Flushing or sintering temperature is too low (Hofmanner, 1973)
distribution; alite surrounded by large amounts of liquid phase;
belite in clusters
Increase in specific crystal surface (surface area of solid par- Results in an increase in specific pore surface and reduction of
ticles/volume of solid particles) and reduction in melt volume power requirement for grinding (Petersen, 1980)
Three zones in clinker: (a) Primary nodules (kiln ring fragments or nodules formed
(a) Dense core before burning zone)
(b) Intermediate porosity (b) Forms in burning zone
(c) Cokelike (c) Forms between burning zone and cooler due to heavy dust
load (Fundal, 1980)
Dense core, high-porosity shell Agglomeration of dust (less than 1 .O mm) on nodule between
burning zone and cooler inlet (Fundal, 1980)
Peripheral zones in clinkers Differentiation or segregation of melt during liquid stage of
groundmass (Gille, and others, 1965)
Fine clinker Soft burning, insufficient liquid phase; extreme hard burning and
abrasion of porous shells on clinkers; Mn mineraliser (large alite
crystals) (Long, 1984b)
Dusty clinker: high porosity, breaded nodules, agglomerated (a) Decomposition of outer clinker shell and concentration of
fine particles, aliterich, large alite crystals, relatively scarce liq liquid phase in clinker core (Allegre and Terrier, 1960)
uid phase (b) Recycling of precipitator dust, reducing zones, lack of AIZO,
in raw slunv (Hofmanner. 1973)
Dusty clinker (poor noduliiation) and snowmen (a) Unfavorable temperature distribution
(b) Too little melt
(c) Too much coarse quartz, lime, slag
(d) Heavy alkali circulation resulting in early crystal growth of
belite and free lime and large silicate crystal size (Miller,
1980)
Belite nest with dense, thick layer of alite with very porous Typical in dust formation (Fundal, 1980)
outermost zones
Clinker dust with abundant belite clusters Inferior bumabilitv (Fundal. 1980)
Dusty clinker, coarsely crystalline silicates, low-porosity nodules, Slow temperature rise, higher clinkering temperature, longer
poor grindability time in burning zone and transition zone (Wolter, 1985)
Coal ash shells on clinkers and nests at boundary zones Nonuniform combustion of fuel and partial reaction on clinker
surface; inadequate grinding of coal and distribution (Kramer,
1960)

44
Gened Features of Clinkers (continued)
obcwmations Inteqwet24ths
Clinker color: earth brown to light brown to dark brown to black In order of increasing degree of burning (Gille, and others,
with greenish brown hue 1965)
(a) Reddish brown (a) Abundance of Fe
(b) Dark gray with reddish hue (b) Fe partly replaced by Mn
(c) Slate gray (c) Normal clinker with Mg in greenish-brown ferrite (Gille, and
others. 1965)
Gray-black clinker color Overall oxidizing environment (Long, 1982b)
Yellow-brown clinker colors Rapid cooling (Long, 1982b)
Gray color of clinker Burning under oxidizing or neutral conditions: Mg0 in lattice of
aluminofemte, presence of trivalent iron (Sylla, 1981)
Gray color of clinker Burned under reducing conditions, cooled in air after removal
from kiln at temperature greater than 1250C (Sylla, 1981)
Brown clinker Burned under reducing conditions, cooled at approximately
1250C under reducing conditions, further cooled in air (Sylla,
1981)
Bleached region in clinker Localized extreme reduction due to partly burned coal deposi-
tion (Long, 1982b)
Well-defined yellow band separating gray-black periphery from Reducing environment with reoxidation (Long, 1982b)
brownish black core
Black oxidized parts of same sample show usual features but Moderate reducing conditions (Woermann, 1960)
with three sets of belite lamellae strictfy oriented crystallographi-
tally with host alite
Clinker is densely burnt, light brown; ferrite has distinctly lower Reducing conditions (Woermann, 1960)
reflectivity than in normal clinker; calcium and iron sulfides
Disappearance of ferrite phase, iron transformed to metallic Extreme reducing conditions (Woermann, 1960)
state, clinker color changes to white, alite decomposition struc-
tures vanish
Brown-centered clinkers, larger alite, lower birefringence Reducing conditions; longer, cooler flame; reduction in set con-
trol and strength (Brugan, 1979)
Spotty, banded coloration Chemical differences or varying burning conditions (Gille, and
others, 1965)
Green clinker nodules, chromium-rich green belite, gehlen- Consumption of refractory brick during production at less than
ite matrix optimum kiln capacity or excessive flame length for rated capac-
ity conditions (Brugan, 1979)
Greenish brown-greenish yellow Entrapped magnesium (Gille, and others, 1965)
Clinker weight (liter) Varies as a function of total porosity (Gille, and others, 1965)
High liter weight High alite content (Brown, 1948); increased time of burning at
high temperature (Hawkins, 1979)
Low liter weight MgO slightly high, CaO distinctly high; aggregated clinkers
(Brown, 1948)
Hydration shells on clinker Air-exposed piles of clinkerwith roofs of partial hydration (Kra-
mer, 1960)
Green, yellow, and brown clinkers Addition of Ci, T?, and Fe3/Mn2, respectively (Laxmi,
Ahluwalia, and Chopra, 1984)
Weathered clinker and low Blaine fineness of cement Problems in thickening time and free water in oil-well cements
(Reeves. Bailev. and McNabb. 1984)

45
Photomicrographs of General Features of Clinkers
Photograph 16 Porous outer zone of ciinker, sur-
rounding relatively dense ciinker core. Eveniy dis-
tributed, round, clear beiite uystais and angular
aiite. Pores filled with epoxy. Modemteiy high maxi-
mum temperature, long burning time, slow heating
rate, quickiy cooled. Dry-process kiin with flash cai-
ciner, 5000 tons/day.

Thin section
Transmitted, plane-polarized light
FD = 0.53x0.53 mm

Photograph 17 Polished section of cement in epoxy,


Wstrating large multiphase (composite) par-tides
and smail, single phase particles, a typical reiation-
ship for most portiand cements.

Nitai etch
FD = 0.38xo.38 mm

Photograph 18 Uniform siiicate distribution in poi-


ished clinker thin section showing angular, equant
to elongated aiite; round, clear beiite with typical
muitidirectionai iameilae; and a tieiy microuystai-
line matrix of aiuminate (Cd) and feuite (Cfl).

T-, pianopolarized light


Section thickness = 15 fl
FD = 0.53x0.53 mm

46
Photograph 19 Same Reid of view as previous
photograph. Different shades of gtay on silicates
indicate different crystallographic orientations in
partially cross-polarized light. High maximum tem-
perature, long burning time, slow heating rate, quick
cooling, 6086 psi (42 MPa). Dry-process, coal- and
coke-fired kiln, 2145 tons/day.

Photograph 20 Clumpy clinker with generally small


uystals. Average alite and belite sizes are 24 and 24
pm, respectively. Coal- and coke-fired, wet-process
kiln, 1000 tons/day. Moderately high maximum
temperature, moderately long burning time, moder
ately quick heating rate, quickly cooled, 7000 psi
(48.3 MPa), Type III cement.

Thin section
Partially crossed polars
FD = 1.9x1.9 mm

Photograph 21 Extremely pomus, sandy clinker


showing silicate aystal chains. High maximum tem-
perature, long burning time, slow heating rate,
slowly cooled, 5050 psi (34.9 MPa). Coal-fired, wet-
process kiln.

Polished section
Nital etch
FD = 0.38x0.38 mm
Photomicrographs of General Features of Clbkers (continued)
photograph 22 Variation in aiite crystai sizes: cius-
ters of smaii crystais (14 fl), noncluster crystals
(38 w). Round beiite crystais in nest in upper
center. High maximum temperature, long burning
time, moderately slow heating rate, quiddy cooled,
6048 psi (41.7 MPa). Gas-fired, dry-process kiln,
770 tons/day.

Thin section
Transmitted, plane-polarized light
FD = 0.59x0.59 mm

Photograph 23 lnhomogeneous coarse feed resuit-


ing in highly porous ciinker with extremely nonuni-
form distribution of silicates. Thin edges of this reia-
tively thick thin section reveal a clear to pale yellow
belite color. High maximum temperature, long
burning time, moderateiy slow heating rate, quickiy
cooled, 6200-6620 psi (42.345.7 MPa).

Transmitted, plane-polarized light


FD = 1.9x1.9 mm

Photograph 24 Porous heterogeneous dinkershow-


ing nests of dark, round belite surrounded by rela-
tiveiy large aiite crystals. insufficient liquid phase.
Very sandy raw mix with abundant metasiltstone.
High maximum temperature, moderately short bum-
ing time, slow heating rate, moderately slow cooling
rate. Gas-fired, dry-process kiln, 3000 tons/day.

Polished section
Nii etch
FD = 0.53x0.53 mm
Photograph 25 Amber to ydow belite in large,
sharply bounded nests and clear, angular alite uys-
tals with a wide range of sizes and nonuniform dis-
tribution. Insufficient liquid phase. Feed contains
abundant coarse met&It&one particles. Estimated
free lime = 1.5 to 2.5%. Gas-fired, dry-process kihx.
High maximum temperature, moderately short bum-
ing time, slow heating rate, moderately slow cooling.

Thin section
Transmitted, plane-polarized light
FD = 0.6oxo.60 mm

Photograph 26 Extremely heterogeneous clinker


containing large concentrations of loosely packed
yellow-amber belite and alite with a wide range of
crystal sizes and, like the behte, a nonuniform dis-
tribution. Free lime is abundant (dark, round ays-
tals). Sandy, silica-rich raw feed with coarse quartz.
Gas-fired dry-process kiln, 3000 tons/day.

Polishedsection
Nital etch
FD = 0.53x0.53 mm

photograph 27 Streak of belite crystals in sulfate-


resisting cement clinker, suggesting nonuniformity
in feed. Gas-gred, dry-process kiln, 770 tons/day.

Polished section
Nital etch
FD = 0.53x0.53 mm
Photomicrographs of General Features of Clinkers (continued)
Photograph 28 Clinker from vertical shaft kiln, In-
dian mini-cement plant, in which clinker hetero-
geneity is the rule. Dark free lime in upper left,
anhedral small alite (center) small, round, zoned
belite (lower left and bottom). Dull ferrite. Coke
breeze as fuel. Reducing conditions. Kiln residence
time is approximateiy 6 hours, 3040 min in burning
zone, 4 hrs in cooling zone. Reported 28-day mortar
strength = 7810 psi (53.9 MPa).

Polished section
Nital etch
m = 0.21x0.21 mm

Photograph 29 Randomly scattered silicates in well-


made clinker. Small, angular, brown aiite. Relatively
large, round, multicolored belite; well-differentiated
matrix of aluminate (Cd) and ferrite (Cfl). Mod-
erate porosity not shown.

Polished section
Nital etch
FD = 0.21x0.21 mm
Alie
ObseNatIons Inteipretations
Increase in alite content, decrease in belite and free lime Increased nucleation of alite by adding 0.5% CS (less than
20pm) to raw mix (Strunge, Knofel, and Dreizler, 1985)
Alite abundant, belite scarce, free lime abundant (evenly dis- (a) Lime saturation too high
tributed) (b) Sintering temperature too low
(c) Too rapid passage through sintering zone
(d) If free lime clustered, carbonate grains too coarse in raw
meal
(e) Insufficient homogenation of raw mix (wide-meshed clus-
ters) (Hofmanner, 1973)
Widely fluctuating C,S abundance in clinker and dusty kiln con Periodic dumping of silica-rich loads resulting from silica build-
ditions ups in dry raw feed grinding mill and consequent surges of fine
calcite (Darn, 1980)
Increase in alite percentage and crystal size, decrease in belite Increase in burning temperature and time with T = 1450C to
percentage, decomposition of C,A 1750C and time up to 800 seconds (Butt, Timashev, and
Starke. 1973)
Alite scarce, belite abundant, free lime absent Lime saturation too low (Hofmanner, 1973)
Increase in abundance of alite and belite Increase in Tii2 content in clinker (Knofel, 1977)
i
Pronounced decrease in alite content Slow cooling under reducing conditions (Sylla, 1981)
Very large alite and belite crystals (averaging or exceeding 100 Burning with fuel oil containing 2.5 to 3.5% sulfur (Hawthorne,
pm), cubic CIA, K2S04, and CaSO., crystals Richey, and Demoulian, 1981)
Extremely large and thick alite (100-200 pm) Contamination of considerable amounts of NazO, KZO, and SO3
in clinker (Ono. Hidaka. and Shirasaka. 1969)
Large, thickcrystals of alite, developing on rhombohedron faces Slow crystalliiation (One, Hidaka, and Shirasaka, 1969)
(Oli2) and ClOil j
Large alite with small inclusions of fine ferrite and alumi- Result of burning at 1450C (Maki and Goto, 1982)
nate crystals; alite is mostly MI variety
Stacked alite crystals High temperature (Gouda, 1980)
Alite crystals, granular, showing strong growth perpendic- Recrystallization of alite during retention for 120 min at 1600C;
ular to basal pinacoid (0001) due to development of pyr& melt is low in degree of supersaturation (Maki, Haba, and Taka-
midal faces: solely T1 variety; concommitant increase in belite hashi, 1983)
size
Alite crystals tabular, indicating growth parallel to basal pina- Recrystallization of alite during retention for 5 min at 1600C;
coid; exclusively M, variety melt is highly supersaturated (Maki, Haba, and Takahashi,
1983)
Xenomorphic crystals Low temperature (Gouda, 1980)
Large alite Long flame, slow heating rate (Ono, 1981); coarse limestone or
calcite in feed (Akatsu and Monna, 1966); coarse quartz (Ono,
1954); long thickening time in oil-well cements (Reeves, Bailey,
and McNabb, 1984)
Large alite Longer burning time, higher temperature, limepoor environ-
ment in the vicinity of belite; coarse raw mix; and high-viscosity
liquid due to alkali or sulfate (Darn, 1979); extreme hard burning
and porous shell on clinker nodule (Long, 1984b)
Relatively large alite crystals, somewhat rounded Clinker burned under reducing conditions, removed from kiln at
1350C cooled in air (Sylla, 1981)
Increasing size of alite Coarse raw feed, coarse quartz, increase in firing temperature,
decrease in strength (Long, 1983)
Large densely packed alite crystals Derived from large belite in nests from coarse silica (Long,
1983)
Cannibalistic (fused) alite Erratic thickening times and unpredictable retarder response
(Reeves, Bailey, and McNabb, 1984); reduced activity level
(Darn, 1985)
Relatively large alite crystals, typically corroded; well-differen- Clinker burned under oxidizing conditions and cooled to 1250C
tiated matrii in the kiln (Sylla, 1981)

51
Alite (continued)
ob!HmatIons Intwretations
Relatively large aliie and beliie crystals, narrow range of size Burning with natural gas (Hawthorne, Richey, and Demoulian,
variation, lower than average reactivity 1981)
Large alite crystals Large quartz grains in raw mix; enhanced MI development
during prolonged heating; abundant So, (Maki and Goto, 1982);
long burning zone relative to flame length (Hansen, letter, 1985)
Large alite in cluster Derived from belite nest from quartz grains near critical size (44
pm) or high temperature burning (Fundal, 1980)
Alite cluster, small crystals (10 pm) plus minor f-&O or belite in Marty grain near cement composition (Fundal, 1980)
same cluster
Coarser alite (average = 50 to 60 pm) with a few large inclusions Longer coal flame (Kramer, 1960)
Increasing alite size, densification of clinker Relatively lower alumina ratio, AR, (Long, 1982a)
Coarsening of alite and belite Clinker at highest temperature for too long or sintering tempera-
ture is too high (Hofmanner, 1973)
Amount of small alite decreases, moderate and large size Slow burning at medium temperature (One, Kawamura, and
alite increases Soda. 1968: Or-0 198Od)
Large to very large, idiomorphic alite crystals Correlated with increasing SO, content in low-alkali laboratory
clinkers; reduced viscosity of melt; strength loss (Dreizler,
Strunge, and Knofel, 1985)
Alite and belite are greater than 30 pm Irregularities during burning do not influence mortar strength so
markedly (Tsuboi and Ogawa, 1972)
Alite and Type I belite greater than 30 pm High mortar strength at 28 days (Tsuboi and Ogawa, 1972)
Alite more than 20 pm and dense belite nests Numerous quartz grains greater than 100 pm (Tsuboi and
Ogawa, 1972)
Large alite adjacent to belite nest Reflects composition gradient of belite to alite with very little
interstitial phases (Fundal, 1980)
Large alite crystals near belite Surrounding area low in lime (Gille, and others, 1965).
Alites more than 20 pm and euhedral, large Type I beliie Well-fired clinker, high mortar strength (Tsuboi and Ogawa,
1972)
Alite size ranges by factor of two at distance of 100-200 pm Insufficient diffusion due to low temperature as a result of too
brief burning (Tsuboi and Ogawa, 1972)
Alite size decreasing, alite abundance increasing Increasing burning temperature from 1500C to 1700C (Su-
zukawa, Kono, and Fukunaga, 1964)
Great difference in sizes of alite and belite in individual clinkers Nonuniform firing: changes in fuel consumption, SO,, and alkali
circulation (Tsuboi and Ogawa, 1972)
Small alite crystals vs. large crystals Limerich vs. silica-rich regions in clinker (Bye, 1983)
Alite size variation Absorbed nests or prior nonhomogeneities (Gille, and others,
1965)
Alite size decreases Increasing feed volume through kiln, burner pipe retraction, and
increase in primary air (Brugan, 1979)
Coarsely crystalline alite surrounded by finer-grained alite and Coarse quartz and locally high LSF converting previous belite
free lime nest to alite (Miller. 1980)
Wide variation in alite size, small alite Nonhomogeneous raw mix; locally high LSF (Fundal, 1980)
Small grains of alite Relatively rapid strength gain (Kramer, 1960)
Thin tabletlike crystals High SiOz in mix, iron-rich liquid phase (Gouda, 1980)
Large, platy alite crystals in eutectic matrix of finely crystal- Fused clinker, quickly cooled from temperature of 1720C
line alite and C, *A7 (halogenated) (Maki, and others, 1984)
Small, thin crystals of alite, developing on basal pinacoid (0001) Rapid crystallization (Ono, Kawamura, and Soda, 1968)
Alite size is small, dominance of Mj variety Rapid crystallization during 10 min retention at 1600C (Maki
and Goto, 1982)
Small alite Short flame, fast heating rate (Ono, 1981); burning zone shorter
than flame (Hansen, letter, 1985)

52
AIite (continued)
obsavatIons Intemnztations
Small alite Short flame, fast heating rate (Ono, 1981); burning zone shorter
than flame (Hansen, letter, 1985)
Relatively numerous small alite crystals K20 without sulfate and increase in melt viscosity (Strunge,
Knofel, and Dreizler, 1985)
Small alite( average = 20 to 50 pm ) containing various inclusions Short oil flame (Kramer, 1980)
Small alite crystals Burning of very fine raw feed at low temperature; silica feed
particles less than 50 pm (Long, 1982a); short thickening time
in oil-well cements (Long, 1984a)
(a) Small alite (15 pm) (a) Fine raw feed or half-burned clinker
(b) Moderate alite (15-30 pm) (b) Well-burned clinker
(c) Large alite (30-60 pm) (c) Coarse raw feed (One, Kawamura, and Soda, 1988)
70- to 1 00-pm alite crystal size Optimal size for greatest effect on cement properties (Okorokov,
1975)
70- to 90.pm alite crystal size; 20- to 70-pm size Optimal size from chalky raw materials: optimal size from marl +
clay (Fataliev, 1985)
20- to 40spm alite crystal size Optimum size (Butt and Timashev, 1965)
Alite, thin tablets, may be attached to compact crystals, skeletal Excess of Si02 in melt (mostly iron-rich); increase in flow media;
overgrowths on older crystals or very high burning temperature (Gille, and others, 1965)
Increase in amount of small alite, decrease in large alite Rapid burning at high temperature (One, Kawamura, and Soda,
1968)
Increase in alite size and idiomorphism Increasing Tii2 content in clinker (Knofel, 1977)
Decreasing alite size, higher burning temperature Relatively higher AR (Long, 1982a)
Increase in alite size and idiomorphism Lowered viscosity of melt resulting from increase in clinker sul-
fate and degree of sulfatization (sulfate to alkali ratio) (Strung,
Kriofel, and Dreizler, 1985)
Decrease in alite size Rapid burning, resulting in growth rate of crystals slower than
formation of nuclei (Butt Timashev. and Starke. 1973)
Decrease in range of alite crystal sizes Increase in burning temperature, decrease in burning time (Butt,
Timashev, and Starke, 1973)
Birefringence = .004.007 in normal alite but reached .Ol 0 Maximum birefringence in clinker rich in Na]O, SOJ, and MgO
burned at hiah temperature (Ono. Kawamura. and Soda, 1988)
Alite with high birefringence Imperfectly inverted monoclinic form, partially rhombohedral
(Ono, 1981). Large, long kilns, high MgO levels, high burning
zone temperature (Dam, personal communication, 1985)
Large alite crystals with high birefringence High MgO raw meal (4 to 5%) high temperature, long flame
(Ono, letter, 1978)
Alite birefringence = 0.005 to 0.008 Mj form, MgO-rich (Maki and Goto, 1982)
Alite birefringence = 0.003 to 0.005 Hybrid (MI and Mx) forms (Maki and Goto, 1982)
Alite birefringence = 0.003 M, form, relatively rich in SO3 (Maki and Goto, 1982)
Alite birefringence = 0.0026 TZ variety, formed during 120.min firing (Maki, Haba, and Taka-
hashi, 1983)
Simple twinning in pure C,S Develops as a result of rhombohedral to monoclinic transition at
approximately 1050C during cooling (Hofmanner, 1973)
Threefold cyclic twinning of alite synthesized at high tempera- Fineness of twinning depends on starting temperature of the
ture and cooled quickly is coarser than texture of alite formed at quick cooling, which is still in stability region of high-temperature
low temperature and cooled slowly form, and does not depend on maximum temperature or
duration of heating (One, 1974)
Polysynthetic twinning (very minute) in alite Triclinic alite due to failure to absorb enough impurities at high
temperatures (Ono, 1975)
Polysynthetic twinning in pure C,S Develops as a result of monoclinic to triclinic transition at ap
proximately 980C during cooling (Hofmanner, 1973)

53
Aliie (continued)
Obsenmtions lnteqmdations
Zoned alite Cooler to kiln recirculation (Long, 1984b); varying burning con-
ditions (Gille, and others, 1965); low temperature core, high
temperature overgrowth (Ono, 1980d and Chromy, 1967); slow
heating to high temperature (Ono, Kawamura, and Soda, 1968)

Zoned alite with dotlike inclusions Clinker burned with long flame (Ono, 1981)

Zoned alite with lower B in inner part Slow burning to a high temperature (Ono, Kawamura, and Soda,
1968)

Zoned alite, normally M, over M,, boundaries marked by liquid Crystallization over wide range of temperatures: slow heating
inclusions rate (Maki and Goto, 1982)

Alite crystals with small liquid inclusions (intergrowth of fine fer- Precipitation of alite at 1450C during 30.min firing (Maki
rite and aluminate) and Goto. 19821

Reversed zoning (M, overgrows M,) Quick precipitation of alite from melt (Maki and Goto, 1982)

Zones in alite broaden toward nearby belite nest Calcium and silica abundant in nest area (Ono, Kawamura,
and Soda, 1968)

Alite with spindle or lancelike bands Monoclinic to triclinic inversion (Gille, and others, 1965); T,
twinning (Maki, Haba, and Takahashi, 1983)

Decomposed alite shows blurred dark spots in thin section Moderately reducing conditions (Woermann, 1960)

Alite interiors diffusely reflecting (soiled) Very slow cooling (Tsuboi and Ogawa, 1972)

Diffusely reflecting alite, appearing unstable and black Decline in 28.day mortar strength by 1% to more than 5%
(Tsuboi and Ogawa, 1972)

ldiomorphous alite Relatively rapid cooling (Kndfel, Strunge, and Bambauer, 1983)

ldiomorphous alite, glassy matrix Clinker burned under reducing or oxidizing conditions, removed
from kiln at T greater than 1250C and quenched in water
(Sylla, 1981)

Straight-sided crystals of alite and belite; continuous, uniform Extremely rapid cooling (quenching) (Brown, 1948)
interstitial glass

Cokelike clinker, rounded alite (more than 100 pm) and Increasing SO, (Tsuboi and Ogawa, 1972)
amoebalike alite

Emerald-green alite, yellow-green belite Presence of chromium (Bozhenov and Kholopova, 1974)

Brownish alite, blue belite Manganese (Bozhenov and Kholopova, 1974)

Brown alite Coarse iron ore or iron fragments in raw mix (Ono, 1975)

Bright yellow alite, brown belite Cobalt (Bozhenov and Kholopova, 1974)

Decomposition of alite Long annealing time or repeated heat treatment at lower


temperatures, approximately 1200C (Ghosh, 1983)

Decomposition of alite to belite and free lime; abnormally large Slow cooling in kiln (Hofmanner, 1973)
belite and alite

Decomposition of alite into belite, free lime, ferrite, and iron sul- Reducing conditions (Woemann, 1960)
fide pseudomorphous after alite; myrmekitic intergrowth

Pseudomorphic crystals after primary alite contain fine inclu- Moderate reduction, and introduction of iron into alite lattice
sions or margins of ferrite, belite, and free lime resultinq in instability and decomposition (Woermann, 1960)

Relatively wide and more numerous belite borders on alite which Clinker burned under reducing conditions, removed from kiln at
shows lamellar structure, the latter well-developed upon with- 1200C air cooled. Similar texture when removed at 1150C and
drawal from kiln at temperatures lower than 1200C quenched in water (Sylla, 1981)

Irregular alitewith wide border of belite, well-differentiated matrix Clinker burned at 1450C for 1 hour, cooled to 1200C in kiln
of large crystals, metallic iron in aluminoferrite (Sylla, 1981)

Decomposition of alite to secondary belite and free lime; Reducing conditions, coarse coal particles falling- into raw mix
decrease in compressive strength; possible abnormal expansion (Hawthorne, Richey, and Demoulian, 1981)

Decomposition of alite varied between 10% to 85%; exceptions in Lab experiment with reducing conditions, slow cooling (5C
low-Fe or no-Fe clinker per min, 90 min from 1450C to 1 oooOC) (Woermann, 1960)

54
Alite (continued)
OhserVatiOnS Intmpretations
Intimate mixture of belite and dicalcium ferrite on alite lattice Low temperature reoxidation (Long, 1982b)
planes; free-lime crystals with inclusions of 2CaO . Fe2Q
Belite fringes on alite (degradation of alite to belite + free lime) Maintenance of clinker at 1200C and slow cooling of clinkers
with high AR, accentuated in reducing environment (Long,
1982b); increased thickening time for oil-well cements (Long,
1984a); and initial viscosity increases in oil-well cement slurry
(Reeves, Bailey, and McNabb, 1984)
Decomposition of alite to belite and free lime presence of bivalent iron (Hofmanner, 1973)
Alite decomposition into secondary belite Overbuming (Dorn, 1979)
Corroded Crystals of alite Slow cooling (Gille, and others, 1965)
Belite coating alite Pseudomorphic resorption of alite from lime-poor melt; slow
cooling (Gille, and others, 1965)
Belitized alite surfaces Slow cooling (Tsuboi and Ogawa, 1972)
Alite decomposed into CaO and CS; corrosion of alite Tempering (Kramer, 1960)
Serrated alite High Alu203/Fe0, especially when alkalies are abundant (Brown,
1948)
Alites greater than 20 pm, with belite fringes Strength decreases about 1% (Tsuboi and Ogawa, 1972)
Mortar strength with average size of alite less than 10 pm Strength decreases usually more than 5% (Tsuboi and Oga-
wa, 1972)
Compressive strength is 10% higher for 20-pm alites than 28.day strength variation with alite size (Tsuboi and Ogawa,
1 O-pm alites, and 10% lower than 30-pm crystals 1972)

Photomicrographs of Alite
Photograph 30 Euhedral to subhedral, zoned, yel-
lowish tan alite; dark, round belite with typical mul-
tidirectional lamellae; and a well-differentiated
matrix of aluminate (CsA) and fenite (C&F).
Epoxy-filled pore at bottom of photo. Coal-fired kiln,
wet-process, 1000 tons/day, 5500 psi (38.0 MPa);
coarse seashell feed (30% greater than 75 e).

Polished section
Nital etch
FD = 0.21x0.21 mm
Phutomicrographs of Alite (continued)
Photograph 31 Euhedral blue and reddish bmwn
aI& round, brown belitewith multidirectional lamel-
lae; well-differentiated, very finely microaystalline
matrix of aluminate and fenite. Moderately high
maximum temperature, long burning time, moder
ately slow heating rate, moderately rapidly cooled.
Coal-fired, wet-process kiln, 1000 tons/day. Clam-
shell, clay, iron-ore feed.

Polished section
Nital etch
FD = 0.21x0.21 mm

Photograph 32 Small, green-yellow angular alite and


round multicolored belite showing a wide range of
uystal sizes in bright fen-k-rich matrix. Highly reac-
tive silicates. Coal-fired, wet-process kiln, 6600-
7000 psi (46.9 -46.3 MPa).

Polished section
Nital etch
FD = 0.21x0.21 mm

Photograph 33 Clinker thin section (appmximateiy


15 q~ thick) showing r&&ively large angular aliie;
smaller, round belite; and normal fenite with its
short slender intersecting uystals, between which
the aluminate occurs (not visible at thii magnifi-
cation).

Tmnsmitted, plane-polarized light


FD = 0.21x0.21 mm
Photograph 34 Same field of view as pnvious ph*
tograph except in partially crossed polars. Various
colors due, in large part, to different aystallo-
graphic orientations.

Photograph 35 Same field as previous photogmph


but with reflected light and nital etch. Euhedral,
brown alite; round belitewith multidirectional lamel-
lae; well-differentiated matrix (almost invisible in
the photograph). High maximum temperature, long
burning time, slow heating rate, quickly cooled.
Coal-fired, dry-process kiln, 2000 tons/day.

Photograph 36 Blue, subhedral alite uystals with


very nan-ow belite fringe (almost the only belite in
the clinker) and matrbt of gray aluminate and dull
fenite. Average alite size is approximately 26 pm.
Coal-fired, dry-process kNn, 550 tons/day.

Polished section
Nital etch
FD = 0.12x0.12 mm
Photomicrographs of Alite (continued)
Photograph 37 Stacked, blue, strongly zoned euhe-
drai alite with abundant inciusions. Small, round
belite aystais; well-differentiated matrix. Beiite coat-
ing on aiite. High maximum temperature, long bum-
ing time, slow heating rate, siowIy cooled, 5050 psi
(34.8 MPa). Coal-fired, wet-process kiln.

Polished section
Nital etch
FD = 0.21x0.21 mm

Photograph 38 Mzuked topographic relief accen-


tuating silicate crystai internal structures. produced
by lo-second nitai etch followed by lo-second pol-
ish on Texmet with 0.05-m alumina.

Polished section
FT3 = 0.14x0.14 mm

Photograph 39 Coamely uystalline silicates from


coarse seasheii feed. Angular, strongly zoned aiite
and round, reiatively small belite with coarse lamel-
lae. Coal- and coke-fired, semidry process kiln, 1850
tons/day. High maximum temperature, long bum-
ing time, slow heating rate, quick to moderately
quick cooling, 6390 psi (44.1 MPa).

Polished section
Nital etch
FD = 0.21x0.21 mm
Belite
obselvations Interpretations
Large proportion of belite Low LSF (Long, 1982a; Fundal, 1980)
Equal alite and belite LSF = approximately 88% (Fundal, 1980)
Belite agglomerations: Classification of belite agglomerations (Hofmanner, 1973)
(a) Sharply outlined clusters
(b) Diffuse limited clusters
(c) Streaks
(4 Spots
Belite nests Ash shortage, excessive quartz grain size, presence of feldspar
and blast furnace slag (Gille, and others, 1965)
Nests of belite Inadequately mixed raw material, decline of mortar strength
(Tsuboi and Ogawa, 1972)
Nests of belite Vestigal quartz grain (Kramer, 1960)
Round, compact belite nests of large, Polygonal, well-lamel- Large quartz or flint, +44 Frn (Fundal, 1980)
lated crystals
Pore-centered belite nests with relatively large, densely packed Coarse quartz in feed (Long, 1982a)
crystals, producing large alite at higher temperature if lime is
available
Belite nests, possibly with central pore Low lime inclusions such as quartz splinters, ash droplets (Gille,
and others, 1965)
Glass core in belite nest, large alite adjacent to belite nest Residual Si02, a frequent component of insoluble residues
(Fundal, 1980)
Glass CS in center of belite nests Quartz grains are large or poorly burned (Tsuboi and Ogawa,
1972)
Closely spaced belite Large quartz grains in raw mix (Tsuboi and Ogawa, 1972)
Tiqht belite crystals in nests with sparse liquid phase Coarse quartz (Miller, 1981; Gille, and others, 1965)
Large belite clusters Unstable ring formation, especially in sulfate-rich clinkers, if no
large quartz grains in raw mix (Fundal, 1980); segregation of raw
mix (DeLisle, 1979); Poor strength development in oil-well
cements (Reeves, Bailey, and McNabb, 1984)
Large clusters of belite associated with high contents of free lime High LSF (Fundal, 1980)
Large patches of belite; belite nests from coarse quartz Selective reaction of raw mix components: clay at lower tempera
ture than that for quartz, muscovite, hornblende, and Ca-feld-
spars resulting in early nodulation (micronodules) and clinker
dust with high LSF (Fundal, 1980)
Rounded belite in dense nests Intense burning (Tsuboi and Ogawa, 1972)
Belite nests with curved boundaries and very little liquid phase Concentration of siliceous component (lack of lime) (Hof-
manner, 1973)
Lame number of belite clusters Decrease in arindabilitv (Darn, 1985)
Peripheral annular region of belite and flux-rich material in clinker Late deposition of coal-ash layers (Long, 1982)
nodule
Belite concentrations on the clinker surface, free lime in clinker Coal-ash deposition on already formed clinker nodule; similar
interior effects in coatings and clinker rings (Pollitt, 1980)
Belite nests (loosely packed) with aluminaterich melt Coarse aluminosilicate grain, perhaps a feldspar (Miller, 1980)
Amoeboidal clusters of belite (crystal > 30 to 40 pm) Marl or calcite shale (35% CaCO,) with feldspar in a prenodul-
ized raw meal (Fundal, 1980)
Belite clusters rich in liquid phase, relatively small crystals Coarse shale particles (Long, 1982a)
Decrease in belite nests, increase in liquid phase Added iron reduces liquid viscosity and promotes reduction of
belite nests (Dom, 1985)
Belite nests rich in melt phase (loosely packed) Nonquartz argillaceous particles or fuel ash particles (Miller,
1980)
Decrease in belite nests Increase in amount of clay or shale in mix (Frederick, 1985)

59
Belite (continued)
obsewatIon!3 Intemretations
Belite cluster with small periclase crystals Large diopside (Cdu\gSiz06) grain (Fundal, 1980)
Large areas of belite and flux with high-limed clinker nodules Very late deposition of coal ash or insufflation of raw feed
adhering or embedded (Long, 1982a)
Clinkers with belite and flux-rich cores Kiln coating fragment (Long, 1982a)
Belite streaks, generally in peripheral areas of small clinker Local coal ash deposition (Hofmanner, 1973)
Belite coatings on clinkers; heterogeneous clinker Wet process, raw mix leaves chain system still wet (Hawthorne,
Richey, and Demoulian, 1981)
Belite streaks in central areas of large clinkers Inhomogeneity in raw mix (Hofmanner, 1973)
Large belite clusters, peripheral layers, veins, cores in clinkers, Coal ash deposition (Long, 1983)
dispersed in aluminate and ferrite
Belite streaks Local inhomogeneities due to sandy raw mix (Fundal, 1980)
(a) Belite streaks (a) Coal-ash contamination on clinker surfaces during burning
results in low-lime area and belite
(b) Zones of normal composition between belite streak and (b) Products of low abrasion coated on belite streak (Ciille,
surface of clinker and others, 1965)
Crusts of belite on clinkers; crystals of various sizes Semi-dry process, coal fuel with 15% to 20% ash, 0.5% to 1.5%
sulfur (Hawthorne, Richey, and Demoulian, 1981)
Relatively large belite in clinker fines, small belite in nodules Comparatively long time in burning zone for clinker fines (Sam-
uel, Rao, and Chopra, 1984)
large belite with rough exterior surface Overheating or overbuming (Don-r, 1979)
Large belite crystals prolonged heating below liquid-formation temperature (Maki
and Cioto, 1982); coarse quartz or quartzite in feed (Akatsu and
Monna, 1968)
Belite size increasing, belite abundance decreasing Increasing burning temperature from 1500C to 1700C (Su-
zukawa. Kono. and Fukunaaa. 1964)
Coarsening of belite, aluminate, and aluminofemte; irregular Clinker burned under oxidizing conditions, cooled to T below
belite outline, idiomorphous alite 1250C in the kiln (Sylla, 1981)
Relatively large belite inclusions in alite, large belite crystals Abundance of coarse quartz in feed; belite and alite became
(45 km) much smaller upon use of finely ground friable silica (Darn,
1980)
Large, irregularly shaped belite Very slow cooling (One, Kawamura, and Soda, 1988)
Belite is l-4 pm diameter at 1300C but grows to 20 -40 pm Recrystallization during burning at high temperature (One,
crvstals Kawamura. and Soda, 1988)
Multidirectional lamellar structure of belite Formed and coarsened during alpha to alpha prime transition
during cooling (Hofmanner, 1973); clinker burned at greater
than 1420C (One, 1975)
Increase in orooortion of cross laminations in belite ctvstals Increase in Tii, content in clinker (Knofel. 1977)
Amber belite with Type I microstructure (multidirectional lam Belite kept at alpha temperature in kiln coating (Ono, 1981)
ellae)
Small, round Type II beliie Low burning temperature (One, Kawamura, and Soda, 1988)
Sharp, wide lamellae Distorted beta, raw mix rich in FezOx and alkalies (Gouda, 1980)
Colorless Type II belie (parallel striations) Belite held at alpha-prime temperature in kiln coating (One,
1981); burning below 1420C (Ono, 1975)
Rounded belite without lamellae, finely intergrown groundmass Rapidly cooled clinker (Ciille, and others, 1965)
Belite crystals with no stripes, commonly with rents and cracks Stress during rapid quenching (Gille, and others, 1985)
Nontwinned belite SO3 more than 1% (Tsuboi and Ogawa, 1972)
Structureless belite crystals (uniform reflection) Extremely rapid quenching, as in lab (Gille, and others, 1965)
Potysynthetic twinning in belie Formed during very slow cooling as a result of alpha prime to
beta transition (Hofmanner, 1973)

60
Belite (continued)
ObtWViStIOllS Inteqmtations
Belite with polysynthetic twinning Normal cooling rate (Kramer, 1960)
Raqaed belite with dotlike inclusions Clinker burned with lona flame (One. 1981)
Ragged crystals of belite Very slow cooling (Kramer, 1960)
Ragged belite with no degradation of alite Slow cooling at certain A/F ratios: also affected by alkali content
(Long, 1984, unpublished ICMA presentation)
Ragged belite Alpha to alpha prime inversion in contact with melt and slow
cooling (One, 1981)
Ragged belite Slow cooling and resolution (Gille, and others, 1965; Midgley, in
Tavlor. 1964: DeLisle. 1976. 1979)
Belite overgrowths Slow cooling (Gille, and others, 1965); very slow cooling (Lee,
1982)
Rough belite surface, prominent lamellae, segmented finger- Reducing conditions (Dom, 1979)
like sections
Secondary belite, free lime corrosion of alite Slow cooling (Gille, and others, 1965)
Erosion of alite crystals to intimate mixture of belite and free lime Slow cooling (temperature at approximately 1200C for an
pseudomorphic after alite aDDreciable time) (Lana. 1983)
Erosion of alite crystals to form surface belite; pinhead belite in Slow cooling; AR above 2.5; up to 10% reduction in 28-day
matrix strength (Long, 1983)
Droplike belite in liquid phase; commonly associated with den- Excess Siiz (Hofmanner, 1973)
dritic wriclase
Secondary belite, free lime, periclase; autoclave problems Failure of solid fuels (fly ash, carbonaceous shales, coal tailings
as part of raw mix) to bum before granulation zone (Hawthorne,
Richey, and Demoulian, 1981)
Secondary belite coating on alite Resorption into liquid phase (Hofmanner, 1973); slow cooling
(Midgley, in Taylor, 1964)
Myrmekitical intergrowth of belite in alite, pseudomorphous free Decomposition via slow cooling: sometimes accelerated by
lime, and remnants of nondecomposed alite foreign ions, excess alkalies, embedded Fe, and moderate
reducina conditions (Gille. and others, 1965)
Belite laminae on rhombic alite planes, usually three groups Reducing conditions in sinter zone (Gille, and others, 1965)
intersecting
Tinv belite inclusions suaaestive of lamellae in alite Deficient air SUDD~J in sinterina zone (Gille. and others. 1965)
Dismembered, finely dendritic crystals of belite Excess crystallization of belite (Gille, and others, 1965)
Belite next to free lime in normally burned clinker Alkali belite (Gille, and others, 1965; DeLisle, 1976)
Irregular belite Overbuming (Pro& 1979)
Overlapping belite Too much MgO, ZnO, and others that lower viscosity (Tsuboi
and Ogawa, 1972)
Wide lamellae on belite, corroded alite, and cooling cracks Alkali in clinker (Gille, and others, 1965)
Large belite crystals, colorless, low birefringence (0.012-0.015), Alkali belite (Ono, letter, 1977)
sharp striations, coarse sandwich structure of alpha and beta
seen under crossed nicols, crystal surface free from iron phase
Clear belite ring Alpha belite, alkali-rich, derived from melted feldspar which
reacted with f-0 (One, 1981)
Dendritic belite High alkali (K-feldspar) in raw mix (Gille, and others, 1965). Low
primary air volume or pressure, excessive burning-zone tempera-
ture, slow cooling rate, high MgO level-approximately 4.5%
(Don-r, personal communication, 1985)
Alite containing K may tend to decompose Above a certain potassium percentage aliie does not form, but
instead belite and free lime (Woermann, 1968)
Clear belite crystals Quick cooling, no exsolution of impurities (One, 1975)
Pale yellow belite Medium cooling rate (One, 1975)
Yellow nested belite Coarse quartz, lack of lime diffusion into nest (Darn, 1985)

61
Belite (continued)
obseIvations Inteqmt2kions
Belite crystals of normal type microscopically but with extra Sodium- or potassium-stabilized belite; alkalies in excess of
XRD reflections sulfur (Tang and Gartner, 1986)

Colorless, yellow, brown belite Alpha percentages are 15% to 30%, 10 to 25%. and 0 to 15%,
respectively (One, letter, 1981)

Muddy yellow belite Slow cooling rate (One, 1975); relatively hard to grind if nested
(Ono, in Dom, 1985)

Zoned belite with yellow or muddy colors in outer zone Differences in absorption of impurities produced by alpha prime
to alpha transition (One, Kawamura and Soda, 1968)

Belite containing abundant alpha form, alite with high birefrin- High temperature and quick cooling; high strength (Ono,
gence Kawamura, and Soda, 1968)

Scarcity of alpha form in belite Slow cooling, low strength (One, Kawamura, and Soda, 1968)

Dotted, colorless belite (crystals with internal particulate disper- Very slow cooling (One, 1981)
sions)

Dots of imourities in belite Extremelv slow coolina (Ono. Kawamura. and Soda. 1968)

Cracks and fissures along belite lamellae, partial decomposition Belite transition from beta to gamma during cooling, due to solid
of belite crystal solution with foreign ions; insufficiently rapid cooling (Hof-
manner, 1973)

Disintegration due to beta to gamma belite transformation and 4-hour bum in reducing atmosphere, air cooled (Sylla, 1981)
dusting. Nondusted nodule shows partly idiomorphous alite,
belite lamellae in alite; large belite crystals; matrix almost totally
aluminate, metallic iron, and finegrained periclase

(a) Gamma belite, dusted (a) Entrapped Fe and reducing conditions:


(b) Grains with rents and cracks (b) long-lasting tempering occurs in kiln scale and results in
dusting (Gille, and others, 1965)

Dusting in samples of same composition in oxidizing and reduc- Low lime content, beta to gamma transformation of primary
ing atmosphere belite (Woermann, 1960)

Dusting Half-burned clinker at very low temperature: belite cooled from


alpha prime form (One, Kawamura, and Soda, 1968)

Type I belite, with slight excess MgO or burning under reducing Strength decrease up to 5% (Tsuboi and Ogawa, 1972)
conditions

Large quantity of belite next to free lime High alkali and sulfate content in mix hinders reaction of belite
and free lime to alite in laboratory clinkers (Dreizler, Strunge, and
Knofel, 1985)

Decreasing lamination in belite, increasing stabilization of alpha Increasing NazO content of clinker and low degree of sulfatiza-
form tion (Strunge, Knofel, and Dreizler, 1985)

Belite inclusions in alite Relatively large ( 12 to 13 pm) in clinker made with quartz sand;
8 pm in clinker made with sponge-silica (Dorn, 1980)

62
Photomicrographs of Belite
Photograph 40 Experimental laboratory bum with
raw mix containing mart instead of quartz as a silica
source. Resulting behte was well scattered in clinker
and, to a minor extent, as nests. 1OOOC for 30 min.
1425C for 10 min. Very rapid temperature change.
Average alite size = 20 fl. Clinker courtesy of Joe
Garcia, Capitol Cement, San Antonio, Texas.

Polished section
Nital etch
FD = 0.53x0.53 mm

Photograph 41 Experimental laborato~ bum with


raw mix containing quartz (44-75 fim) as a silica
source. Average alite aystal size = 44 w. 1000%
for 30 min. 1425C for 10 mtn. Very rapid tempera-
ture change. Note abundant free lime inclusions in
alite. Clinker courtesy of Joe Garcia, Capitol Cement,
San Antonio, Texas.

Thin section
Transmitted,planepolarized light
FD = 0.21x0.21 mm

Photograph 42 Raggedy behte uystals and belite coat-


ing on alite, one of which is twinned. Note abundant
dotlike impurities in alite. Coarsely crystalline matrix
with g-ray aluminate and relatively bright fenite. Slowly
cooled clinker.

Polished section
Nital on KOH etch
FD = 0.21x0.21 mm
Photomicrographs of Belite (continued)
Photograph 43 Polished section of cement centrifuged
in lo~viscosity epoxy to produce a partide size and
density gradation. Arrow on coarse particle (left) indi-
cates alkali sulfate. Arrow on fine paxtide (right) indi-
cates gypsum. See Campbell (1986).

Reflected light
FD = 0.21x0.21 mm

Photograph 44 Zoned euhedml to subhtximl alite; rag-


gedy, round, intemaIly disorganized belite; well-dif-
ferentiated matrix; and round Pore (upper center) with
perlpheml alkali sulfate. Coal- and coke-fired, dry
process kiln, 900 tons/day. High maximum tempera-
ture, moderatety long burning time, slow heating rate,
slow to moderatety slow cooling rate.

Polished section
Nital etch
FD = 0.21x0.21 mm

Photograph 45 Raggedy belite fmm veny slow cooling.


Extension of fingers into matrix. Note dotlike impuri-
ties. Kiln coating. Coal-fired, dry-process kiln, 2350
tons /day.

Thin section
Transmitted, plane-polaiized light
FD = 0.21x0.21 mm
Photograph 46 Same field of view as previous photo-
graph, butwith partialty crossedpolam, showing highly
birefringent and strongly pleochroic ferrite.

Photograph 47 Same clinker sample as above but dif-


ferent nodule, showing relatively small, irregular, brown
belite wrapping around blue alite crystals, thought to
be typical for clinkers burned at a high temperature for
a long time.

Polished section
KOH followed by nital etch
FD = 0.21x0.21 mm

photograph 48 Inegular to normally round, brown


belite; subhedral, angular, blue alite with cleavage
cracks; and matrix of finely micmcqstalline aluminate
(CsA) and lath-form ferrite. High maximum tempera-
ture, long burning time, slow heating rate, quick cool-
ing, 6000- 6100 psi (41.4-42.1 MPa). Coal-fired, dry-
process tin, 2750 tons/day.

Polishedsection
Nital etch
FD = 0.21x0.21 mm
Photomivqhs of Belite (continued)
Photograph 49 Belite aystals comprising sharply
delineated nest around pore (black), probably the
site of a coarse quartz grain in the feed. Coal- and
cokeAired, dry-process kiln.

Thin section
m = 0.53x0.53 mm

Photograph 50 Clear be&e ring around central pore


formed by silica mobilization during sintering of
coarse quartz in feed.

Thin section
Thickness = applwdmately20 pm
FT3 = 0.53x0.53 mm

Photograph 51 Tightly packed dear belite nest from


coarse quartz in raw feed. Crystals exhibit wide
range of interference colors due to different crystal-
lographic orientations. Note also the generally mot-
tled pattern within indhvidual crystals, suggesting a
somewhat disorganized lamellar structure.

Thinsection
crossed polaM
FD = 0.6oxo.60 mm
Photograph 52 Bimodal belite inlaboratorybumed
clinker made from a raw feed containing coarse
quarts sand. Large nest of tightly packed belite uys-
tats and much smaller crystals showing wide lamel-
lae. Note gradational color response in nital etch of
nest. 55% of the alite crystals were said to be greater
than 75 pm. Clinker courtesy of Joe Garcia, Capitol
Cement, San Antonio, Terms.

Polished section
FD = 0.21x0.21 mm

Photograph 53 Circumscribing cracks around belite


(center left) and linear cleavage in aliie. Low liquid
phase. Shrinkage cracking during clinker cooling.
Epoxy penetrates many of the cracks; therefore,
cracking occurred prior to impregnation. Coat-fired,
dry-process kiln with flash calciner, 5000 tons/day;
moderately high maximum temperature, long bum-
ing time, slow heating rate, quickly cooled, 5850 psi
(40.4 MPa).

Polished section
No etch
FTB = 0.21x0.21 mm

Photograph 54 Gamma be& fmgment in thin sec-


tion. Note semisplintery fracture and internal micro-
stmcture.

Transmitted, plane-polarized light


FD = 0.21x0.21 mm

67
PhotomkrograPhs of Belite (continu
Photograph 55 Thin section of gamma belite frag-
ment in cross-polarized light.

FD = 021xo.21 mm

Photograph 56 Slowly cooled kfln buildup contain-


ing, for the most part, polysyntheticaUy twinned
be& (Qpe II, In&y) in lower left and slightly splin-
tery gamma belite (upper right) in matrix of
c-=b. miaocrystall ine fenite and aluminate.
Thinsection
- polam
FD = 0.21x0.21 mm

Photograph 57 As above but in transmitted, plant


pohized light.

68
Photograph 58 Dark Mue belite (Type II, In&y) at
upper right, subhedral to anhedral alite (pale blue),
and pti puldase (center left). Coarsely crystalline
matrix. Coal- and coke-f%-& Idln, wet process, 950
tons/day. Moderately long burning rate, slow heat-
ing rate, moderately sknv cooling rate.

Polished section
Nital etch
FD = 0.21x0.21 mm

Photograph 59 Polysynthetically tinned belite


(Type II, Insley) in slowly cooled kiln buildup.

Polished section
Nital etch
FD = 0.14x0.14 mm

Photograph 60 Blue, amoeboid b&e in a coarsely


txydalhe, matrix-rich dinker. Amoeboid belite ays-
talsseemtobemostcommonindinkersburnedata
high temperature and slowly cooled. Angular, tan
alite. Other dinkers in this section contained alite
that produced a blue color.

Polished section
Nitai etch
FD = 0.14x0.14 mm
Photograph 61 Polished section of coarsely uystal-
line clinker. Belite uystals exhibit relatively large
areas which are either nonlamellar or show a single
set of parallel lamellae. Type I bellte (Insley) domi-
nates clinker. KOH extra&ion of matrix and concen-
tration of silicates, followed by XRD analysii indi-
cating7%to1O%ofthebelitecomprisedofalphafonn.
Wet-process kiln, 1000 tons/day. High maximum
temperature, long burning time, slow heating rate,
moderately quick cooling.

NM etch
FD = o.21x0.21 mm

Photograph 62 Very coarse, yellow-brown lamellae


ln bellte graln (lower center), perhaps residual from
an earlier polymorph. Coal-fired kiln, wet process.
High maximum temperature, long burning time, slow
heating rate, quickly cooled, 6030 psi (41.6 MPa).

Polished section
Nii etch
FD =0.13x0.13 mm

Photograph 63 Round bellte uystals (brown) show


lng mlnlmal development of lamellae. Coarse feed.
Low maximum temperature, moderately long bum-
lng time, slow heating rate, moderately slow cooling
rate. Dry-process kiln, gas fired, 3000 tons/day.

Polishedsection
Nital etch
FD = 0.38xo.38 mm
Photograph 64 Large, joined aystals of blue alite
and round, brown-tan belite with unusually wide
lamellae. WeU-differentiated matrix.

Polished section
Nital etch
lm = 0.21x021 mm

Photograph 65 Dense, coarsely aystalline cltier


showing large, blue belite uystals (center right) with
numerous exsohred dotlike inclusions; tan areas
(upper left) of apparently nonlamellar be&e; sec-
ondary be&e dots In fenite matrix (center left).
Coal-flred, wet-process kiln with temperature known
to be approxknately 3000F.

Polished section
Nital etch
FD = 0.21x0.21 mm

Photograph 66 Blue, subhedral alite with well-


developed belite coating (tiges); raggedy and
dismembered round belite (intemallysomewhat dis-
organized); and a well-differentiated matrix of alum-
inate and dull-reflecting f&e. Modemtely high
maximum temperature, moderately long burning
time, slow heating rate, moderately slow cooling
rate; reducing conditions. Coal- and coke-fired wet-
process Idln, 950 tons/day.

Polishedsection
Nital etch
FD = 0.21x0.21 mm

71
Photomicrographs of Belite (continued)
Photograph 67 Dismembered and dend&lc belite,
ordinary round belite, and belite coatings on alite.
Coamdy aystalline matrix. Gas- and coal-fired din-
ker from wet-process kiln, 500 tons/day. High max-
imum temperature, long buming time, slow heating
rate, modmtely slaw cooling.

Polished section
Nital etch
FD = 0.21x0.21 mm

Photograph 68 Dendritic belite in furittrich matrix


of clinker containing fragments of refractory brick
(not shown). Brightly reflecting fenite in plane-
polarized light is unusually pieochroic, suggesting
compositional change from refmctow brick con-
sumption.

Polished section
Nital etch
FD = 0.14x0.14 mm

Photograph 69 Dendritic Wite in coameiy cry&al-


line clinker. Raw feed has almost 36% greater than
No. 325 mesh (44 w). Moderately high tempera-
ture, long buming time, slow heating rate, and quick
cooling rate. Coal-fired wet-process kiln; 960
tons/day.

Polished section
Nital etch
FD = 0.21x0.21 mm
Photograph 70 Clinker thin section in Hyrax show-
ing dotlike products of exsolution and raggedy,
inclusion-free overgwvth (arfow) on large belite
uystal. Bruwn-centered dinker. Redudng conditions
and slow cooling are suggested.

Transmitted, plantpolarized light


FD = 0.21x0.21 mm

Photograph 71 Kiln coating showing beIite aystals


with Type II fIngem around reIatively disorganized
core. Coardy uystalline maMx containing large
peridase cqstaIs (mw)). Slow cooling through
alpha-prime belite temperature range. Dry-process
kiln, 2350 tons/day.

Polished section
Nital etch
FD = 0.14x0.14 mm

Photograph 72 Radial cracking in round belite uys-


tals. Subparallel microcra cks on a much smaller
scale (amow) in angular alite aystals. Class G oil-
well cement dinker.

Polished section
Nital etch
FD = 0.21x0.21 mm
Photomicrographs of Belite (continue Id)
Photograph 73 Beiite laminae in light blue aiite.
Muiticolored, round beiite showing typical iameiiae,
but somewhat scaiioped cross section. Small sec-
ondary belite in brightiy reflecting ferrite matrix.
Clinker contains remnants of chrome-magnesia
r&actmy brick.

Polished section
Nitai etch
FD = 0.21x0.21 mm

Photograph 74 Alite aystals with secondary beiite


iaminae (arrow) and beiite hinges. Coarsely crystai-
line matrix of aluminate and dull ferrite. Slow cooi-
ing and redudng conditions.

Polished section
Nitai etch
m = 0.21x0.21 mm

Photograph 75 Coarsely uystalline siiicates from


coarse seashell feed. Pale olive to tan, angular aiite
uystais with beiite lameiiae (arrow): round, coarsely
iameiiar beiite; and a fineiy microuystailme matrix
of aiumhuite and duii fenite. High maximum tem-
petature, long burning time, slow heating rate, quick
to moderateiy quick cooihtg, 8390 psi (44.1 MPa).
Coal- and coke-fired, semidry-process kiin, 1850
tons/day.

Polished section
Nitai etch
FD =0.21x0.21 mm
Photograph 76 Green belite nest in center of broken
dinker. Energy dispersive X-ray analysis (EDXA)
indicates calcium, silicon, potassium, and traces of
chromium, magnesium, aluminum, sulfur, chiotine,
and iron.

Reflected light
FD = 1.25x1.25 mm

Photograph 77 Crushed clinkers with yellowish


brown centers, produced in a kiln with a reducing
environment. Examination at high magnification
reveals belite coatings on alite, dull ferrite refiectiv-
ity, and aikaii aluminate.

Polished section
No etch
FD = 1.2x1.2 mm
Matrix
obsemations lnteqmdations
Abundant aluminate Hiah Al,O? to Fe,O? ratio. AR (Gille. and others. 1965)
Abundant aluminate, abundant ferrite Low AlzOl to Fez03 ratio, less than 0.7 (Gille, and others, 1965)
Plenty of liquid phase Silica ratio (SR) low (Hofmanner, 1973)
Aluminate greatly dominates liquid phase High AR (Long, 1982a); strong reducing conditions (Dorn, per-
sonal communication, 1985)
Aluminate greater than ferrite AR high (Hofmanner, 1973)
Ferrite greater than aluminate AR low (Hofmanner, 1973)
Large quantity of liquid phase, high ferrite content Low SR and AR (Long, 1982a)
Great relative increase in aluminate content Cooling under reducing conditions and temperature range
between 1OOOY and 1200C (Sylla, 1981)
Small auantitv of liauid chase. dustv fine clinker Hiah SR (Lana. 1984b)
Low quantity of melt phases High silica modulus (Miller, 1980); SR too high (Hofmanner,
1973)
Differentiation of interstitial aluminate and ferrite; alite and belite Equilibrium cooling to complete crystallization through 1250C
lose sham reoularitv (Brown. 1948)
(a) Groundmass structure of large crystals (a) Extended conditions for development
(b) Tight, interlaced structure of small crystals (b) Quenching (Gille, and others, 1965)
Coarse structure of aluminate and ferrite: belite frinaes on alite Verv slow coolina (Lona, 1982a)
Large separated ferrite and aluminate crystals surrounded with Reducing conditions (Brugan, 1979)
normal matrix; brown areas in clinkers
Coarsening of aluminate crystals, aluminoferrite, and belite; Clinker burned under reducing conditions, removed from kiln
increase in aluminate at expense of aluminoferrite at temperature less than 1250C slow cooling under reducing
conditions (Sylla, 1981)
Aluminate growth at expense of aluminoferrite; additional metal- 1 -hour bum in reducing atmosphere, cooled to 1050C in kiln
lit iron; large, irregularly shaped beliie crystals (Sylla, 1981)
Simply bounded, rectangular aluminate and bright ferrite Slow cooling (Brown, 1948)
Coarsely crystalline liquid phase Slow cooling (Hofmanner, 1973)
Microcrystalline matrix; two distinct phases: ragged alite (belite Slow cooling rate (Fundal, 1980)
coating) and irregular belite; prismatic aluminate
Large aluminate (CA) crystals Extremely slow cooling; fast-setting cement (Eby, 1985)
Microcrystalline matrix: primary, aluminatelike gray phase; set Intermediate cooling rate (Fundal, 1980)
ondary ferritelike white phase, containing third interstitial phase
with lower reflectivky, possibly aluminate
Fine structure of aluminate and ferrite Rapid cooling from high temperature (Long, 1982a)
Finely crystalline liquid phase Fast cooling (Hofmanner, 1973)
Submicroscopic crystals in matrix; rectilinear alite, sometimes Fast cooling rate (Fundal, 1980)
with thin layer of belite; spherical matrix belite
Increasing CJA crystal size and number; change in etch color Clinker drops out of kiln at successively lower temperature from
maximum of 1500C (Hawkins, 1979)
Cryptocrystalline aluminate, ferrite, and periclase in matrix (seen Very rapid cooling (Hofmanner, 1973)
with SEM)
Rodlike (somewhat dendritic) intergrowth of groundmass Relatively rapidly cooled clinker (Gille, and others, 1965)
phases
Separation of matrix phases, ferrite and aluminate, but without Reducing conditions, quenched, lab experiment; melt rich in
typical eutectic intergrowths; content of free lime high; alite silica, poor in lime; resorption of belite which was prevented by
coated with thin ferrite seam, then by thick belite cover quick cooling (Woermann, 1960)
Same texture as aircooled clinker with distinctly recognizable Clinker burned under oxidizing conditions, removed at tempera-
aluminate and aluminofenite ture of 1250C and below, and quenched in water (Sylla, 1981)
Mottled interstitial phases Burning time too short, and temperature too low (Brown, 1948)

76
Matrix (continued)
0-N lntmprdations
Submicroscopic crystalline liquid phase (apparently undifferen Laboratory quenching (Hofmanner, 1973)
tiated with microscope)
Xenomorphous, void-filling aluminate Low alkali clinker (Gille, and others, 1965)
Zoned aluminate Changing chemical environment during crystallization (Hof-
manner, 1973)
Nonprismatic dark interstitial Low mortar strength (Tsuboi and Ogawa, 1972)
Alkali aluminate; alkali-modified belite Excess alkali over equivalent sulfate (Long, 1983)
Alkali aluminate Alkalies, mainly sodium, in clinker (Hofmanner, 1973); more
pronounced with NazO-bearing laboratory clinkers than in K,O.
bearing clinkers: neqative effect on cement properties (Dreizler,
Strung;, and Knofec 1985)
ldiomorphous laminae or long staves (prismatic) alumi- Alkali aluminate and relatively high-alkali clinker (Gille, and
nate others, 1965)
Prismatic C,A (alkali modified) Reducing conditions (DeLisle, 1979; Rader, 1985)
Alkali-modified lath-shaped aluminate Slow cooling or reoxidation (Long, 1982b)
Ragged, dark interstitial; dark prismatic phase prominent Rapid cooling: high alkali clinker (Brown, 1948)
Disappearance of prismatic aluminate; decline of mortar MgO more than 1% (Tsuboi and Ogawa, 1972)
strength
Brown aluminoferrite Absence of MgO in aluminoferrite, presence of divalent iron
(Sylla, 1981)
Dark brown-yellow, strongly pleochroic ferrite Normal clinker (Gille, and others, 1965)
High reflectivity of ferrite, eutectic intergrowth of ferrite and alum Normal, oxidized clinker (Woermann, 1960)
inate, no decomposition of alite
Lower reflectivity of ferrite; aluminate increases; no massive Equilibrium through slow cooling under reducing conditions
belite seams around alite (Woermann, 1960s
Massive ferrite Quick cooling (Long, 1984a)
Zoned ferrite crystals with earliest formed (inner) zones having Disequilibrium during crystallibation (Glasser, 1979)
different A/F ratios
Local concentrations of ferrite Possible coarse mill scale (Long, unpublished ICMA presenta-
tion, 1984)

PhotomicrographsIllustratingtheMatdx
Photograph 78 Brown, coarsely crystalline alumi-
nate in slowly cooled clinker. Belite crystals exhibit
short lamellar extensions into matrix. Coarse raw
feed. High maximum temperature, long burning
time, slow heating rate, quick to moderately quick
cooling. Coal-fired, wet-process Mln, 633 tons/day,
6000 psi (41.4 MPa).

Polished section
KOH etch
FT.) = 0.21x0.21 mm
Photomicrographs IlIustmting the Matrix (continued)
Photograph 79 Secondary coating of belite on alite
in very dense,coamely qstalline, mat&&h clinker.
Mati is well-differentiated gray aluminate and dull-
refletig fenite. Clinker breaks with subconchoidal
fracture. Peridase uystals (not shown) up to 120
pm. High maximum tempemture, slow heating rate,
reducing conditions. Coal-fired, wet-process kiln.

Polished section
Ni etch
FIB = 0.14x0.14 mm

Photograph 80 Multicolored, round ii-ee lime uys-


tals in alumhmterich mati (dull gray). Estimated
Cd = 14% to 18%. Anhedral to subhedral, tan to
bluish red alite. High maximum temperature, long
burning time, moderately slow heating rate, moder
ately fast cooling rate, 5800 psi (40 MPa). Coal-
fired, dry-process Mln, 1600 tons/day.

Polished section
Nii etch
FD = 0.21x0.21 mm

Photograph 81 Ultrathin section, approximately 10


pm tbidq shawing tan to beige aluminate (C+)
uystals comprising most of the matrix in thii clinker.
Round belite uystals, angular alite crystals.

Transmitted, plane-polarized light


FD = 0.14x0.14 mm
Photograph 82 Well-differentiated matrix of bright,
lath-form crystals of fenite between which the aium-
inate (Cd) occurs. Small, bluish green beiiie uys-
tais tend to be irreguiady shaped. Gas-fired wet-
process kiin, 770 tons/day. High maximum tem-
perature, long burning time, moderateiy slow heat-
ing rate, quickly cooled.

Polished section
Nil etch
FD = 0.21x0.21 mm

Photograph 83 Strongly pleochmic red fenite in


clinker containing partially consumed chmme-mag-
nesia refractory brick (not shown). Beiite with abun-
dant exsohred impurities. Beiite uystais in other
parts of this clinker are pale green.

Thin section
Transmitted, plane-polarized light
FTJ = 0.21x0.21 mm

Photograph 84 Thin, typical lath-form uystais of


fenite and extremeiy fineiy microuystaliine crevice-
filling aluminate (Cfi). Clear, anguiar aiite aystais
stacked on the basal pinacoid (001). Coal- and coke-
fired, semidry-process kiln, 1850 tons/day. High
maximum temperature, long burning time, slow
heating rate, quick to moderately quick cooling,
8390 psi (44.1 MPa).

Ultrathin section
Transmitted, plane-polarized light
Thickness = approximately 10 pm
FD = 0.21x0.21 mm
Pholmnicrographs Illustmting the Matrix (continued)
Photograph 85 Same fkid of view as previous pho-
tograph but in partiaiiy crossed poiam. Note rein-
tiveiy high interference colors of some fenite
crystals.

Photograph 86 UbatJdn section of clinker of dinker


showing lengthy aikaii aluminate prisms in matrix.
Angular aiite and clear, round beiite. Coarse, akaii-
rich feed. Low maximum temperature, long burning
time, medium to slow heating rate, quickly cooled;
slight redudng conditions. Dry-process kiln, 1440
tons/day.

Section thidmess approximateiy 12 w


Oblique iiiumination
Transmitted, plane-polarized light
FD = 0.14x0.14 mm

Photograph 87 Pdsmatic alkali aluminate uystais


in crushed dinker powder mount. High maximum
temperature, long burning time, slow heating rate,
moderately quick to moderately slow cooling rate.
Gas- and coai-fired, wet-process idin, 500 tons/day.

Transmitted, plane-polarized light


FD = 0.21xo.21 mm
Photograph 88 Brown prismatic (alkali-rich) alumi-
nate crystals, some entrapping alite and appearing
zoned or twinned along a prism face. Dry-process
kiln.

Polished section
Water etch
Diameter of field = 0.12 mm

Photograph 89 Alkali aluminate aystals (arrow)


exhibiting typical prismatic form. Brightly reflecting
ferrite in the matrix Blue, subhedral alite crystals.
Area shown within brown core of clinker probably
represents reducing conditions. Porous shell on
clinker contains normal CzA. Moderately high maz-
imum temperature, long burning time, slow heating
rate, moderately quir4dy cooled.

Polished section
Nital over KOH etch
FD = 0.1ozo.10 mm

Photograph 90 prismatic alkali aluminate (light


tan) in matriz in which the ferrite displays a dull
reflectivity. Thin belite coatings on many greenish
blue alite crystals. Clinkers commonly exhibit brown
areas. Moderately reducing conditions are inferred.
Coal-and coke-fired, dry-process kiln.

Polished section
Nitd on KOH etch
FD = 0.21zo.21 mm
Photograph 91 Dark prismatic alkali aluminate
(amw) in gas- and coaMred dinker from wet-
process tin. Slightly reducing conditions. High
maximum temperature, long burning time, slow
heating rate, moderately quick to moderately slow
cooling. 500 tons/day.

Polished section
Nital over water etch
FD = 021x0.21 mm
Free Lime
o-ons lnteipr&ations
Decrease in freelime percentage Correlated with increase in burning temperature (Akatsu and
Monna, 1986)
Increase in freelime percentage Correlated with increase in particle size of quartzite, slag, and
limestone (Akatsu and Monna. 1966)
Free lime as primary phase; belite only as inclusions in alite High LSF (Long, 1%2a)
Dispersed free lime, low belite content Overlimed mix, high LSF (Miller, 1980)
(a) Equal distribution of free lime (a) CaO content too high
(b) Local free lime (b) Incomplete absorption of limestone in raw mix
(c) Uniformly distributed free lime in clinker with high porosity (c) Low burning temperature (Gille, and others, 1965)
Spherical grains of free lime High temperature equilibrium (Brown, 1948)
Clusters of free lime Pieces of raw mix, indicating fineness of grinding and uniformity
of raw mix (Brown, 1948)
Differentiated zones of high and low concentrations of CaO Insufficient homogenization of raw mix (Kramer, 1980)
Irregular distribution of free lime Inadequate homogenization of large calcite grains in raw mix
(Fundal. 1980)
Nodules of CaO, melt-rich nodule, alite dust, belite nodules Improper nodulation and not raw-meal inhomogeneity (Fundal,
1980)
Clusters of free lime and belite with almost rectilinear boundaries Large feed particles, limestone and quartz, respectively (Hof-
manner, 1973)
Freelime cluster with sharp boundaries Calcite particles (Miller, 1980)
Intimate mixture of free lime and belite Sufficient excess alkali such that belite does not react to form
alite (Lona. 1983)
Freelime nests Local concentration of limestone (Tsuboi and Ogawa, 1972)
Free-lime cluster with open structure and small interstitial alite Marly grains (> 125 pm) (Fundal, 1980)
Dense freelime clusters Pure calcite oarticles (Fundal. 1980)
Free-lime nests Relics of limestone grains (Kramer, 1960); calcite above critical
size of 125 wrn (Johansen, 1978); coarse calcite (Long, 1984b)
Free-lime cluster with alite and liquid phase Concentration of carbonate component (local surplus of lime)
(Hofmanner. 1973)
Freelime nests and belite nests Quartz above critical size of 44 Mm in feed (Johansen, 1978)
Freelime nests near belite accumulations or many small pores Low burning degree (Gille, and others, 1965)
Nests of freelime or belite Coarse limestone, dolomite, or quartz, suggesting insufficient
grinding (Gille, and others, 1965)
Zones at Pores, for example, free lime on pore surface Reducing conditions; possiblyvolatization of silicon as Sii (Gille,
and others, 1965)
Central clinker region rich in lime, deficient in flux Occurs in high temperature reoxidation (Long, 1%2b)
Hoopstress cracks around free lime nests Expansion due to lime hydration, typical for aged clinker (Bru
gan, 1979)
Popcomlike secondary crystals associated with free lime Epezite, a form of calcium hydroxide, originating by air slaking of
free lime, leading to clinker disintegration (Brown and Swayze,
1938)

83
Photmmicrographs of Free Lime
Photograph 92 Free-lime nest colored bywater etch
in polished section. Chemical analysis gave clinker
free-lime value of 2.69%. High maximum tempera
ture, moderately long burning time, moderately
slow heating rate, moderately slowly cooled, 4490
psi (31.0 Mpa). Gas-fired, dry-process kiln, 3000
tons/ day.

FD = 0.21x0.21 mm

Photograph 93 Strongly zoned, tan allte wlth f+ee-


lime inclusions and round, coarsely lamellar belite
with tan cores. Coarse seashells in feed. Coal- and
cokofired, semlwet-process kiln, 1850 tons/day,
6390 psi (44.1 MPa).

Polished section
Nltal etch
FD = 0.21x0.21 mm

Photograph 94 F-lime nest from coarse calcite


particle In raw feed. Very low liquid phase. Coal- and
coke-flred, dry-process kUn. Moderately high maxi-
mum temperature, long burning time, moderately
fast heating rate, quick cooling rate.

Polished section
Water etch
FD = 0.53x0.53 mm

84
Photograph 95 Free lime in clinker thin section.
Crystais exhibit prominent cubic cleavage chaqc-
te&t.ic of free lime. An abundance of free-lime nests
(some showing original limestone partide outline),
anhedral aiite, and extremely nonuniform distribu-
tion of silicates suggests poorly mixed coarse feed.
Dty-process Mln, coal fired.

Transmitted, plane-polarized light


FD = 0.21xo.21 mm

Photogaph 96 Clear popcomlike aystais of epe-


zite, Ca(OH)z, floating in refractive-index oil. A pro-
duct of air slaking of free lime, the 97% change in
crystal volume results in clinker disintegration, even
in sealed containers. Gushed clinker, 44 to 75 pm.

Transmitted, plane-polarized light


FD = 0.21x0.21 mm

Photograph 97 Cauliflowerlike cyst& of epezite,


Ca(OH)z, floating in refractive-index oil. Note green
alite, perhaps related to chromium contamination
as a result of refractory consumption. High maxi-
mum temperature, long burning time, slow heating
rate, and quickly cooled. Coal-fired, wet-process
kiln.

Transmitted, plane-polarized light


FD = 0.21x021 mm
Observations Inteqwetations
Periclase More Mg than can be incorporated in lattices of other phases
(Hofmanner, 1973). Crystallized from melt or residual from raw
mix (Brown, 1948). MgO concentration greater than 2% in total
clinker or locally (Ciille, and others, 1965)
Relatively low C,S content and high periclase; improved crystal- Effects of slow cooling in laboratory test. Suggested remedy is
linity of CJA; unsoundness at MgO of 4.0% with C,A greater than to lower alumina modulus and increase fineness of cement
7% (Chopra, and others, 1982)
Relatively large periclase in liquid phase; large, clustered, silicate Effects of slow cooling in lab test; similar interpretation for com-
crystals with less defined boundaries; irregularly shaped CS; 8% mercial clinkers (Chopra, and others, 1982)
to 30% drop in 28-day strength
Large number of periclase crystals in high MgO clinker Slow cooling of clinker (Gouda and Bavles, 1981)
Small number of periclase crystals in high MgO clinker; retention Quick cooling (Gouda and Bayles, 1981)
of MgO in silicate and interstitial-phase solid solutions
Large periclase High temperature and slow cooling (Long, 1982a); slow cooling
(Hawkins, 1979)
Periclase departure from perfect octahedral form, developing Nonattainment of high temperature equilibrium (Brown, 1948)
skeletal, lacy, or large intricate designs
ldiomorphic periclase Slow cooling (Hofmanner, 1973)
Dendritic periclase Rapid cooling (Hofmanner, 1973); rapid cooling from above
1400C (Hawkins, 1979)
Dendritic periclase associated with belite, also dendritic Slow cooling from high temperature and coprecipitation of
phases (Hawkins and Havden, 1976)
Periclase resorption into alite Variations in burning conditions (Gille, and others, 1965)
Periclase with high reflectivity and low polishing hardness Wustite in solid solution with periclase (Woermann, 1960)
Wide areas of secondary periclase and autoclave problems Coarse coal particles, high MgO raw mix (Hawthorne, Richey,
and Demoulian, 1981)
Lime nest with periclase Dolomite particle (Gille, and others, 1965)
Periclase nest with free lime Coarse dolomitic limestone (Long, 1982a)
Small periclase crystals with free lime Dolomite grain (Fundal, 1980)
Open cluster of periclase plus free lime nest with interstitial peri- Large dolomite, depending on local surrounding chemistry
clase (Fundal. 1980)
Large crystals of CaO and MgO Volume unsoundness (Kramer, 1960)
Crystals of +45 to -63 pm size range. Greater autoclave expansion than that with equal amount of -90
pm periclase (Goswami, Mohanty, and Panda, 1984)

86
Photomicrographs of Periclase
Photograph 98 Dendritic periclase forming sub
8t.mt.e for belite overgmwth (center left). Alite uys
tals exhibit facial extensions into matrix of very
finely microuystalline aluminate and ferrite. Slowiy
cooled from high temperature.

Polished section
Water etch
FD = 0.14x0.14 mm

Photograph 99 Marked topographic relief produced


on polished section by IO-set nital etch followed by
1 0-set application on Texmet with 0.05yun alumina.
Note dendritic periclase (pinkish gray in matrix) and
silicate zonation. High maximum temperature, mod-
erately long burning time, slow heating rate, and
slow to moderately slow cooling. Coke- and coai-
fired, dry-process kihr, 918 tons/day.

FD = 0.95x0.95 mm

Photograph 100 Ultrathin section showing den-


dritic periclase within irregular belite crystals (cen-
ter and upper left). Section thickness is approxi-
mately 10 fim. Coal-Rred, wet-process kiln, 444
tons/day. High maximum temperature, long bum-
ing time, moderately slow heating rate, and moder
ateiy fast cooling rate.

Transmitted, plane-polarized light


FD = 0.21x0.21 mm
Miscellane!ous
observations Intapretatkms
Metallic iron Residual from pyrite cinder (Brown, 1948)
Iron metal Very strong reducing conditions, lack of air (Gille, and others,
1965)
Wustite (FeO) Clinker rich in iron, very rapid quenching (Gille, and others,
1965)
Iron sulfides Reducing conditions (Gille, and others, 1965)
Calcium sulfide Slight reduction (Gille, and others, 1965)
Calcium sulfide dendrites Reducing atmosphere (Gille, and others, 1965)
Dendritic calcium sulfide Reducing atmosphere (Kramer, 1960)
K, Fe sulfide Reducing conditions (Gille, and others, 1965)
Formation of calcium sulfide and KFeS More extreme reducing conditions (Long, 1982b)
Unburned fuel (coke, graphite) Reducing conditions, lack of air (Gille, and others, 1965)
Alkali sulfates Increased early mortar-cube strength, decreased late strength
(Jons, 1981)
Halo of unetched phases around central sulfate deposit Characteristic for alkali sulfate deposits in clinkers (Pollitt and
Brown, 1988; Long, 1984a)
Deliquescent alkali oxide associated with aluminate phase Dissociation of alkali sulfates or alkali-calcium sulfates in reduc-
ing environment (Long, 1982b)
Calcium langbeinite in interstitial phase Excess sulfate over equivalent alkalies (Long, 1983)
Anhydrite in laboratory clinker voids, bonded to aluminate Sulfaterich raw mix with SO, greater than 2.3% (Dreizler,
and ferrite Strunge, and Knofel, 1985)
Glassy spheres containing Si, Ca, K, and Ti in clinker Wet process, 90% fuel oil and 10% combustible material contain-
ing titanium in feed (Hawthorne, l&hey, and Demoulian, 1981)
Gehlenite glass Severe local decrease in CaO (Gille, and others, 1965)
Glass in matrix Impossible to establish microscopically with certainty; very
unlikely in normal plant clinker (Hofmanner, 1973)
Fine silica intimately dispersed in limestone (cement rock) Easily burned, even if as coarse feed (Long, 1982a)
Coarse, very acidic or very basic particles in heterogene- Generally requires increases in burning temperature (Long,
ous feed 1982a)
Increases in LSF, SR, AR; increase in combinability tem- Result from burning in reducing environment (Long, 1982a)
perature
Higher burning temperature required for adequate combina- Coarse raw feed (Long, 1982a)
tion; increase in alite crystal size
Increase in SR, decrease in melt volume Results in decrease in power for grinding, providing that small
crystals are produced and that the clinker is not dusty (Petersen,
1980)
Air-setting of cement during storage, poor workability Alkali-water combination, alkalies developed upon quick cooling
of reduced clinker (Long, 1982a)
Relatively rapid set of cement Clinker burned and cooled under reducing conditions; highly
reactive, well-crystallized, more abundant CA, slowly cooled
(Sylla, 1981)
Relatively high 28day mortar strength Clinker burned in oxidizing atmosphere (Sylla, 1981)
Decrease in 28day mortar strength Excess carbon or sulfide in raw feed clinker burned and slowly
cooled in reducing atmosphere (Sylla, 1981)
Depression of 28day strength; premature stiffening; loss of Reducing conditions, slow cooling (Long, 1982b)
workability: cement flowability problems; silo blockages; lighter
colored cement
Increase in aliie and interstitial percentage; decrease in Correlated with decrease in 28-day mortar strength (Akatsu,
belite percentage Monna, and Maeda, 1965)
Miscellaneous (continued)
obselvations lnterpntations
Increase in free lime and belite percentages; decrease in aliie and Correlated with increase in porosity (Akatsu, Monna, and Maeda,
interstitial percentages; decrease in alite size 1965)
High proportion of biogenic material, negligible matrix, small Ideal limestone raw material for high degree of burning (Gott-
amount of organic substances; compact microstructure hardt and Wilder, 1981)
Increasing consumption and premature failure of basic brick in Poor raw feed composition and unifon-nity, resulting in excessive
burning zone, difficulty in forming coating and fluctuating burning temperatures (Chen, Conjeaud, and
Lehoux, 1985)
(a) Fast-setting cement, small C3S crystals, faster cooling rate, (a) Oil-fired cements
potassium in K2SOs (b) Gas-fired cements
(b) Fast-setting cement, higher porosity resulting in higher water (c) Ash-rich coal (Philipp, and others, 1981)
demand and changing viscosity
(c) Lower initial hydraulic activity and hardness, higher long
term hardness, higher C2S, and decrease in grindability

Photomicrographs of Miscellaneous Phases


Photograph 101 Dark alkali sulfate deposits on wall
of void now fllled with epoxy. Coal-fired Mln, wet
process. High maximum temperature, long bum-
hg time, slow heatJng mte, quiddy cooled, 6030
psi (41.6 MPa).

Polished section
No etch
m = 0.21xO.21mm

Photograph 102 DadmUmlisulfateaspomandchan-


nel R&ngs (amter and left center). Remainder of
pore is filled with epoxy. XRD analysis indicates
arcanite and aphthitalite. Coal- and coke&xxi kih~,
wet process, 920 tons/day. Moderately high maxi-
mum temperature, moderately long buming time,
moderately slow heating rate, quiddy cooled.

Polished sectJon
No etch
FD = 0.21xo.21 mm

89
Phases (continued)
photograph 103 Dark alkali sulfate in clinker void.
prominently zoned alite. Cleatiy defined lamellae in
relathrely small, round belite. Low maximum temper-
ature, long burning time, slow heating late, slow
cooling rate, reducing conditions.

Polished section
f?nal polish with mixtune of 0.05 brn, alumina iso-
propyl alcohol, and propylene glycol
FD = 0.21x0.21 mm

Photograph 104 Thin section view of alkali sulfate


(-4 as pattial filling of void. High maximum
temperature, moderatety long burning time, slow
heating rate, slow to moderately slow cooling. Four
stage preheater dry-process kiln, coal- and coke-
fired, 918 tons/day.

Transmitted, plane-polarized light


FD = 0.14x0.14 mm

Photograph 105 Alkali sulfate deposits (arrows) in


clinker voids. Clinker SO3 = 1.12%. Moderately high
maximum temperature,, moderately long burning
time, slow heating rate, moderately slow cooling
rate, 4812 psi (33.2 MPa). Coal- and coke-fired, wet-
process kiln, 950 tons/day.

Thii section
Transmitted, plane-polarized light
FD q 0.21x0.21 mm
Photograph 106 Alkali sulfate stained purplish red
with a &i(&-K!%lO4 solution.

Clinker powder, 44- to 75-q liaction


Transmitted, plane-polarized light
FD = 0.21xo.21 mm

Photograph 107 Isotropic glass ma&ix (arrows) in


clinker formed at nearmelting temperature. Belite
shows prominent lamellar extensions; fen&e is red
and strongly pleochroic. Numerous exsohred dots in
belite.

Thin section
TIiinsmitted, plane-polarized light
FD = 0.21xo.21 mm

Photograph 108 Polished section of clinker paiticie


after KOH-sugar solution extraction, leaving partly
uystalline material (arrow) and brightly reflecting
residual ferrite (center).

Nital etch
FD = 0.21X0.21 mm
Photograph 109 Kiln feed in thin section. Multi-
colored partides are grains of limestone (calcite).
Gray quartz in center. Brown shale partides indi-
catedwitharrows.

Crossed p&us
FD = 1.9x1.9 mm

Photograph 110 Feed particles in thin section. Gray


quartz (upper center), microuysMline limestone
(left center and bottom right), and dark shale
(center).

Pabtiauy crossed polaM


m = 0.6oxo.60 mm

Photograph 111 Kiln feed containing coarse parti-


des of sandstone in which miuwAne feldspar
(showing @d twinning) is common and presumably
a source for potassium in the clinker. Fine particles
of limestone comprise most of the feed.

Thin section
crossed $mlam
FD = 0.53x0.53 mm

92
Chapter 8
Miiinterpretations in Clinker Microscopy
After several years of practice in making and studying thin Etching and staining should be consistently timed. Micro
sections and polished sections, one gradually develops an scope light intensity and use of filters should also be
ability to discern quickly the differences between artifacts employed consistently. Use of a sonic cleaner is also
of preparation technique and properties of the specimen advisable, but, even so, lint from the polishing cloth or
examined. Unfortunately, misidentifications caused by concentrations of dried polishing debris may remain in
cracks, scratches, holes, pits, and other surface irregulari- clinker pores. Grinding or polishing powder that dries in
ties (as well as interference from residual liquids used in clinker pores is almost impossible to remove. Therefore,
the grinding, polishing, etching, and cleaning) are com- temporary storage of polished sections in a shallow tray of
mon in the published literature of clinker microscopy. The propylene glycol between grinding and polishing steps is
writer has found that only with methodical patience, and recommended to keep the section surface from drying.
with the proper equipment, can a perfect polished section
or thin section be produced. If the proper procedure is
followed the first time, returns to the preparation sequence
are rare and, consequently, hours spent trying to interpret
a misidentification are few.
Photomicrographs 112 through 122 illustrate some of
these artifacts and will help the beginning clinker micros-
copist to discriminate actual clinker properties from the
effects of sample preparation. Some problems, however,
are not easily solved. For example, interference of exuding
polishing or cleaning liquids with etching media may lead
to halo patterns of discolored or unetched crystals
around clinker pores and absorbent phases. Poorly under-
stood chemical reactions may create whiskers near
pores. Polishing vehicles must be chemically pure or, at
least, the impurities must not react with any of the clinker
phases. Ethanol denatured with methanol is not recom-
mended (Prout, letter, 1984). Water is a common delete
rious contaminant in isopropyl alcohol used for both a
polishing vehicle and cleaning solution. Drying with moist
air (as from a house air line) may lead to a patchy pattern of
discoloration, some of which could be caused by oil,
grease, water, or other impurities. Cracks and gaps
between phases typically contain polishing powders or
pastes. Scratches are particularly troublesome. A few
coarse particles producing scratches during final polish-
ing will quickly ruin an otherwise perfect section.
One should not, therefore, immediately draw the con-
clusion that a clinker phase is particularly reactive if its
freshly polished surface exhibits a slight etch or stain due
to impure polishing vehicles or cleaning solutions. Keep
ing the etchants at constant temperature is recommended
to eliminate that persistent question of temperature effects.

93
Photomicrographs of Artifacts
Photograph 112 Grinding pits remaining on hastily
polished surface of clinker appear somewhat lie
dark alkali sulfate.

Polished section
No etch
FD = 0.21xo.21 mm

Photograph 113 Exudation of polishing vehicle (pro-


pylene glycol) or cleaning medium (isopropyl alco-
hol) from an alite cleavage on polished section SW
face. The exudation could be misinterpreted as
chemical attack of the aKte uystal.

No etch
FD = 0.21x0.21 mm

Photograph 114 Etch halo around free lime nest


observed after NH&l etch ( W in text, Chapter 3).
The halo may be the result of etch interference by
liquid exuding f+om the porous free lime uystals and
neartrypo-.
Polished section
FD = 021xo.21 mm
Photograph 115 Residual liquid and halo (arrows)
from polishing, cleaning, or etching, extending
across aliie into blue belite nest.

Polished section
Nital etch
FD = 0.21x0.21 mm

Photowaph 116 Residual liquid fn>m polishing or


clean& sample and halo of unetched belite sur
rounding central pore. Liquid could be mismter
preted as free lie. Liquid eventually dried.

Polished section
Nitai etch
FD = 021xo.21 mm

Photograph 117 Nonuniform nital etch on polished


section. Cross-cutting stipes and patches in sil-
icates could be misinterpreted as st~ctural wuia-
tions or aluminate concentrations.

FD = 0.21x0.21 mm
Photemicrographs of Artifacts (continued)
Photogaph 118 Polished section showing polishing
me, ~robabty shallow suatches, extending across
three blue alite crystAs.

NM etch
m = 021xo.21 mm

Photograph 119 Unidentifkd, presumably organic,


uystals fonned on unetched Polished-section sur-
face, puhaps as a result of mixing of propylene
glycol, used as a polishing vehicle, and isopropyl
alcohol used in cleaning.

m = 0.21x0.21 mm

Photograph 120 Residual Polishing, deaning, or


etching liquids causing blotchy patterns (an-ows) on
blue alite aystals. Patterns removed after repolish-
ing and drying before etching. Well-differentiated
matrix of aluminate (QA) and ferrite is made dearly
visible by application of nital over a previous KOH
etch.

Polished section
FD = 0.21x0.21 mm
Photograph 121 Mer&rencebyr&dual liquid orair
bubble (anrnv) on nital-etched, polished clinker sup
face. Note ghost boundary (an-ow) transecting
several alite aystals but not visible on the matrix.

m = 0.21xo.21 mm

Photograph 122 Residual liquid inte&rence with


etch, produdng dark blobs (arrow) on silicates.

Polished section
KOH followed by nital etch
FTJ = 0.21x0.21 mm
Chapter 9
Scanning Electron Microscopy
Although this publication is not designed to portray details (Minnis, 1984) in which the mineralogy of a sandstone
of all the various methods and results of microscopical thin section is determined and expressed in volumetric
analysis, mention of some of the applications and possi- percentages; the method also provides an approximation
ble pitfalls of the scanning electron microscope (SEW of phase grain size and a graphical description of grain
and Electron Dispersive X-ray Analysis (EDXA) is appro- locations.
priate. Most of the SEM and microprobe studies to date The techniques of sample preparation described in the
have dealt with the general characterization of clinker following paragraphs are those used by the author.
phases, including their compositional variations. Among Clinker powder mounts for SEM-EDXA study are made
the recent articles describing use of the SEM in analysis of by scattering an alcohol-washed, 44- to 75-pm fraction of
clinker microstructure is the work of Gouda (1979a and crushed clinker on a thin film of fresh epoxy resin (plus
1980) in which the various clinker phases are identified hardener) on a glass microscope slide. The particles
and described in order to interpret the manufacturing stand above the general level of the epoxy film and, after
process. Other publications in this field are those of the epoxy hardens, can be subjected to repeated examina-
Yamaguchi and Takagi (1988); Regourd and Guinier tion with different refractive-index oils with cover glasses.
(1974); Skalny, Mander, and Meyerhoff (1975); and Using photographs (or marking the area of interest with
Cirattan-Bellew, Quinn, and Sereda ( 1978). The latter pub India ink) and knowing the orientation of the slide in the
lication emphasizes some of the possible problems in SEM-EDXA sample holder, a specific particle can be
SEM analysis, including preparation techniques, surface found again and analyzed. Thus the same particle is exam
charging, image distortion, phase abundance, and other ined with light and electron microscopy. Particles are also
factors. mounted directly on the stub for SEM study.
Use of the SEM and EDXA in this book has been Polished thin sections are also examined in transmitted,
primarily for phase identification, photography, and, in polarized light and, after etching for 15 to 30 seconds with
some cases, to gain specific compositional information. nital, certain areas are selected and marked with India ink
Much of the time spent with the SEM-EDXA has also been for SEM-EDXA. The thin section is then mounted on silver
for the purpose of developing sample polishing and etch- adhesive tape attached to an aluminum sample holder.
ing techniques to facilitate examination. A word of caution Colloidal graphite is painted over the tape and holder,
is given to workers who examine only fractured clinker covering all exposed areas except the sample. After drying,
surfaces with the SEM: Such surfaces may not present the the sample is carbon-coated (approximately 10 nanome-
observer with a representative cross section of the clinkers ters thick) in a vacuum evaporator. Elemental analyses are
many phases. Moreover, attention is too often directed to done with the thin section or powder mount at -10 to
well-formed crystals projecting into clinker voids, which +25 tilt, 15 to 25 keV, timed mode = 100 to 250 seconds.
are ideal places to study deposition of alkali sulfates on The problem of smearing over the polished-section
previously formed crystal surfaces, but are poor localities surface is not totally eliminated but appears to be minor.
for analysis of matrix-silicate relationships. The problem might be resolved by slight ion-beam
Used properly, the SEM-EDXA allows one to precisely etching.
elucidate some of the microstructural and compositional
details unseen with other techniques of microscopy. Rou-
tine application of SEM-EDXA to daily production prob
lems is not common. However, a semiautomatic SEM-
EDXA system for routine production quality control may
not be beyond the realm of possibility and practicality. A
computer-controlled method of SEM-EDXA already exists

98
Photograph 123 Semiconchoidal fracture surface
of dense, hard-to-grind clinker.

SEM
Length of Field (LF) = 182 q

Photograph 124 Angular alite and round belite


aystals. Boxlike pattern of fetrite crystals in center.
Sulfate-l-&stant cement clinker.

SEM
Fractured surface
LF=131pm

Photograph 125 Microcradrs in alite crystals in


fenite matrix.

SEM
Nitaktched polished section
w=7o@l
Scanniag Electron Plhoscopy (SEH) (continued)
Photograph 126 Euhedral alite uystals in dinker
void.

SEM
Broken surface
LF=70pm

Photograph 127 Nit&etched polished dinker sec-


tion showing tightly packed beIite in nest.

SEM
LF=131pm

Photograph 128 Nit&etched, broken surface of


clinker, revealing belite lamellar structure. Note
small be& indusion in alite crystal (left center).

SEM
LF=131pm
Photograph 129 Apparently fsatunless swfaces of
rrmnd beliteaystals onbroken dinker. Light-colored
ferrite.

SEM
LF=28w

Photograph 130 Belite uystal shawing lamellae on


outer surface and fenite deposit (white material).

SEM
L.F=28)cm

Photograph 131 Nitaktched polished dtier sec-


tion showing belite fringe on aiite (upper half) and
lamellar extensions of belite (lower border).

SEM
LF=46jun
scanning Electron Microscopy (SEM) (continued)
Photograph 132 Sulfate-resistant clinker, slowty
cooled and fenite-tich, showing belite lamellae ex-
tending into mat&. Gas-fired, wet-process kiln, 830
tons/day.

SEM
Nit&etched polished section
LF=70pm

Photograph 133 Nits&etched polished section show-


ing well-developed lamellae in belite crystals.

SEM
LF=7o@l

Photograph 134 Lamellar structure of belite re-


vealed after nital etch on polished section.
Photograph 135 Polished section of Class G, oil-
well cement clinker showingwidenonlamellarareas
in belite uystal.

SIN
20-sec. nital etch
LF=46pm

Photograph 136 Belite lamellae (anew) in alite and


belite footprint in 1 O-sec. nit&etched clinker pol-
ished section. Reducing conditions.

SEM
LF=7o@n

Photograph 137 Fe&eaysM boxworkexposedon


broken, nit&etched clinker surface. Note faintlyvis-
ible lamellar belite structure in upper right.

SEM
LF=28-
S&g Ekctmn Microscopy (SEM) (continued)
Photograph 138 Fe&teaystalsshowingtypicalhoL
low boxwork and lathlike uystal fomr.

SEM
Brokur surface of dinker
LF=28pm

Photograph 139 Polished se&on of dinker, show-


ing effects of 10+x. etch from water applied to
MiaDdothJel&sakmlinate(highlyiKegularfomls)
and ferrite (smooth surface) in sulfattx&stant
cement clinker. Scratches on alite uystals. Modes-
ately high maximum temperature, mod-My slow
heating rate, quickly cooled, 5392 psi (37.2 MPa).
Coal-fired, wet-process kiln, 1300 tons/day.

photogaph 140 Alkali aluminate aystals in nital-


etched dinker.

SEM
Brokm surface
LF=28pm

104
Photograph 141 Pollshed section of clinker with a
nltal etch (20 seconds) showlng a mdase skeleton
(arrow) wlthln bellte.

SEM
LF=7op

photograph 142 Mdase uystal amkist caldum


hydroxide, left and right, the latter resulting from
free-he hydration (alrslaklng).

SEPI
Broken dlnker surface
LF=l4@ll

Photograph 143 Caullflawuiike calcium hydroxide


aystals (presumably epezlte), from hydration of
free lime (air slaking), and round, gray peridase
uystals In a nest, suggesting coarse dolomite In the
feed.

SEM
Broken dlnker surface
LF=?O)un
Scanning l%sctron Microscopy (SEM) (continued)
Photograph 144 Calcium hydroxide aystals (pre-
sumably epezfte) growing on free-lime substrate in
clinker. Poxthndite crystal in upper center.

SEM
Broken surface
LF=70pm

Photograph 145 Calcium hydroxide aystals (pre-


sumably epezite) derived from free lime in dinker.
Indicative of air slaking.

SEM
Broken dinker suhce
LF=70-

Photograph 146 Round on


ah! clystal.

SE&l
Broken dinker surface
LF=28@

106
Photograph 147 Alite crystal with attached alkali
sulfates. LameMar structure in belite revealed in
upper right comer. 30-min. maleic acid etch on
crushed, sieved clinker.

SEM
LF=46q1

Photograph 148 Alkali-sulfate deposit on void wall


in nit&etched clinker polished section. EDXA
data (expressed in percentages) on bright ridges:
S = 36.0, K = 38.5, Ca = 25.4, Fe = 0.1; dark
pits between ridges: S = 37.8, K = 46.1, Ca = 14.9,
Fe = 0.4.

107
Chapter 10
Recommended Procedures and Materials
The suggested procedure for detailed clinker examination from the median clinker size, i.e., (16th - 64th) + 2
given in this chapter requires more observation than a = *s, assuming a population with a normal size
routine analysis would necessitate. However, answers to distribution.
many of the questions posed in the suggested procedure D. Microscopical description (powder mount, polished
have not been published, and, therefore, the outline may section, polished thin section). Each clinker phase is
point to some needed research that may have very practi- described in this recommended order:
cal consequences. For example, little is known about 1. Percentage (state method, such as point count, line
belite inclusions in alite (their size, abundance, and com- count, etc., if other than estimation with comparison
position) in relationship to burning conditions and raw charts).
feed characteristics. Crystal size distributions of most of
2. Occurrence and distribution pattern-uniformly,
the clinker phases in relation to feed characteristics are
randomly, or patchily distributed; occurrence near
also poorly known. In short, detailed quantitative studies of
or in pores, near certain other phases, clinker core,
phase varieties are needed, not only as subjects of scien-
shell, sharply bounded groups (nests) of crystals,
tific inquiry but also for the purpose of improving the
diffuse boundaries, and so on.
quality and extending the usefulness of portland cement.
3. Orientation of crystals-random or preferred, local
or general.
Suggested Procedure for 4. Crystal size-mode, extreme range, and gradation
(estimation of s as described above); unimodal or
Detailed Clinker Examimtion bimodal; comparison between clinkers. In order to
A. production date and time establish a classification and nomenclature for
.. clinker texture (that is, crystal size), the following
B. Examination date scheme is proposed, based on the average alite
C. Megascopic properties-hardness, color, porosity, crystal length:
shape; note variations in these properties within and Alite Cgstal Length Descriptive Term
between clinkers and establish predominant charac- (in micrometers)
teristics; agglomerated or single nodules.
<IO Extremely finely crystidline
Size uariation-if sieving is impractical, estimate the 1oto20 Very finely crystalline
following, in metric terms, from a random sample: 20 to 30 Finely crystalline
modal clinker size-the most frequently occurring 30 to 40 Medium crystalline
4oto50 Coarsely crystalline
diameter
5oto60 Very coarsely crystalline
extreme (100%) range-maximum and minimum >60 Extremely coarsely crystalline
sizes
16th and 84th percentiles-determine which clinker 5. Facial development on crystals-euhedral, subhe
diameter has 16 of the clinker diameters larger than dral, anhedral; areas of preferential development in a
itself . . . this is the 16th percentile diameter on a single clinker.
cumulative percentage curve. Next, determine which 6. Contact features-is phase indented by others, or
clinker diameter has 16 of the clinker diameters does it indent its neighbors?
smaller than itself . . . this is the 64th percentile
diameter. The difference between these percentiles *Modified after Folk, R. L., Petrology ofSedimentary Rocks, Hemphill
includes approximately k one standard deviation (s) Publishing Co., Austin, Texas, 1980, 184 pp.
7. Cleavage, fracture, or parting- how many cleavage
directions,intersecting at what angles and parallel to
which crystal faces? Are microcracks preferentially
oriented in the clinker? Do they exhibit phase
specific patterns?
8. Zoning and internal structure-note differences in
zonal birefringence and refractive index (on broken
crystals); twinning or crystal intergrowths; number
of sets of lamellae; lamellar width variations.
9. Refractive index, color, and pleochroism in trans-
mitted light; luster and color in reflected light
(without etch); characteristics in reflected light (oil
immersion); note variations within species.
10. Interference color, birefringence; straight or wavy
extinction; biaxial or uniaxial; negative or positive 2V;
dispersion in transmitted light
11. Etch or stain effects-consistent or variable within
individual crystals? Within clinker? Within species?
12. Inclusions-identify and describe each type with
above outline as completely as necessary: note size,
distribution among and within host crystals, and
abundance of each.
13. Freshness, alteration products, homogeneity of
decomposition or alteration within same species.
14. Definition of species varieties and description-for
example, raggedy, round, vs. dendritic varieties of
belite or euhedral, large periclasevs. anhedral, den
dritic periclase, and so on, and state relative abun-
dance and preferred locations of each.
15. Affinities and antipathies of occurrence-that is,
does alkali aluminate selectively occur in more por-
ous zones or is free lime preferentially associated
with periclase, and so on?
16. Age relations-is one phase being replaced or
attacked by others in cracks and voids; is it euhedral
against others; formed earlier or later?

Quan~eMicroscopy
Determination of the percentage of the various phases in
clinker can be accomplished by (a) visual comparison
with known (measured) clinker standards (Long, 1982a),
(b) visual comparison with percentage diagrams (Figure
5), (c) point counts, or (d) linear traverse. All techniques
require polished sections or polished thin sections. Point-
count procedures entail the identification and recording of
the phase under cross-hair intersections or dots in an
eyepiece reticle.
Hofmanner ( 1973) has clearly discussed the problem of
accurate determination of phase abundance and recom-
mends a point count of at least 4000 points on a polished
section of epoxy-encapsulated, crushed clinkers, using a
25point grid reticle placed in the microscope eyepiece.
According to Hofmanner, a competent microscopist can
count approximately 1000 points per hour with a distance
between points approximately equal to the average diame Figure 5 Compfuison chart for visual percentage
ter of the crystals. The following equation was given by estimation (after Teny and Chilingar, 1955).

109
Hofmanner (1973) to estimate the measuring error, A, in the clinker produced. Monitoring the free lime content will
point counting: suffice.
P(100 - P) Linear traverse methods, which record crystal chord
A = 2.0235 Eq.12 lengths and calculate volume and weight percentages as
J n
well as specific surfaces of alite and belite, have recently
where P = percent of points representing a given phase, been used to study clinker thermal history and grindability
and n = total number of points. (Scheubel, 1983). Quantitative microscopy, like that in the
This equation indicates that the measuring error previously mentioned paper, is greatly needed in clinker
changes only slightly after 4000 points have been tallied. analysis.
Semiautomatic tallying devices (multiple channel count- Hicks and Dom (1982) have shown the practicality of
ers) and automatic mechanical microscope stages are using a computer to calculate correlation coefficients
available to streamline the counting and make it less from Ono test data, stating The computer remains a
time-consuming. powerful tool for drawing correlations from masses of data
Confidence in using percentage diagrams for abun- and discovering new paths of usefulness as the program
dance estimates could be strengthened by combining matures.
point counts on the same clinkers until the microscopist Statistical methods were used by OKelly and Fortune
feels that his or her visual estimates are sufficiently accu- ( 1983) to relate microscopically determined silicate per-
rate, that is, within a tolerable range of error. For normal centages and clustering tendencies to grindability.
clinker investigations, however, a simple estimate, either Hargave, and others (1983) quantitatively related (a)
based on comparison with point-counted standards or phase assemblage (weight ratios), (b) stabilization of
percentage diagrams, will often suffice. Corroboration by phase modifications, (c) silicate crystal size, (d) silicate
XRD analysis can be quite helpful, especially with com- crystal morphology, and (e) clustering of phases to type of
puter-integrated systems. burning process (wet, semidry, and dry). Least square
Comparisons of statistical analyses of phase percen- linear regression techniques established some general
tages determined microscopically by various workers, trends in relation to compressive strength and showed the
laboratories, and techniques have been presented by the negative effect of phase clustering (Hargave, and others,
Chemical Commission of theTechnical Studies Commit- 1985).
tee of the Cement Industry (1978), a French organization.
The methods and principal conclusions from their anal-
yses are:
1. The sample is made from 5 kg of clinker, crushed in a
jaw crusher with a gap of 2 mm and screened on a
Microscopical Equipmen&
150-pm sieve. The fraction larger than 150 pm is Supplies, and Thin Section
used. Services
2. A polished section is etched with an ammonium Equipment needed for microscopy in a cement plant may
nitrate solution in a mixture of water and alcohol to range from only a polarized-light microscope required for
reveal the silicates, followed by a nital etch, which, in powder mount analysis to sawing, grinding, and polishing
turn, is followed by a sodium hydroxide solution etch equipment necessary for thin-section and polished-section
to reveal the interstitial phases. study. Two somewhat idealized lists of equipment are
3. Magnification is adapted to the dimensions to be given in Table 4. The Economy column in the table
measured, with 4000 points tallied. Chemical dissol- contahs only the minimum equipment for powder-mount
ution of clinkers with salicylic acid to selectively study and polished-section examination. The other
remove silicates and free lime, followed by removal of column also contains items for preparation of thin sections.
CA by sugar-water, results in a fairly good micro- Refractive-index oils are normally used in transmitted
scopic correspondence with the silicates but poor light. However, some oils, when continuous between the
correlations with aluminates and ferrite. polished section and the objective lens, utilizing reflected
light, reveal an amazing detail, especially in the clinker
4. Alite and belite percentages determined by micros-
matrix. Cedar-wood oil (R = 1.5 1) and a 100X objective are
copy are generally higher and lower, respectively,
than the values calculated by the Bogue equations. recommended for oil-immersion reflected-light studies.
Major errors in microscopical percentages of matrix For use in transmitted light, a set of refractiveindex liquids,
ranging from n = 1.40 to n = 2.0, will suffice for most
phases are due to small crystal sizes.
examinations. Many of these liquids are toxic and ade
Chromy (1983), utilizing a 2OOOpoint count on 22-mm quate ventilation is required.
diameter polished sections of a sieved crushed clinker A list of common permanent mounting media is given
sample, demonstrated the usefulness of the microscope in in Table 5, followed by names and addresses of some of
determining the mineralogical composition of clinker, the the companies specializing in commercial thin-section
data from which were related mathematically to clinker preparation.
and raw mix composition and cement strength. He con The use of X-ray diffraction (XRD) data can clearly be
eluded, If conversion constants linking the equilibrium supportive to microscopy in almost all materials investiga-
clinker composition and strength are determined, it is not tions. One obvious advantage of XRD analysis is that it is a
necessary to carry out the quantitative phase analyses of reliable mode of identification and quantification for

110
almost all of the major phases commonly seen in raw feed,
clinker, and cement. However, XRD analysis suffers one
Complete Lab Economy Lab
major disadvantage: It cannot tell you where, in the exam
ined mass of clinker, the belite is located or how the belite is Trim saw (150.mm diam., oil
coolant)
related to alite. XRD analysis can indicate the presence of lsomet saw
lsomet saw (Buehler) with
belite and, with some calibrated standards, the amounts of small flanges and all
belite polymorphs, but only the microscope can tell you available chucks
that the belite occurs mostly as decomposition of alite 3 Grinder-Polishers with 1 Grinder-Polisher with
extra wheels and Minimet 2 extra wheels or Minimet
crystals or that the belite occurs only as inclusions in alite. (Buehler), the latter with
XRD analysis may indicate the presence and quantity of slide holder for thin sections
more than trace amounts of free lime, but only micros- 2 Glass plates (3OOx3OOmm) 2 Glass plates (3OOx3OOmm)
copy will tell you that the free lime occurs within alite or that Vacuum impregnator
Epoxy and hardener and Epoxy and hardener and
the free lime is associated with periclase. The human eye polyethylene cups (several polyethylene cups
can microscopically detect phases that, because of their varieties of each)
small percentage or amorphous character, are not de Cyanoacrylate adhesive Cyanoacrylate adhesive
tected by XRD. Xf?D analysis, therefore, should be used in (Super Glue) (Super Glue)
Slide warmer
a corroborative manner with microscopy.
Polaroid and 35.mm cameras, Polaroid camera
Photography* is virtually essential in providing pictorial television, video system
evidence for the interpretations drawn from microscopical Hot plate
examination. A Polaroid-type camera is most convenient, Thin-section grinder*
producing photomicrographs quickly and easily for re- Thin-section cut-off saw*
ports. For projection screen presentation, a 35-mm color Oil coolant (lapping oil)*
slide is, thus far, unexcelled. Films such as Kodak Koda- Stereomicroscope
color II (W-1 00) Ektachrome 64, andVTlOO0 have been Polarized-light microscope Polarized-light microscope
Reflected-light Reflected-light
used satisfactorily by the writer for color photographs. (metallographic) microscope (metallographic) microscope
Tungsten 160 film is recommended by Dom (personal Petrographic slides Petrographic slides
communication, 1985); this slide film requires no filters. (46x24 mm) (46x24 mm)
llford Pan F film, in the authors opinion, is excellent for Diamond pencil or electric Diamond pencil or electric
engraver engraver
black and white photographs.
Cover glasses Cover glasses (several sizes)
One of the most effective means of quickly conveying
Refractive-index oils Refractive-index oils
microscopical information is through the use of a tele Mortar and pestle
Mortar and pestle
vision camera and monitor with which one can show a Alcohol (isopropyl) and Alcohol (isopropyl) and
wide range of clinker features while the audience, in a spray bottles spray bottles
sense, participates in observation and analysis. As a teach- Propylene glycol Propylene glycol
ing tool, television is unsurpassed. The television camera Acetone
and monitor, combined with videotape attachments, also Stage micrometer Stage micrometer
Polishing cloths and powders Polishing cloths and powders
provides a permanent visual data base for clinker compar-
Adhesivebacked grinding Adhesivebacked grinding
isons. And lastly, the computer, having already been
papers papers
proven adept at data analysis, may find routine application Sieves, 76.mm diam. Sieves, 76.mm diam.
in image and phase analysis, storing the visual data Hot air blower Hot air blower
acquired during an automatic linear traverse of a pol- Calculator Calculator
ished and suitably etched section. Vials and caps (15 ml) for Vials and caps (15 mL) for
powders powders
Sample jars and caps Sample jars and caps
Steel file (fine) Steel file (fine)

*For thin-section preparation


( 1) Propylene glycol may be substituted for lapping oil

Miapscopical Equi$xnent suppliers


Buehler Ltd. M&one G Associates
41 Waukegan Road 2820 South Michigan Avenue
Lake Bluff, Illinois 68044 Chicago, Illinois 60616
(312) 2956500 (312) 842-7100
Frank E. Fryer, Co. Microtec Development Lab
36 East Main Street P.O. Box 1441
Carpentersville, Illinois 60110 Grand Junction, Colorado
(312) 4266731 81501
(303) 242.5716
Hacker Instruments, Inc.
Box 657 Wards Natural Science
Fairfield, New Jersey 07006 Establishment, Inc.
(201) 2268450 P.O. Box 1712
Rochester, New York 14603
Hillquist, Inc.
1545 Northwest 49th Street (800) 962-2660
Photomicrographs in this publication were custom printed by Doug
Goddard, ASTRA Photo Service Inc, Chicago, Illinois. Seattle, Washington 98107
(206) 784-l 960

111
Table 5. Permanent Mounting Media Table 6. Thin-Section Sendces
Canada Balmam Resin, index of refraction n = 1.537. and Lakeside Cal-Brea Roberts Petrographic Section
70 (a synthetic resin, n = 1.54) available from most chemical and 1515F N. Kraemer Blvd. Service
petrographic supply houses. Anaheim, California 92806 1300 Monterey Pass Road
(714) 6304135 Monterey Park California
Meltmount, n = 1.539, 1.582, 1.662, 1.704 for grain mounts: 91754
Cargille Laboratories. Inc. Leonard J. Cannone (213) 2626246
Cedar Grove, New Jersey 07009 102-03 47th Avenue
(201) 2396633 Corona. New York 11368 San Diego Petrographics
(718) 4786242 27118 North Broadway
Hyrax, n = 1.71 to 1.715, for grain mounts and thin sections: Escondido, California 92026
Custom Research and Development Central Petrographic (619) 749-9272
8500 Mt. Vernon Road Service, Inc.
Auburn, California 95603 2514 Nicholson Drive Thresher & Sons, Inc.
(916) 8853341 Dallas, Texas 75224 Establishment Inc.
(214) 942.0644 2828 Regent Street
Quklanount, a medium-viscosity resin mixed at 2 parts powder to 1 Madison. Wisconsin 53705
part liquid, by volume, for grain mounts and clinker encapsulations: Hillquist, Inc. (608) 233.0297
F&on Metallurgical products Corp. 1545 Northwest 49th St.
P.O. Box 188A, Saxonburg Blvd. Seattle, Washington 98107 Rudolf Von Huene
Saxonburg, Pennsylvania 16056 (206) 784-l 960 Thin Section Laboratory
(412) 2651575 1555 East Walnut Street
National Petrographic Pasadena, California 91106
Epoxy Resins Service Co. (818) 792.1511
5933 Bellaire, Suite 112
Addite 506 Resin with Hardener HY-2964, low-viscosity, mixed
Houston. Texas 77081 Wards Natural Science
at 2 parts resin to 1 part curing agent for n = 1.56:
Ciba-Giegy Corporation (713) 661-1884 P.O. Box 1712
Mktg. Resins Division Rochester, New York 14603
Pacific PetroLabs l(800) 962-2660
Ardsley, New York 10502 8613 Easy Bird Road
(914) 4783131 P.O. Box 68 Western Petrographic
EpoxMe Resin with Hardener and Epo-Kwick mixed at 5 pans Mokelumne Hill, California 20 West Flores
resin to 1 part hardener, by weighf for n = 1.565 95245 Tucson, Arizona 85705
Buehler Ltd. (209) 286-l 650 (602) 7924348
41 Waukegan Road pioneer Thin Sections
Lake Bluff, Illinois 60044 12234 South 1840 East
(312) 2956500 Draper, Utah 84020
(801) 571-2476
Stsuem Epofix and Hardener, a low-viscosity medium mixed at 9
pans resin to 1 part hardener by weight (81 by volume), for 4
n = 1.57:
Frank E. Fryer, Co.
60 E. Main St.
Carpentersville, Illinois 60110
(312) 4266731

Armstrong C-4 Resin with Acthrator H-20, a low-viscosity medium


mixed at 4 parts resin to 1 part activator for n = 1.57:
Armstrong Products co.
P.O. Box 657
Warsaw, Indiana 46580
(219) 267.3226

S~UIT Resin (soluble in xyiene) with four-part kit


Ladd Research Industries, Inc.
P.O. Box 901
Burlington, Vermont 05461
(802) 862-5799

*For thin sections. whole grain mounts, clinker impregnations,


and encapsulations.

112
Chapter 11
Conclusions
The industrial application of the microscopical study of by the numerous research reports by Oriental microscop
portland cement and clinker is seen to be comprised of ists and the increasing use of the method in North Amer-
several fundamental and interrelated parts: (a) data- ica. The Ono method, however, is not the only technique
gathering, consisting of phase identification, description of kiln control through microscopy, nor is it a complete
of the phases and their mutual arrangements, measure analysis. The results of microscopy using the Ono
ment of crystal sizes, and estimation of phase abundan- method are almost always fortified by reflected-light
ces, (b) analysis, encompassing the correlation of micro- observations of polished sections. To challenge the
scopical data with raw-feed characteristics, burning con method, therefore, is also to question the theory, and one
ditions, and cement performance with and without admix- must be proficient in powder-mount microscopy in order
tures, and (c) prediction of clinker grindability, cement to make such a challenge. Proficiency is developed only
performance, and, perhaps most importantly, the formu- by diligent observational practice (eye-training).
lation of microscopical criteria for maintaining optimum Now that phase analyses with electron microscopy are
kiln conditions. available, one might foresee a routine, somewhat auto-
Routine clinker microscopy as an economical and mated microscopical basis for quality control. Computer
rapid method to control the quality of portland cement programs and equipment for automating simultaneous
should be obvious from the numerous observations and microscopical and chemical analyses of polished sec-
interpretations given on previous pages. Adherence to the tions do not appear to be beyond our reach and may,
methodological habits of patience and perseverance in indeed, already be employed on a day-today basis in
microscopy will sharpen ones ability, likely resulting in some plants. The utility, however, of computer-generated
those energy savings so frequently sought in cement data, like all data, is only as good as the quality of the
manufacture. interpretations. Consequently, the microscopist must
A choice between reflected-light or transmitted-light continue to serve in a role of objective verification, using
techniques for plant use may, of necessity, be made on the finely honed techniques of observation and inference
the basis of personal ease of application, tradition, equip to relate cause and effect.
ment availability, or other reasons. In the writers opinion, a Of major importance in future work is the quantification
combination of the two modes of analysis is best. and statistical treatment of microscopical data from syste
Reflected-light observations of polished sections of whole matic investigations. Unfortunately, some of the observa-
or crushed clinkers from the modal size class is recom- tions and interpretations presented in Chapter 7 (Micro-
mended for silicate crystal morphology, size, and internal scopical Interpretation of Clinkers) do not appear to be
structure and for matrix and void phase descriptions. founded in systematic experimental design or statistical
Transmitted-light observation of powder mounts (44- to analysis. Statistical measures to determine the degrees of
75-pm fraction) may be best for belite colors and apparent correlation and association of the observations, and their
birefringence of alite. relationship to the various physical and chemical causal
With quickly setting epoxy resins or similar materials, factors of the production process, are essential and
such as cyanoacrylate ester (Super Glue), and modem urgently needed for several very important reasons:
semiautomatic grinding and polishing equipment, pol-
ished sections can be made within a few minutes, while an 1. To quantify microscopical data in order to remove as
alcohol-washed, sieved clinker powder, mounted in refrac- much subjectivity as possible;
tiveindex oil, is studied. 2. To strengthen the science of clinker and cement
Onos theory, on which the Ono Method is based, microscopy in general, that is, to fortify the founda-
succinctly set forth in 1981 by Ono (pp. 200-204), tion with statistical rigor; and
appears to have a wide and growing acceptance, judging 3. To enable the microscopist to communicate pre

113
cisely with others who are interested in quality control
at the cement plant.
Because of the wide variety in types of kilns, and the
large number of possible equipment changes that may be
necessary to modify burning conditions, little has been
said in the present publication regarding these specific
operational modifications. As a result of data from
powder-mount study and polished-section examination,
Prout (1985) recommended the following production
process changes: location of burner pipe, feed rate, pri-
mary air, and the intergrinding of gypsum with kiln feed so
as to produce a molecular sulfur to alkali ratio of not less
than 0.8. Cement quality greatly improved after the pro
posed changes were made, providing a clear-cut illustra-
tion of the successful application of the microscope to
cement quality problems and, no less importantly, estab
lishing support from operational personnel. Other recom-
mended equipment changes related to the improvement
of clinker quality can be found in papers by Hansen
(1983) and Miller (1978).
Microscopical examination of clinkers that produce a
less-than-top-quality cement may not be able to determine
the entire cause of the cements inferior performance.
Cement particle size distribution, variations in crystal
chemistry, mineral and chemical admixtures, as well as
the effectiveness of the set-controlling material (normally
gypsum or similar minerals) may have stronger effects on
cement hydration than the clinker production problems
inferred by routine microscopy. Some cement problems
are simple and easily solved; others require the analysis of
a tangled set of multiple causes and effects. Microscopy,
however, should be one of the first steps in that analysis.

114
Glossary
anhedral. A crystal showing no crystal faces; syn. light vibration directions in the crystal. syn. refractive
xenomorphic. index (RI).
anisotropic. Material whose physical properties vary in isometric system. A crystal system in which the symme
different directions; in optical terms, the property of divid- try is characterized by four threefold axes as body diago-
ing light into two rays with differing velocity and direction nals in the cubic unit cell of the lattice; synonymous with
(double refraction); all crystals, except those of the isomet- cubic system. Crystal axes (a,, a2, a3) are of equal length
ric system, are anisotropic. Alite and belite are examples. and mutually perpendicular.
basal pinacoid. The crystal form that cuts off the pyra- isotropic. A material in which physical properties do not
mids (or rhombohedra) of alite. Basal pinacoids are parallel vary with direction; in optical terms, light rays pass through
to the lateral crystallographic axes and cut the c axis: a substance without dividing (that is, without double refrac-
designated (001). tion); isometric crystals and amorphous substances are
Becke line. A band of relatively high-intensity light, visible isotropic. Free lime is isotropic.
around or in nonopaque particles observed under the lamella. A thin plate, lamina, or layer; one of the units in a
microscope; apparent movement of the band during polysynthetically twinned mineral (such as plagioclase
focus adjustment relates to differences in indices of refrac- feldspar); or a unit within a set of lamellae in belite.
tion between the particle and adjacent liquid or solid lath. A crystal habit in which the crystal is long and thin
medium. and of moderate to narrow width; cross sections of platy or
biaxial. A crystal having two optic axes and three principal tabular crystals are lathlike.
indices of refraction; for example, a monoclinic, ortho- length slow. Certain anisotropic crystals in which the
rhombic, or triclinic crystal. slow vibration direction of light is parallel to the length of
birefrlngence. The difference between the greatest and the crystal; determined by use of accessory plates and
least indices of refraction of an anisotropic crystal. observation of interference colors.
monoclinic system. Crystal system characterized by a
dendritic. A branching pattern of crystallization; may single, twofold axis of symmetry; a single plane of symme
resemble a treelike form.
try; or a combination of the two: three unequal axes (a, b,
euhedral. A crystal on which the faces are well developed; c),, two of which are perpendicular and form a plane at an
syn. idiomorphic. angle (beta) to the third axis.
extinction. In crystal optics, darkening an anisotropic nest. A concentration of several crystals within a small
crystal four times during a 360 rotation in cross-polarized area; crystals may be tightly packed or loosely packed, the
light; darkening occurs when light vibration directions of latter nest exhibiting a relatively large amount of matrix
the crystal are parallel to those of the microscope polars. A between belite crystals, for example.
shadowy, nonuniform extinction, called undulatory, is optic axis. A direction in a crystal along which both
common in alite. refracted light rays travel at the same velocity.
form. A crystallographic body having all faces occupying orthorhombic system. A crystal system characterized
a similarly related position with respect to the planes or by three unequal, mutually perpendicular axes (a, b, c).
axes of symmetry. Forms are said to be open (for example, plane-polarized light. An electromagnetic wave in which
a prism) if they do not enclose space or closed (for exam the electric vector and the magnetic vector reach simul-
ple, a cube) if they do enclose space. Various closed forms taneous maximum and minimum intensities and vibrate
include octahedron, tetrahedron, dodecahedron, and oth- in mutually perpendicular planes.
ers; open forms include pinacoids, prisms, pyramids, and pleochroism. The ability or property of an anisotropic
others. crystal to absorb differentially various wavelengths of
hexagonal system. A crystal system characterized by transmitted light in certain crystallographic directions,
one unique axis of threefold or sixfold symmetry that is thereby showing different colors as the crystal is rotated.
perpendicular and unequal to three lateral and equal axes, Ferrite is pleochroic.
the latter mutually intersecting at an angle of 120; that polymorphism. The characteristic of a substance to cays-
group of crystals showing the threefold symmetry are, in tallize in more than one form, such as alpha and beta
some classifications, separated to form the trigonal quartz or alpha, alpha-prime, beta, and gamma belite.
system. Axes are labeled aI, az, a3, and c. prism. A crystal form having three, four, six, eight, or
idiomorphous. Describes a crystal completely bounded twelve faces, with parallel intersection edges, and which is
by crystal faces. Alite is typically idiomorphous. Obsoles- open only at the two ends of the axis parallel to the face
cent synonym for euhedral. intersection edges; prisms are closed by other forms.
index of r&action, n. A constant number equal to sine pseudomorph. A mineral whose outward crystal form is
of the angle of incidence(i) divided by the sine of the angle that of another species.
of refraction ( r): n = sin i/sin r, a relationship also known as pyramid. An open crystal form consisting of three, four,
Snells Law. The index of refraction is, in common usage, six, eight, or twelve nonparallel faces that meet at a point.
the inverse of the velocity of light within the studied mate An alite crystal is said to be constructed of pyramids (Maki,
rial. Subscripts such as e, o, E, 0, X, Y, or Z, etc., indicate Haba, and Takahashi, 1983).

115
Glossary (continued)
retardation. The path difference between two light
waves, referring to the fact that one wave has fallen behind
or advanced ahead of the other wave by a certain number
of whole or fractional wavelengths. Path difference is meas-
ured between similar points on each wave and has a
dimension of length (normally nanometers).
rhombohedron. A trigonal crystal form comprised of a
parallelepiped whose six identical faces are rhombs.
According to Ono, Kawamura, and Soda (1968) alite is
comprised of two rhombohedra.
scalenohedron. A twelvefaced crystallographic form in
the rhombohedral class of the hexagonal system. Each
face is a scalene triangle. Calcite commonly crystallizes in
this form.
subhedral. A crystal on which faces are incompletely or
only partly developed; syn hypidiomorphic.
tetragonal system. A crystal system characterized by a
fourfold rotation or rotary inversion axis of symmetry.
Three crystallographic axes (aI = a2, c) are mutually
perpendicular.
triclinic system. A crystal system characterized by three
axes (a, b, c) intersecting at angles of alpha, beta, and
gamma, none of which are 90; crystals in this system have
a onefold axis of symmetry.
Mgonal system. See hexagonal system.
twin. The intergrowth of two or more single crystals of the
same mineral, described in terms of crystallographic
symmetry (rotation axis, reflective plane, center). Twinning
is the development of a twin crystal by growth, transforma-
tion (as from higher to lower symmetry), or gliding (slip
along a crystal plane).
uniaxial. A crystal having one optic axis and two principal
indices of refraction; for example, a tetragonal or hexago
nal crystal.
vitreous. A type of material luster resembling that of
broken glass or china.
xenomorphous. A crystal showing no outward crystal
form (crystal faces); an anhedral crystal.
zoning. Variation in the composition of a crystal from core
to margin; may result from crystallographic or chemical
changes.

116
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124
AuthorIndex
Adams, A. E., 11, 117 Grade, K., 5 Matkovk, B., 25, 121
Adams, L. D., 7,39, 118 Gmttan-Bellew, P. E., 98, 119 Matzko, J. J., 11,21, 118
Ahluwalia, S. C., 45, 120 Green, G. W., 28,119 Mau, K. T., 31, 121
Aizawa, T., 39,117 Gregg, N., 3 McMurdie, H. F., 120
Akatsu, K., 51,60,83,88-89, 177 Groves, G. W., 25,119 McNabb, P. R., 45, 51, 55, 59, 123
All&g-e, R., 44,117 Guilford, C., 11, 117, 121 Meyerhoff, M H., 98,123
Amafuji, M, 28-29,117,122 Guinier, A., 24,26,28,98, 123 Midgley, H. G., v, 4,61, 121-122
Asakura, E., 40,117,122 Gutt, W., 24,29, 119 Miller, F. M, 44,52,59,76,83, 114, 121
Aspdin, J., 1, 3 Guttmann, A., 3 -4,119 Minnis, M M., 98, 121
Aspdin, Wm., 3 Haba, H., 23,51,53-54,115,121 Mizukami, K., 24,26, 123
Bailey, D. E., 5,45,51,55,59, 117, 123 Hansen, E. R., 44,52-53,114,119 Mohanly, S. K., 86,119
Bambauer, H. U., 43,54, 120 Hargave, R. V., 110, 119 Moir, G. K., 27, 121
Bayles, J., 86, 119 Hams, R., 18, 119 Monna, I., 51,60,83,88-89, 117
Blezard, R. G., 3, 117 Hawkins, P., v, 37,45, 76,86, 119 Moore, A. E., 22,121
Bogue, R. H., 22, 117 Hawthorne, F., 43,51-52,54,60-61,86, Morikoshi, H., 23,42, 121
Boikova, A. I., 23-24,117 88,119 Nagase, T., 26,124
Bozhenov, P. I., 54,117 Hayashi, R., 26, 124 Nagashima, M., 40,122
Brown, A W., 27.88.123 Hayden, K. L., 86,119 Naito, R., 30, 122, 124
Brown, L. S., 3-4,9-10,27,45,54-55, Heilmann, T., 43, 119 Nekhoroshev, A. V., 44, 118
76 -77,83,86,88,117 Heir&h, E W., 11, 120 Nurse, R. W., 4,122
Brugan, J. M., 45,52, 76,83, 117 Hicks, J. K., 6, 110, 120 Ogawa, T., 43,52,54-55,59-62,77,
Butt, Y. M., 4,42,53, 117 Hidaka, T., 26,31,51, 122 83,124
Bye, G. C., 27,42, 52, 117 Hofmanner, F., 5-6,22,42,44,51-55, OKelly, B. M., 110, 122
Campbell, D. H., 16,39,64, 117 59-62,76 -77,83, Okorokov, S. D., 52, 122
Carin, V., 22-23,25, 118 86,88,109-l 10,120 Okumura, T., 29,122
Carver, R. E., 8, 11, 117 Hoodmaker, F., 18 Ono, Y., v, 5-6,9, 14,20,22-26,29-34,
Caveny, W. J., 5, 10, 117, 123 Hornain, H., 6, 120 36-42,51-54,60-62,113,
Chen, H., 40,89, 118 Hutchison, C. S., 8, 11, 120 121-122124
Chilingar, G. V., 109, 124 Idorn, G. M., 3, 117, 120 Osborne, G. J., 24,119
Chopra, S. K., 5,45,60,86, 118, 120, 123 Imlach, J. A., 22,120 Panda, J. D., 86,119
Chlf;@ 6,22-25,37,42,54, 110, lnsley, H., 3,22-25,28,30,120 Parker, T. W., 4, 122
Johansen, V., 83,120 Petersen, I. F., 44,88,123
Conjeaud, M., 40,89, 118 Jons, E. S., 88, 120 Peterson, O., 29, 123
DeLisle, F. A., 24, 59,61, 77, 118 Jyo, Y., 44, 124 Philipp, O., 89, 123
Demoulian, E., 51-52,54,60-61, Kanai, Y., 31, 122 Pollitt, H. W., 27,43, 59,88, 123
86,88,119 Kato, K., 22-23,40, 121 Poole, A. B., 10,27, 123
Donaldson, C. H., 11, 121 Kawabata, H., 40,117 Prout, J.,v, 16, 18,38-39,61,93, 114, 123
Dorn, J. D., 6-7,10-l 1,24,39,41,51,53, Kawamura, S., 22 -23,30 -31,38 -39, Pyze, M. W., 29,123
55,59-62,76,110-l 11,118,120 52-54,60,62,120,122 Quinn, E. G., 98,119
Dreizler, I., 5, 51-53,62, 77,88, 118, 123 Kawashima, A., 38,124 Rader, T., 44, 77, 123
Eby, C., 43,76, 118 Kerr, P. F.,v, 11, 120 Randolph, J., v
Ellson, D. B., 8, 118 KhOlOoo~, L I., 54, 117 Rankin, G. A., 3,22,123
Entin, Z. B., 44, 118 KM&;, c1143,51-54,60,62,77,88,118, Rao, V. V. S., 5,60, 123
Fatal&, S. A., 53,118 Reeves, N. K., 5,45,51,55,59, 123
Fleischer,M., 11,21, 118 Kolenova, K. G., 43, 120 Regourd, M., 6,24,26,28,98, 120, 123
Folk, R. L, 108,118 Kono, H., 52,60,123 Richardson, C., 3, 123
Fortune, J., 110, 122 Kotani, H., 44, 124 Richey, F., 51-52,54,59-61,86,88,119
Frechette, V. D., 4,28, 120 Kramer, H., 4-5,43-45,52-53,55, Rowe, W. W., 37
Frederick, J., 59,118 59-60,83,86,843,120
Samuel, G., 5,60, 123
Fujimura, K., 30, 122 Laxmi, S., 45, 120
Sansoni, G., 22,123
Fukunaoa. K.. 52,60,123 Lea,F.M., 11,27, 120
Scheubel, B., 110, 123
Fundal,-& 5,23,.40&, 52,59-60,76, LeChatelier, H., 1,3,22, 120 Sereda, P. J., 98, 119
83,86,118,120 Lee, R. F., v, 40-41,61, 120
Shvetsov, M. S., 124
Garcia, J., 63,67 Lehoux, P., 40,89, 118 Shimota, T., 31, 122
Gartner, E. M., 62, 124 Lon G. R v 6 8-10,43-45,51-55,
Shim&a, M., 24,26,31,51,122-123
Ghosh, S. K., 22-23,26,54,118 5&61, %77,83,86,88,109,120
Love, H., v Skalny, J., 98, 119, 123
Gille, F., 3-5,22,43-45, 52-55, 59-62,
MacKenzie, W. S., 11,117,121 Smith, M. A., 29,119
76-77,83,86,88,118,119
Soda,Y., 22-23,26,30-31,39,52-54,
Glasser, F. P., 77, 119 Maeda, K., 88-89, 117 60,62,122-123
Goswami, G., 86,119 M&a&, li;5y2;23, 26,37,40,42,51-54,
Sorby, H. C., 1
Goto, K., 51-54,60, 121
Mander, J: E., 98, 123 Sorochkin, M. A., 44,118
Gotthardt, R., 89, 119
Marlin, J., 8, 121 Sprung, S., 43, 123
Gouda, G. R., 27,51-52,60,86,98,119

125
(continued) Alite, 3,22,51-55 alkali-rich, 24,30,61, 62
Photos: 5-6 (pp. 1 1 - 12). 8 (p. 12). alpha, 3,24 -25,30,62
Spurr, A R., 112, 123 124-125 (p. 99). 126 (p. 100)
Stark, D. C., 39 alpha prime, 24 -25,62
abundance, 21,43,51
Stake, J., 51,53, 117 amoeboid, 59
apparent birefringence, 39, 53 Photos: 60 (p. 69). 136 (p. 103)
Stem, E., 3, 123 Photos: 1 1 - 12 (p, 24)
beta, 3,24 -25
Stn;~ei;3 43,51-54,62,77,88,118, birefringence, 23,33,37,39,53
birefnngence, 23,41,61
cannibalistic, 51
classification, 23 -24
Sundius, N., 29, 123 clusters, 52
color, 23, 25, 37,40-41
Suzukawa, Y., 52,60, 123 color, 23, 54 Photos: 13-15 (pp. 34-35). 25 (p. 49). 76
Suzuki, Y., 38,124 cooling rate, 54 (p. 75)
Swavze, M. A., 3.27.117 decomposition, 22,54-55,61 dendritic, 61
Syllii, H. M., 45, 51, 54,60,62, 76-77, Photos: 67-69 (p. 72). 141 (p. 105)
etching degree, 9-l 0,23,31
88,124 distribution, 59 -60
fluorine modified, 10
Tachihata, S., 44,124 dusting, 24
form factor, 40
Takagi, S., 23,38,98, 124 etching degree, 23,31
inclusions, 23, 54
Takahashi, S., 23,42,51,53-54,115,121 Photos: 42 (p. 63). 93 (p. 84) gamma, 24,62
Takashima, S., 26, 124 Photos: 54-57 (pp. 67-68)
lattice constants, 32.
Tanaka, T., 124 in alite, 41, 60-62
MI and MI varieties, 23,40,51,53 Photos: 73-75 (p. 74). 136 (p, 103)
Tang, F. J., 62, 124 morphology, 23,51,54 inclusions, 37, 61-62
Tavasci, B., 3 -4, 124 mortar strength, 52,54-55 Photos: 45 (p. 64). 70 (p. 73)
Taylor, H. F. W., v, 22,61, 121, 124 origin, 22,26,42,54 Insleys classification, 23-24
Taylor, W. C., 4. 124 polymorphs, 23,31,53 internal structure, 3, 24 -25, 30, 60
Terrier, P., 44, 117 recrystallization, 23,51 Photos: 29 (p. 50). 35 (p. 57). 61-66 (pp. 70-71).
72 (p. 73). 127-128 (p. IW). 130 (p. 101).
Terry, R. D., 109, 124 size:Vl, 23,32,33,43,45,51-53,55, 108 133-135 (pp. 102-103)
Thaulow, N., 3, 117, 120 Photos: 22 (p. 48), 32-36 (pp. 56-57).
40-41 (p. 63) inversion, 24 -25, 30
Thomas, A., 10,27, 123 nests, VI, 39,59
size gradation, 108
Timashev, V. V., 4,42, 53, 117 Photos: 26-27 (p. 49). 49-5 1 (p. 66)
thickness, 33,36,39
Tomita, K., 26, 124 origin, 42
Ttirnebohms terminology, 3
Tornebohm, A. E., 3,22,43, 124 polymorphs, 4,30
twinning, 23,53
Tresouthick, S., v Photo: 42 (p. 63) raw+, 61
Trojer, F., 29, 124 Photos: 3 (p. 2). 45 (p. 64). 70-71 (p, 73).
x-ray diffraction, 30 -32 131-132 (pp. 101-102)
Ts;G&, 43,52, 54 -55,59-62, 77, zoned crystals,. 23, 54 secondary, 40 4 I,6 1
Photos: 37 (p. 58). 44 (p. 64) Photos: 62 (p. 70). 6566 (p. 71). 79 (p. 78).
Tsumagari, A., 28,117 Alkali aluminate, 8, 26, 76-77 131 (p. 101)
Uchikawa, H., 39, 124 Photos: 86-91 (pp. 80-82). 140 (p. 104) size, 23, 37, 39, 60
Uda, S., 40, 117, 122 Alkali sulfate, 4, 8, 10, 22, 27, 88 twinning, 24 -25, 60
Photos: 101-106 (pp. 89-91). 146-148 Photos: 56-59 (pp. 68-69)
&da, Y., 38, 124 (pp. m--107)
Uno, T., 31, 122 x-ray diffraction, 26, 111
Alumina ratio, 52,55, 76,88
Vanisko, Ci., v Biaxial, 115
Anhedral, 115
Wahlstrom, E. E., v, 124 Birefringence, 22, 36 37, 39
Anhydrite, 28
Warbenowa, C., 29,124 Blaine specific surface, 31, 38
Anistropic, 33
Weigand, W., 5, 10, 117 Burning degree, 39,43,83
Aphthitalite, 27
Welch, J. H., 4, 122 Burning rate (see also Ono method), VII,
Arcanite, 27
32 -33,40
Wetzel, T., 3, 124 Artifacts, 93
Weymouth, J. H., 8,118 Photos: 112-122 (pp. W-97) Burning time (see also Ono method), VII,
32,37
Wieja, C., 24, 124 residual liquids, 93
Photos: 113-l 16 (pp. 96-97). 118-121 Calcite, 27, 83
Wreja, K., 24, 124
(pp. 96-97) Calcium aluminate, 8
Wilcox, R. E., 11,21, 118
surface irregularities, 93 Calcium aluminoferrite, 1
Wilder, H., 89, 119 Photo: 112 (p. 94)
Calcium hydroxide
Wrncheil, A. N., 21,27-28, 124 Aspdin cement paste, 13
Photos: l-4 (pp. l-2) epezite (air slaking), 4, 7, 27
Wrnchell, H., 21,27 -28, 124
Photos: 96-97 (p. 85). 143-145 (pp. 105-106)
Woermann, E., 5,45,54,61-62,76-77, Austenite-martensite, 3
portlandite, 4
86,124 Autoclave problems, 86 Photo; 144 (p. 106)
Wolter, A, 44, 124 Automated microscopy, 98, 111 Calcium langbeinite, 27
Wright, F. E., 3,22, 123 Babinet compensator, 36 Calcium oxide (see also free lime), 4, 8, 27
Yamaguchi, G., 23-24,30,98,124 Basal pinacoid, 23 Calcium sulfide, 28
Zybell, H., 22, 123 Becke line, 115 Calcium sulphosilicate, 29
Belite, 3,23, 59 -62 Canada balsam resin, 112
Photos: 5 (p. 1 I). 124 (p. 99). 129 (p. 101)
Celite, 3
abundance, 23,59
Cement
agglomerations, 59 Photo: 17 (p. 46)

126
air setting, 88 Equipment, 15 Monoclinic system, 115
examination (see also On0 method), recommended items, 15,111- 112 Mortar strength
14-21,30,32,108 suppliers, 1 1 1 - 112 alkali relationship, 26,31,88
Photo: 17 (p. 46)
Etchants (see Stains and etches) belite, 31, 59,61-62,89
fineness, 30-31,38
Euhedral, 115 crystal size, 44,51-52.55
flowability, 27, 88
Extinction, 33 matrix phases, 77,86
rapid setting, 88 -89
Felite, 3 prediction equations (see also On0
sampling, 7
Ferrite, 4,26 -27,31,76-77 method), 31-32
strength prediction, 31-32,38 Photos: 5 (p. 11). 42 (p. 63). 4648 (p. 65). prediction table (see also Ono method), 38
unhydrated (UPCs), 3 83 (p. 79), 108 (p. 91). 137-138 (pp. 103-104)
Photos: l-4 (pp. l-2) Mounting media, 15-16,20,115
Fineness, 30-31,38
workability, 88 Nests, 43
Flame length, 31,45,51-54
Centrifuge, 16 belite, 4 1, 59
Fly ash (see Coal ash) Photos: 26 (p. 49), 49-51 (p. 66)
Photo: 43 (p. 64)
Form, 115 free lime, 27,83
Character Index, 38
Free lime (calcium oxide), 8. 27.83 Photos: 92-94 (p 84). 95 (p. 85)
Clinker, 43-45
clusters (nests), 83 periclase, 27,86
burning time (see also Ono method), 32 Photos: 92-95 (pp. 84-85) Photo: 143 (p. 105)
color, 3 1,45 percentage, 4,31,83 Oil immersion, 19,21,110
Photo: 77 (p, 75) Photo: 10 (p. 13)
Whites test, 27
cooling rate (see also On0 method), Oil-well cement, 5, 26,45, 51, 53, 55, 59
31-32,37 Fuel type, 45,51-54,59-61,86,88-89
Gehlenite, 4, 28,88 Ono method, 30,32
crystal size (classification), 108 equipment, 33
dusty, 43 -45 Glass, 3-4,28, 54,59,88
Photo: 107 (p. 91) interpretation of parameters, 30,32
examination procedure, 30,32,108
Graphite, 28 parameters, 30 -32
flushing, 44 Grindability, 3 1,44,59,88 -89 Orthorhombic system, 115
general features, 22,43 -45 Photo: 123 (p. 99) Oxidizing conditions, 45, 51, 55,60,
granulometry, 6,43 Gypsum, 28 76 -77,88
grindability, 31,44,59,88-89 Hexagonal system, 115 Particle mounts, 10,21,98
Photo: 123 (p, 99)
High-alumina cement, 8-l 0 Percentage comparison chart, 109
heating rate (see also Ono method), 32 Hyrax,4,20-21,112
ideal microstructure, 22,43 Periclase, 22,86
Photos: 18- 19 (pp. 46&47), 29 (p. 50)
Impregnation, 16 * abundance, 86
liter weight, 45 Index of refraction, 115 crystal morphology, 22,86
megascopic properties, 108 Interference colors, 22 dendritic, 22,86
microscopical description, 108 International Cement Microscopy Photos: 98- 100 (p. 87), 14 1 (p. 105)
Association, 5 size, 4,86
modal size class, 7, 108
Iron (metal), 29,54,62,88 Photomicrography, 111
porosity, 22,31,43 -45,89, 104
Photos: 16 lp. 46). 21 (p. 47). 138 (p. 104) Isomet, 15-16,19,21,111 Plane-polarized light, 115
process type, 43,60,88-89 Isometric system, 115 Plaster, 28
temperature curve, 32 Isotropic, 115 Pieochroism, 115
weathering, 45, Lamellae, 115 Pleochroite, 10
zoned clinkers, 43-44 Lime saturation factor, 43,59,88 Point count, 109
Coal ash, 28,43-44,59,89 Limestone relicts, 83,86 error calculation, 110
Coke, 28 Linear traverse, 110 Polished sections, 14
Compensators Liter weight, 39 artifacts, 14,03
Photos: 112-122 (pp. W-97)
Cabinet, 36 Magnesium oxide (see also Periclase), 38
Martensite, 3 equipment, 15,
Senarmont, 33
Matrix, 22,76-77 polishing cloths, 15
Cooling rate, 31-32,37,61-62, 76-77,86
Photos: 9 (p. 13), 10 (p. 13), 42 (p. 63). 48 (p. 65), quick method with epoxy, 18
Diamond preparation materials, 17 -18 58 (p. 69). 60 (p. 69), 82 (p. 77). 123 (p. 99). techniques, 15
Dicalcium silicate (see Belite) 139 (p. 104)
crystal size, 76 Super Glue method, 18
Dolomite, 86
Photos: 78-79 (pp. 77-78). 84-85 (p. 79) Polishing compounds, 15
Double salt, 29
phase proportions, 76 Polymorphism, 23 -24,115
Dusty clinker, 45
Photos: 65 (p. 71). 80 (p. 78) Potassium iron sulfide, 28,88
Ecomet, 15-17,19,21 Maximum temperature, VII, 32 Pseudomorph, 115
Electron microscopy and microprobe, V,
Melilite, 9 pyramid, 24, 115
VII, 98,113
Embedding material, 15 -16 Meltmount, 115 Quantitative microscopy, 109 -110,113
Michel Levy Color Chart, 36 Quartz, (see also Raw feed), 28
Encapsulation, (see Epoxy resin)
Microcloth, 15 Raw feed, 30,43
Epezite, 4,27,83 Photos: 109-l 11 (p. 92)
Photos: 96-97 (p. 85) Microcracks, 6
Epoxy resin, 15, 112 Microscopy alite crystal size, 30
desirable characteristics, 16 application to the cement industry, Vl aluminosilicate grains, 43, 59
encapsulation and impregnation, 15 -16 modes of sample preparation, 14 clinker size, color, burning time, 43
thin films, 21 Minimet, 15-16,19,21,111

127
Subject Index (continued)
coarse quartz, 30,43,51,59,88 polishing equipment, 19, 111, 113
Photos: 49-5 1 (p. 66). 52-53 (p. 67). rocks and minerals, 11
109--110 (p. 92)
ultrathin sections, 20
diopside, 69 Photos: 81 (p. 78). 86 (P. 80)
dolomite, 86 Tricalcium aluminate, .l, 26, 76-77
feldspar, 41, 59 Photos: 5 (p. 11). 9 (p. 13). 37 (p. 58). 42 (p. 63).
Photo: 111 (p. 92) 48 (p. 65). 66-67 (pp. 71-72). 74 (p. 74).
inhomogeneity, 43,52,59,83,88 78-82 (pp. 77-79). 84-86 (pp. 79-80)
Photos: 23-24 (p. 48). 26-28 (pp. 49-W) abundance, 26,76
limestone, 51,83,86,88 crystal size, 26,76
Photos: 94 (p. 84). 109-l 11 (p. 92) Tricalcium silicate (see Alite)
particle size effects, 43,53,83,88 Triclinic system, 116
Photos: 30-3 1 (pp. 55-56). 39 (p. 58)
Twinning, 116
phase changes, 30 -32
alite, 23, 53
Reducing conditions, 4,45, 54, 76-77,88
Photos: 70 (p. 73). 77 (p. 75) aluminate, 26
Refractive index, 116 belite, 24 -25
Refractory brick, 45,89 Underburning, 43-45,52-53,55,60,62,
Photos: 68 (p. 72). 73 (p. 74). 83 (p. 79) 76,83
Relief polish, 9 Uniaxial, 116
Photo: 38 (p. 58) Whites reagent, 27
Resins, 112 Wustite, 28
Retardation, 33,36,116 X-ray diffraction, 7, 110
Rhombohedron, 23,116 Zoning (crystal), 25, 53, 77
Sample
preparation, 14-21
sample storage, 7
Sampling, 6 -7, 110
Scanning electron microscopy, 98-l 07
Senannont compensator, 33
Setting time, 44,88
Shaft kiln, 5,43
Photo: 28 (p. 50)
Sieving
cement, 33, 118
clinker, 6, 7, 113
Silica ratio, 43, 52, 76,88
Slide holders, 18, 19
Spunite, 28
Stains and etches, 8 -13,93
Photos: 5-10 (pp. 11-13). 52 (p, 67)
aluminates, 8
artifacts, 14,93
calcium fluoroaluminate, 10
clinker silicates, 9
free lime, 8
fluorosilicates, 10
rocks and minerals, 8, 11
sulfates, 8, 10
Subhedral 116
Sulfates, 27 -29
Sulfides, 28
Super Glue, 16,18
Syngenite, 27
Temperature (maximum), 32
Temperature curve, 32
Tetracalcium aluminofenite (see Ferrite)
Tetragonal system, 116
Texmet, 15
Thin sections, 3-4,14,19
commercial services, 112
epoxy resin techniques, 19
grinding equipment, 19, 111, 113
Hyrax method, 4,20

128