Chemistry for Everyone

edited by

Products of Chemistry

George B. Kauffman
California State University
Fresno, CA 93740

Cement: Its Chemistry and Properties

Douglas C. MacLaren and Mary Anne White*
Department of Chemistry and Institute for Research in Materials, Dalhousie University, Halifax, Nova Scotia B3H 4J3,
Canada; *Mary.Anne.White@DAL.ca

One of the most active areas in scientific research is the

development of new and exciting materials for a wide variety of applications. In this context, it could be easy to lose
sight of the importance of more common materials that are
vitally important in many areas of our lives. Cement is one
such material, and its rich chemistry links well with a number of concepts in most undergraduate chemistry curricula.
This paper addresses several important questions concerning cement, including: What is its optimal composition
and why? Why do cement truck barrels roll? What are the
processes involved in cement setting, and how long does it
take? How does cement break down?
A Brief History of Cement
Cements and cement-containing materials comprised
some of the first structural materials exploited by humanity
(1), as cements components are common materials: sand,
lime, and water. On a molecular level, cement is a paste of
calcium silicate hydrates polymerized into a densely crosslinked matrix (2). Its most important property is called
hydraulicitythe ability to set and remain insoluble under
water (3, 4). Cement can be used as a mortar to bind large
stones or bricks. When sand and stones are added to cement,
the aggregate is called concrete. The word cement comes from
the Latin phrase, opus caementum, or chip work, in reference
to the aggregate often used in applications (3).
Cement production dates back to the ancient Romans,
who produced mortars using a mixture of lime, volcanic ash,
and crushed clay. These cements are referred to as Pozzolanic
cements after the Pozzulana region of Italy, which contained
Italys chief supply of ash (1, 5 ). Pozzolanic cements derive
their strength from rich aluminate phases present in the volcanic ash that promote efficient hydration of the final cement powders (6). Fine grinding and attention to consistency
are also fundamental to the success of Roman cement, much
of which is still in existence today in structures such as the
Pantheon, the Pont du Gard, and the Basilica of
Constantinople (2, 5). An example of a structure made with
Roman cement is shown in Figure 1.
The art of cement production was lost in Europe after
the fall of the Roman Empire (2, 5). At that time, the access
to volcanic ash was limited and the grinding and heating techniques required for cement precursor production were lost.
Cements of this period, if still in existence, are inconsistent
in composition and are composed almost exclusively of unreacted starting materials (1, 2, 5). There was no significant
breakthrough in the development of cement chemistry until
1756, when Smeaton was commissioned to rebuild the
Eddystone lighthouse in Cornwall, England. In contrast to

the methods of his contemporaries, Smeaton found superior

results through experimentation by using an impure limestone with noticeable clay deposits. This produced extremely
strong cement that would equal the best merchantable Portland stone in solidity and durability(5).1
Another major advance came in the early 19th century
when the French engineer Vicat performed the first empirical study on the composition of cements. Although crude
and incomplete, it was one of the most comprehensive examinations of cement chemistry for the next 80 years (3, 4,
810).
The term Portland cement did not become officially recognized until 1824 when Aspidin filed the first patent for its
production (2, 5). Cement compositions at this time were
poorly understood but closely guarded secrets. Portland cement was introduced into the United States by Saylor in 1871
(3, 4).
By the start of the 20th century, cement manufacture
was common but was still regarded as more of an art than a
science. Emphasis was placed on bulk manufacture, not quality control or consistency (10, 11). Early in the 20th century, cement research became more scientific, incorporating
the relatively new Gibbs phase rule and Le Chtelier equilibrium principles (3). In 1904 the first set of ASTM standards2 for cement were presented and in 1906 the geophysical
laboratory of the Carnegie Institution began an extensive investigation of cement chemistry. These advances resulted in
the development of uniformity in the cement industry, allowing a rapid expansion in the application of cement to large
construction projects such as skyscrapers, roads, and dams
(2, 3, 8, 11).

Figure 1. Roman aqueduct in Segovia, Spain, from the first century C.E. Courtesy Stephen L. Sass. Reproduced, with permission,
from ref 1.

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More recent advances in materials-characterization techniques, such as X-ray crystallography, electron microscopy,
nuclear magnetic resonance spectroscopy, Mssbauer spectroscopy, infrared spectroscopy, and thermal analysis, have
allowed the systematic examination of cements chemistry and
the complex processes surrounding its production and hydration (2, 12). Scientific research has led to a better understanding of the properties of cement, cement production, and
cement corrosion. In fact, breakthroughs in cement research
have provided us with cements of increasing quality and
strength.
Cement is prepared in a two-step process. The first step
is the high-temperature mixing and processing of limestone,
sand, and clay starting materials to produce a cement powder. The second step involves the hydration, mixing, and setting of the cement powder into a final cement product (2, 6,
13). The dry portion of Portland cement is composed of
about 63% calcium oxide, 20% silica, 6% alumina, 3%
iron(III) oxide, and small amounts of other matter including possibly impurities (7). Calcium silicates and calcium aluminates dominate the structure.
The cement literature uses abbreviations for the many
calcium oxide, silicate, aluminate, and ferrate compounds
important to cement. We have used the same abbreviations
here and present the correspondence between the chemical
formulas and abbreviations in Table 1 (14).

Cement Formation

Preparation of Cement Precursors: Clinkers

The raw materials for cement production are blended
in the required proportions, ground, and heated to high temperatures, usually with rotation. Heating first releases H2O
and CO2 and then causes other reactions between the solids,
including partial melting. Cooling results in clinkers, a term
from the coal industry in the 19th century to describe stony,
heavily burnt materials that were left after the burning of coal
(7). Ironically, Aspiden and Vicat both dismissed the hard
glassy clinker material (which was expensive to grind) as being useless to cement manufacture (8, 11), although we now
know that clinkers are essential for good cement production.
After heating, cement clinkers are reground for use in the
production of cement. Commercial cement manufacture incorporates a wide variety of minerals, including: calcium oxide, silica, alumina, iron oxide, magnesium oxide, titanium
dioxide, and many others (5, 14). Of these, three are most
important to the final cement product: calcium oxide, silica,
and alumina. Consideration of all the possible phases produced by these multicomponent systems is simplified by considering a ternary system of primary importancethe calcium
oxidesilicaalumina system (14).
High-quality cement powders require the presence of two
major components, tricalcium silicate, C3S, and dicalcium

Table 1. Common Cement Component Names, Compositions, Formulae, and Abbreviations

C ompone nt N ame

C ompos it ion

Empirical Formula

A bbre v iat ion

C alcium ox ide (lime )

C aO

C aO

Silicon diox ide (s ilica)

SiO2

SiO2

A luminum ox ide (alumina)

A l 2O 3

A l 2O 3

Iron(III) ox ide

F e 2O 3

F e 2O 3

Dicalcium s ilicat e

2C aO
SiO2

C a2SiO4

C 2 S

Tricalcium s ilicat e

3C aO
SiO2

C a3SiO5

C 3 S

Tricalcium aluminat e

3 C a O
A l 2 O 3

C a3A l 2O 6

C 3 A

Te t racalcium aluminof e rrat e (B row nmille rit e )

4C aO
A l2O3
Fe 2O3

C a4A l 2F e 2O 10

C 4 A F

C alcium s ilicat e hy drat e ge l

(C aO)x
SiO2
yH 2O w it h x < 1.5

in s olid s olut ion w it h C a(OH )2

(v ariable )

C S H

C alcium s ilicat e (W ollas t onit e )

C aO
SiO2

C aSiO3

C S

C alcium s ilicat e (Rankinit e )

3C aO
2SiO2

C a3Si2O7

C 3 S 2

C alcium aluminum s ilicat e (Ge hle nit e )

2C aO
A l2O3
SiO2

C a2A l2SiO7

C 2 A S

A luminium s ilicat e (M ullit e )

3A l2O3
2SiO2

A l6Si2O13

A 3 S 2

C alcium aluminum s ilicat e (A nort hit e )

C aO
A l2O3
2SiO2

C aA l2Si2O8

C A S 2

A luminium s ilicat e

2A l2O3
2SiO2

A l4Si2O10

A 2 S 2

C alcium aluminat e

C aO
A l2O3

C aA l 2O 4

C A

C alcium dialuminat e

C aO
2A l2O3

C aA l 4O 7

C A 2

Dode cacalcium s e pt aluminat e

1 2 C a O
7 A l 2 O 3

C a12A l 14O 33

C 1 2 A 7

C alcium he x aluminat e

C aO
6A l2O3

C aA l 12O 19

C A 6

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Chemistry for Everyone

For this discussion, the important region of the

CaOSiO2Al2O3 phase diagram is the C3SC2SC3A
phase field, the region close to the CaO vertex in Figure 4. A
three-dimensional view of the ternary phase diagram in this
region is shown in Figure 5. As the temperature of the sysSiO2
1723
1698

1500

Cristabolite + L

x
A2S2

bo

1385
1405
1380

Corundum

1475

x 1850

1840

(-Al2O3)

(CaO)

C A

x15423
C3A

CA

1415 1605

C12A7

CA

x
CA6
1789

1860

CA2

CA6 Al2O3

Tridymite + L

C 3S2+

-CS

CaO + -C 2S

C 3S2+

C 3S +
-C 2S

C 3S2+
-CS -CS + Tridymite
-CS + Tridymite

1000

C 3S C 2S C 3S2
0

1553 1547

1590
1552
1380
1512 1500
1455
1350
CA2
1335
1470 1335

Lime

1512

CAS2
1265

C2AS

C3S

Figure 4. The ternary phase diagram of calcium oxide, silica, and

alumina. The region nearest the CaO vertex represents the primary
phase field for the formation of tricalcium silicate. Temperatures
are presented in C (13, 16).

Two
Liquids

-CS+L

C 3S 2+
-C 2S

-C 2S

Temperature / C

C 3S +
-C 2S
C 3S2 + L

CaO + C 3S

CaO

Cristabolite + L

(CAS2)

1545

)
S2

2000

-C2 S + L

-C2S

C3S

1170

1318

1315

1345

(A 3

2570

C 3S + L

2130
2050
2150

ite

llite
Mu

C3S2
C2S

1368

Anorthite

1544
1460
C3S2 1307
1464
1310

2500

CaO + L

-CS

CS

x
1470

ym

d
Tri

1470
1436

Cr
ista

x
1698

1598

lite

Two x
liquids

e
nit
hle S)
Ge(C 2A

silicate, C2S, in the clinkers. These materials react vigorously

with water to produce the cement paste formed in the final
product. Of the two, tricalcium silicate is the more desirable
clinker material because it hydrates and sets much faster than
dicalcium silicate (hours for C3S, days for C2S) (2, 15).
The binary phase diagram of SiO2 and CaO is shown
in Figure 2 (16, 17). Most important is the 030 mass %
SiO2 region. C3S is formed at less than 30 mass % SiO2
but is not stable below about 1250 C or above about 2200
C. In the low end of this temperature range C3S will form,
but extremely slowly because it involves a reaction between
two solid phases. For example, forming C3S at temperatures
of 12001400 C would require heating for days and is not
economical. At the other end, production from the melt at
2200 C is also impractical because of the very high temperature.
Therefore, the temperature of the C3S production for
the clinker is lowered by fluxing3 the reaction mixture with a
third component, alumina (7, 14, 15). The binary phase diagram of CaO and Al2O3 is shown in Figure 3 (16). Comparison with the ternary CaOSiO2Al2O3 phase diagram (7,
14, 16), Figure 4, shows that the addition of Al2O3 lowers
the preparation temperature of C3S.

20

CS
60

40

100

80

(CaO)

(SiO2 )

mass % SiO2
Figure 2. The binary phase diagram of calcium oxide and silicon
dioxide. The region of interest is 030 mass % SiO2 where
tricalcium silicate (C3S) is formed (14).

CA 6+ L
CA 2+ L

CaO + L

1800

Al 2O3
+L

CA + L
C 3A + L

C 12A 7 + L

1400

CaO + C 3A

C 3A
C12 A 7
+ C 12A 7 + CA

CA +
CA 2

CA 2
+
CA 6

CA 6 + Al 2O3

Temperature / C

2200

1000
0

20

C3 A

40

C12 A 7

CA
60

(CaO)

CA 2
80

CA 6

100

(Al 2O3)

mass % Al2O3

Figure 3. The binary phase diagram of calcium oxide and alumina

(Al2O3). The temperature of the liquidus of the binary system decreases significantly as Al2O3 is added to the mixture (13).

Figure 5. Three-dimensional view of the CaO-rich portion of the

ternary phase diagram of calcium oxide, silica, and alumina emphasizing the tricalcium silicate primary phase field. The composition of the liquid will follow the minimum path along the liquidus,
which deeply slopes into the tricalcium silicate phase field as the
temperature of the system is lowered from 2150 C to 1450 C (5).

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tem decreases from about 2100 C, the composition of the

liquid goes into the C3SC2SC3A phase field (5). Adding 20 mass % alumina to a silicalime system lowers the
liquidus into the region of stable C3S formation, from the
reaction of C2S and CaO in the liquid phase. This, of course,
is much faster than the solidsolid reaction (5, 7, 15, 18).
Therefore, heating a composition in the C3S phase field to
14501500 C results in a liquid phase that can be quenched
to form the final C3S-rich cement clinker. Although neither Smeaton nor the Romans fully realized the chemistry, it
was the addition of rich aluminate matter in the form of volcanic ash or clay impurities that allowed their production of
strong cement precursors (5).
The total process of cement-clinker formation is summarized in Figure 6, which shows the main components as a
function of temperature (18). Calcium carbonate (limestone),
quartz, clay (primarily Al2O3), and water are combined and
heated. (Iron oxide, clay, and other minor components are
neglected in this discussion.) As the temperature rises, first
water is lost, and then above 700 C, the limestone decomposes forming CaO and carbon dioxide. CaO reacts with
silica to form C2S and with the aluminate phases to form a
calcium aluminate phase (an Ettringite phase4), which melts
at about 1450 C (18). The formation of this liquid phase is
associated with the rapid production of tricalcium silicate.
The final mixture at 1500 C is primarily tricalcium silicate
with smaller portions of dicalcium silicate, aluminate, and
aluminoferrate phases.
The minor components present in cement paste (e.g.,
iron oxide) have only subtle effects on the properties of the
final cement properties (5, 14). One of the reasons for using
them is that they also help to flux the system to a lower temperature. Table 2 lists a group of multicomponent clinker materials in the C3S phase field. It is apparent that adding small
amounts of other minerals can lower the temperature at which
a liquid phase is formed (5).
After quenching, the resulting clinker is milled and
ground into a fine powder. At this stage various other materials can be added to the cement powder prior to packaging.

Cement Hydration
Cement hydration is a familiar process. The cement powder is mixed with water and then is poured for the desired
application. The final cement product generally contains
about 3040 mass % water after hydration, and this value
varies little with the composition of the cement clinker. Although it might appear simple, cement hydration consists of
a complex series of chemical reactions, which are still not
completely understood (13). Cement hydration rates can be
affected by a variety of factors, including: the phase composition of the clinker, the presence of foreign ions, the specific surface of the mixture, the initial water:cement ratio,
the curing temperature, and the presence of additives (13,
18).
The rate of hydration of C3S in a Portland cement clinker is shown in Figure 7. Immediately upon contact with
water C3S undergoes an intense, short-lived reaction, the
pre-induction period (I). The rate (d/dt, where is the degree of hydration or the fraction of cement precursor material that has been hydrated) is as high as 5 day1. This process
begins with the dissolution of C3S. Oxygen ions on the sur626

face of the C3S lattice react with protons in the water and
form hydroxide ions, which in turn combine with Ca2 to
form Ca(OH)2 (13):

O2(lattice) + H(aq)

2OH (aq) + Ca2(aq)

OH(aq)

(1)

Ca(OH)2(aq)

(2)

Figure 6. A schematic view of the components of cement-clinker

formation, their reactions, and the products formed as the temperature of the mixture is raised. Calcium carbonate decomposes to
form calcium oxide and carbon dioxide. Calcium oxide reacts with
silica to form dicalcium silicate at temperatures below 1250 C,
which converts to tricalcium silicate at temperatures above 1250
C. Formation of a liquid aluminate, Ettringite, phase at about 1450
C facilitates the conversion of dicalcium silicate to tricalcium silicate (18).

Table 2. Clinker Components in the C3S Cement Phase

Field and Their Temperatures of Liquid Formation (5)
Components

Temperature of
Liquid Formation /C

CaOSiO2

2065

CaOSiO2Al2O3

1455

CaOSiO2Al2O3Na2O

1430

CaOSiO2Al2O3MgO

1375

CaOSiO2Al2O3Fe2O3

1340

CaOSiO2Al2O3Na2OMgO

1365

CaOSiO2Al2O3Na2OFe2O3

1315

CaOSiO2Al2O3MgOFe2O3

1300

CaOSiO2Al2O3Na2OMgOFe2O3

1280

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Chemistry for Everyone

At the same time, silicate material from the C3S lattice surface enters the liquid phase (13):

SiO44(lattice) + n H(aq)

HnSiO4(4-n)(aq) (3)

The dissolved components combine to form the calcium

silicate hydrate CSH gel, an amorphous two-component
solid solution composed of Ca(OH)2 and a calcium silicate
hydrate of low Ca:Si ratio, hydrated as in this example (13,
19, 20):
2 (3CaO
SiO2)(s) + 6 H2O(l)
3 CaO
2SiO2
3 H2O(s) + 3 Ca(OH)2(aq)

(4)

However, the reaction would not likely be of this exact stoichiometry.

Most cement powders have gypsum (CaSO4) added prior
to packaging. Gypsum acts to slow down the pre-induction
period to avoid rapid setting of the cement (3, 8). It reacts
with tricalcium aluminate (C3A) to form various aluminate
and sulfoaluminate phases, collectively referred to as Ettringite
phases (7, 13, 15, 19). Some examples are:
3CaO
Al2O3(s) + 3 CaSO4(s) + 32 H2O(l)
3CaO
Al2O3
3CaSO4
32 H2O(s)

(5)

Fraction of 'C3S'
Hydrated

0.25

IV
0.20

III

0.15
0.10

II
I

0.05
0.00
0

10

15

Hydration Time / h

B
Fraction of 'C3S'
Hydrated

1.0
0.8

IV

0.6
0.4
0.2
0.0
0

50

100

150

Hydration Time / days

Figure 7. A graphic representation of the rate of consumption of
tricalcium silicate (C3S) as a function of hydration time: (A) changes
in hydration rates in the first few hours as a result of (I) pre-induction, (II) induction, (III) acceleration, and (IV) deceleration processes.
(B) an expanded view showing the length of time required for complete cement hydration (13).

3CaO
Al2O3(s) + 3CaSO4(s) + 12H2O(s)

3CaO
Al2O3
3CaSO3
12H2O(s)

(6)

C3A and C4AF can also hydrate independently of calcium

sulfate:
3CaO
Al2O3(s) + 6H2O(l)

3CaO
Al2O3
6 H2O(s) (7)

4CaO
Al2O3
Fe2O3(s) + 2Ca(OH)2(aq) + 10 H2O(l)

3CaO
Al2O3
6 H2O(s) + 3CaO
Fe2O3
6 H2O(s)

(8)

During the pre-induction period about 525% of the C3A

and C4AF undergoes hydration, causing a saturation of
Ettringite in the solution (13).
After a few minutes of hydration an induction period
(II in Figure 7) begins where the reaction slows significantly, d/dt = 0.01 day1. The exact reason for this induction period is not known. Several theories have been
proposed that involve some sort of mixture saturation from
the intense burst of hydration in the pre-induction period
(13). One theory states that the CSH layer quickly covers the surface of dissolving C3S, slowing the reaction.
As time passes, the CSH becomes more permeable and
the reaction accelerates. Another theory states that the solution may become supersaturated with Ca(OH)2 because
the surfaces of Ca(OH)2 crystal nuclei are poisoned by silicate ions. The high concentration of aqueous Ca(OH)2
limits the rate of dissolution of the silicate species to negligible rates. Eventually the level of aqueous Ca(OH)2 becomes too high and calcium hydroxide crystallizes,
allowing the hydration reactions to continue. Another
theory speculates that two types of CSH are formed. The
rate of first-stage CSH is dependent on the concentration of aqueous Ca(OH)2. As the concentration of aqueous Ca(OH)2 decreases, the production of first-stage
CSH stops, causing induction. Hydration resumes later
when the thermodynamic barrier for the nucleation of
second-stage CSH is overcome (13).
At any rate, an induction period occurs and varies in
time depending on the type of cement and the desired
application, usually lasting several hours. This property of cement hydration is what makes it easy to use as a construction materialit is a semi-solid that can be easily poured into
desired shapes for application. Aqueous gels are often semisolid owing to interaction between water molecules and the
surfaces of the particles. Mixing of the system provides energy
to overcome these interactions and allows the gel to become
more fluid. In the case of cement mixtures, constant mixing
is required to keep the material in a fluid state (15). This is
why wet cement is often stored in large rotating drums until
it is poured. During this induction time, so long as it is
continuously mixed, the cement can be held ready for
pouring.
Following induction, the reaction rate accelerates to approximately d/dt = 1 day1. At this point the hydration processes are limited by the nucleation and growth of the
hydration products. This acceleration stage (III in Figure 7)
is characterized by rapid hydration of C3S, followed slowly
by the hydration of C2S (13):

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2(2CaO
SiO2)(s) + 4H2O(aq)
3CaO
2SiO2
3H2O(s) + Ca(OH)2(aq)

(9)

During this process, calcium hydroxide reaches its maximum

concentration in the solution and then begins to precipitate
out as crystalline calcium hydroxide, referred to as Portlandite
by cement chemists (7, 13, 15). As the solution becomes concentrated with solid product the rate of hydration slows and
becomes diffusion controlled. The reactions slow to nearly
negligible rates but continue for weeks as the CSH gel continues to form.

Calcium Silicate Hydrate (CSH) Gel Formation:

NMR Studies
In its final form, cement is a suspension of calcium hydroxide, Ettringite, and unreacted clinker materials in a solid
solution of mineral glue called CSH gel (13, 15). The formation of CSH gel is vital to the understanding of cement
hydration processes.
One of the most powerful tools for studying the reactions of cement hydration is solid-state nuclear magnetic resonance spectroscopy (2123). Cements are rich in several
NMR active isotopes: 1H, 29Si, 27Al, and 23Na. 29Si magic
angle spinning (MAS) NMR can be used to examine the siliconoxygen bonding in a cement sample as a function of hydration time. This facilitates the understanding of CSH
formation (6, 22).
Various forms of SiO bonding are shown in Figure 8
(24, 25). The basic tetrahedral unit, (SiO4)4, is referred to
in this field as a Q0 unit, where the superscript on Q refers
to the number of (SiO4)4 units attached to the central
(SiO4)4 unit. Q1 represents a dimer and Q2 corresponds to
silicon atoms within a polymeric chain of (SiO4)4 units. Q3
and Q4 correspond to silicon centers from which increasingly
complex degrees of chain branching occur, as shown in Figure 8 (25).
29
Si NMR is especially useful for examining SiO bonding because an increase in the number of (SiO4)4 units
bonded to each Si center produces an increase in the average
electron density around the central Si atom. This leads to a
more negative chemical shift, relative to tetramethylsilane
(TMS), for successively increasing n values in Qn (see Figure
8 for typical values).
In the pre-induction period of cement hydration, 29Si
MAS NMR shows the presence of monomeric (SiO4)4 units,
Q0. 1H NMR shows that in the first few minutes protonation of the (SiO4)4 units also occurs, an indication that the
surface hydroxylation mentioned previously (eqs 13) is probably the first step of the reaction (13, 24). As the reaction
continues, signals corresponding to Q1 units become predominant, indicating a dimerization of (SiO4)4 units. As time
passes the intensities of the Q1 signals decrease, and signals
corresponding to polymerization of the dimers, Q2, increase.
Crystallographic and NMR studies have shown that the primary species formed are pentamer (Si5O16)12 and octamer
(Si8O25)18 units (13).
It is interesting to note that Q3 and Q4 signals are not
observed for silicon in the hydration of Portland cement, indicating that polymerization takes place predominantly in a
linear fashion without branching. 29Si MAS NMR spectra
628

of pure C2S and pure C3S in comparison with a Portland

cement (PC) sample that had been hydrated for 28 days are
shown in Figure 9. Broad Q1 and Q2 signals in the 75 to
88 ppm region of the cement sample show the presence of
dimer and linear polymer units. However, the signal corresponding to C2S in the hydrated cement sample remains
essentially unchanged after 28 days, which shows the slow
hydration rates of C2S relative to C3S. This is why the production of C3S in the cement clinker is so vital for effective
cement hydration (24).
Data from NMR experiments such as these, combined
with X-ray crystallography and microscopy, can be used to
postulate a general structure for the cement paste. CSH gel
has structural features similar to that of two naturally occurring
minerals: Tobermorite and Jennite (13, 20). In fact, CSH
gel is often referred to as Tobermorite gel in the cement literature. These minerals, shown schematically in Figure 10, are
characterized by linear Q2 type OSiO bonding and are
formed as multiple layers separated by layers of Ca2 or
Ca(OH)2.

O
O

Si

Q0= -70 ppm O

O

Si

Si

O
O

Si

O
O

Si

Q2 = -88 ppm

Si

Q1 = -80 ppm

O
O

Si

O
O

Si

O
O

Si

Q3 = -98 ppm
O

Si

O
O
O

Si

O
O

Si

O
O

Si

O
O

Si

Si

O
O

Q4 = -110 ppm

O
Figure 8. Various arrangements of siliconoxygen bonding are expressed using a superscripted Q, where the superscript refers to
the number of (SiO4)4 units bound to the central (SiO4)4 unit in
the cluster. The average 29Si NMR signals (relative to TMS) are also
shown for each unit. For simplicity, charges are omitted.

Journal of Chemical Education Vol. 80 No. 6 June 2003 JChemEd.chem.wisc.edu

Chemistry for Everyone

Cement Degradation
Crumbling cement, rust stains, and cracks in reinforced
concrete are commonly observed. These are a few examples
of a serious problem that costs North Americans nearly a billion dollars a yearcement corrosion (26). Corrosion in cement and concrete materials is a twofold problem because
the cement material and the steel reinforcement are both susceptible to corrosion, and the weakening of one generally accelerates the degradation of the other. Although cement
corrosion is complicated, the action of water is a common
factor (27).
Cement is a porous material containing a dual network
of pores. The capillary pore system, with a distribution of diameters that range from 50 to 1000 nm, extends throughout
the system, acting as channels between various components
of the system. The cement gel itself contains a network of gel
pores, with diameters on the order of 1050 nm (19, 28).

Physical properties of cement such as its elastic modulus, fire resistance, and durability are directly related to the
amount of water present (29). Cement is generally 3040
mass % water, which is present in three forms:
1. Chemically bound water: Water of hydration chemically bound to the cement precursor materials in the
form of hydrates. This comprises more than 90% of
the water in the system.
2. Physically bound water: Water adsorbed on the surfaces of the capillaries. This water is most predominant in the small gel pores of the system.
3. Free water: Water within larger pores that is free to
flow in and out of the system. The amount of free water depends on the pore structure and volume, the relative humidity, and the presence of water in direct
contact with the cement surface, such as in water-bearing cement pipes and marine structures (19, 27, 30).
A

OH

Si
O

Si

O
Si

Si

Si

Ca

Ca

Ca

Ca

Ca

Ca

Ca

Ca

O
Si

Si

Si
O

O
Si

Si

Si

HO

Ca2+

HO

8 H2O

OH

Si

Ca2+

8 H2O

Tobermorite
[Ca4(Si3O9H)2]Ca2 . 8H2O
B

OH

O
O

Si
O

O
Si
O

Si

Ca

Ca

Ca

Ca

Ca

Ca

Ca

OH
OH

OH OH
OH OH

OH
OH

OH

OH OH

OH

OH

OH OH

OH

Ca

Ca

Ca

Ca

Ca

Ca

Ca

Ca

Ca

O
Si

Si
O

Si
O

Si
O

Si
O

O
Si

Si

6 H2O

Figure 9. 29Si NMR examination of cement hydration: (A) pure

dicalcium silicate, (B) pure tricalcium silicate, (C) Portland cement
sample hydrated at 40% by mass of water for 28 days. (A) and
(B) show Q0 29Si NMR signals (~ 70 ppm). The addition of Q1
and Q2 29Si signals (80 to 90 ppm) is seen upon hydration. The
slow hydration rate of dicalcium silicate is shown by a large peak
of unreacted pure material at about 70 ppm (22).

OH

Si

Si
OH

Ca2+

O
6 H2O

OH
Ca2+

Jennite
[Ca8(Si3O9H)2(OH)8]Ca2 .6H2O
Figure 10. Cement paste is believed to closely resemble the minerals Tobermorite and Jennite. These minerals are characterized by
layers of polymerized silicon oxide cross-linked with calcium oxide
or calcium hydroxide (13).

JChemEd.chem.wisc.edu Vol. 80 No. 6 June 2003 Journal of Chemical Education

629

Chemistry for Everyone

Corrosion of cement due to water can be discussed in terms

of physical and chemical corrosion.

Physical Corrosion of Cement

Physical corrosion of cements is attributable to the physical properties of water, especially its volume change during
freezing and its ability to dissolve cement components. The
most significant problem concerning degradation of cements
is the free water in the system. When cement is hydrated,
most of the water used in the process is taken up as hydrates.
If too much water is present, the remaining water is able to
move through the cement causing various problems.
Drying of a cement or concrete paste is an important
factor in the physical corrosion of cement. As a cement paste
hydrates over a period of several months, its porosity decreases. Initially, the drying process takes place through capillary flow of water in the larger pore system. As porosity
decreases, the drying process slows and becomes diffusive (13,
28).
Higher water:cement ratios in the hydration reactions
result in larger pore sizes as the cement gel forms, and these
pores contain a larger volume of water. Larger pore sizes also
lead to faster drying rates, which is a serious problem in areas with low humidity. When cement is exposed to low humidity, free water in the large pores (> 50-nm diameter)
evaporates quickly. This water removal is not serious if the
cement is in contact with water periodically because large
pores also quickly fill with water. However, if cement is exposed to an extended period of low humidity and high temperatures, adsorbed water in the gel pores of the cement will
evaporate. This process leads to drying shrinkage. Drying
shrinkage is destructive because partially filled gel pores (5
50-nm diameter) contain water menisci that exert considerable tensile stress on the walls of the pores. This stress leads
to microcracking and eventually weakens the material. The
use of aggregates minimizes the effect of drying shrinkage
because aggregates increase the elastic modulus and compressive strength of the finished product (28).
Cements in maritime climates at midlatitudes are particularly susceptible to stress owing to a process known as
freezethaw cycling (6, 28, 30). Freezethaw cycles occur in
winter when ambient temperatures hover near 0 C. In these
climates freezethaw cycles can occur on nearly a daily basis
in a typical winter season. Freezethaw cycles are damaging
to cements because of the 9% volume increase of water upon
freezing (31). When water in the capillary pores freezes, it
expands and exerts stress on the pore walls. This leads to
microcracks, which can in turn fill with water during the subsequent thaw period. Stress exerted in the microcracks during further freezing will extend the cracks until macroscopic
cracking is observed. While freezethaw degradation generally is most serious at the surfaces of the cement structure,
extensive cracking will allow the penetration of water deeper
into the structure leading to the eventual failure of the system (6, 30).
Crystalline calcium hydroxide makes up about 10% of
the volume of most common cements (5, 13, 15), and serious physical corrosion of cements results from the leaching
of calcium hydroxide (15). With a room-temperature solubility of 1.7 gL (15), calcium hydroxide can be easily dissolved in free water within cement pastes. This is especially
630

problematic with pure water, for example, rain water, melted

snow, and condensation within pipes (32). Removal of calcium hydroxide leaves void volumes within the cement, causing a loss of strength and allowing the deeper penetration of
leaching waters (15, 27, 30).
Calcium hydroxide leaching can be observed in a spectacular effect: opaque white material appears to ooze out of
concrete walls or hang in a stalactite formation from concrete ceilings. In this case, water containing dissolved calcium
hydroxide has leached out of the concrete and evaporated,
leaving behind a layer of calcium hydroxide that reacts with
carbon dioxide to form calcium carbonate (15)
Ca(OH)2(s) + CO2(g)

CaCO3(s) + H2O(l)

(10)

in a process known as efflorescence.5 Efflorescence is often a

sign of water seepage problems in the concrete or cement
structure.

Chemical Corrosion of Cement

Water also carries chemical agents into cement pastes that
react to destroy various components of the cement. A serious problem is the action of acidic waters from acid precipitation, industrial effluent, or the decay of organic matter (6,
15, 32). Acids also lower the pH of the pore water within
cement pastes, which otherwise has a pH of 1113 owing to
the large amount of calcium hydroxide present (5, 15, 30).
Lowering the pH will also increase the rate of the corrosion
of the iron in iron-reinforced cement.
The conversion of calcium hydroxide to calcium carbonate through the action of carbon dioxide in the atmosphere
is a problem for all types of cement. This can take place directly on the surface (efflorescence), or as the CO2 diffuses
into the cement (5, 15, 30):
CO2(g) + H2O(l)
H2CO3(aq)
(11)
H2CO3(aq) + Ca(OH)3(s)

CaCO3(s) + 2H2O(l) (12)

H2CO3(aq) + CaCO3(s)
Ca(HCO3)2(aq) + Ca(OH)2(s)

Ca(HCO3)2(aq)

(13)

2CaCO3(s) + 2H2O(l) (14)

This process, called carbonation, depletes the cement of calcium hydroxide and leaves CaCO3 deposits inside the cement.
Another problem, particularly in marine environments,
is the action of corrosive sulfates such as ammonium sulfate
and magnesium sulfate on cement. These salts react with calcium hydroxide to form calcium sulfate (12, 15):

(NH4)2(SO4)(aq) + Ca(OH)2(s)
CaSO4(s) + 2NH3(aq) + 2H2O(l)

(15)

Mg(SO4)(aq) + Ca(OH)2(s)
CaSO4(s) + Mg(OH)2(aq)

(16)

Reactions that deplete cement pastes of calcium hydroxide

are particularly destructive because the products are usually
materials with significantly larger volumes. For example, the
volume of calcium sulfate, 74.2 mLmol, formed in eqs 15

Journal of Chemical Education Vol. 80 No. 6 June 2003 JChemEd.chem.wisc.edu

Chemistry for Everyone

and 16 is more than twice the volume of the calcium hydroxide removed, 33.2 mLmol (5). This volume change
leads to stresses and cracks that further accelerate the processes discussed above.

Behavior of Water in Cement

Understanding the behavior of water in porous cement
is central to the understanding of cement corrosion. Various
theoretical and statistical-mechanical approaches have been
used to try to describe the movement and distribution of
water in the pores of cement (27, 3335). However, for many
years examination of water in cement pastes was hindered
by the absence of viable experimental techniques for observing its presence. Recent developments in nuclear magnetic
resonance imaging have provided valuable experimental data
(6).
Magnetic resonance imaging (MRI) is a common technique used in imaging materials, especially biological materials. MRI is typically used to measure the spatial distribution
of water in a material (21, 36, 37). It is based on the principle that the nuclear magnetic resonance frequency of a
nucleus, such as 1H, in a magnetic field gradient is proportional to its spatial position in the magnetic field gradient
(17)

where is the observed NMR frequency, is the magnetogyric ratio of the nucleus, is the chemical shielding of the
nucleus, B0 is the magnetic field associated with a static field
measurement, Gz(z) is the magnetic field gradient (dB/dz),
0 is the NMR frequency in the static field (B0), k is a scaling constant for the signal, and z is the position of the nucleus
in the field (21). Figure 11(A) shows two nuclei in a magnetic field gradient Gz = dBzdz. In Figure 11(B) an interferogram is produced when a 90 radio frequency pulse is
applied. Fourier transformation of the signal in (B) produces
two peaks separated by = Gzdz , shown in Figure 11(C).
The width of the individual peaks is proportional to (T2)1,
which gives a resolution, dz,
dz

1
Gz T2

Gz =

dBz
dz

z
dz

(1 )( B0 + Gz ( z ))
= 0 + kz
2z

90o pulse

sample is moved through a stationary field gradient of a superconducting magnet. STRAFI experiments have allowed
the detailed examination of water in solid cement samples
(35).
Imaging techniques such as STRAFI are useful for examining the effectiveness of waterproof coatings. One of the
easiest ways to prevent cement corrosion is to prohibit the
movement of water in and out of the material by establishing a waterproof barrier on the exposed surfaces (6, 30). A
wide variety of surface coatings are used in the waterproofing of cements; for example, a common class of waterproofing agents is silanes (22). The rate and depth of surface water
absorption into the cement surface can be compared for a
series of coatings and treatments. The depth and durability
of the surface treatment can also be examined for various applications (6, 22). A STRAFI image of a Portland cement
sample coated with methyltrialkoxysilane is shown in Figure
12. The images show penetration of the silane coating as it
is repeatedly applied to the surface. After 24 hours the coating penetrates to a depth of about 2.5 mm. A comparison of
the water penetration in treated and untreated Portland cement is shown in Figure 13. The treated sample shows water
on the surface (intense surface signal) and the silane coating

(18)

where T2 is the spinspin relaxation time of the nucleus (22,

23). The shift in the NMR frequency of a nucleus is proportional to the position of the nucleus in the sample, while the
signal intensity corresponds to the amount of that nucleus
present.
Water in gel pores is tightly confined and is susceptible
to the effects of various paramagnetic species in the sample
including iron and aluminum (6). These factors combine to
make the spinspin relaxation times short, dramatically decreasing the effective resolution (6, 37). For example, using
conventional MRI techniques, a field gradient of about 10
Tm is necessary for a resolution of 10 mm in a cement paste
(6). This is much greater than the normal field gradients used
in MRI, but is on the order of the stray fields associated with
the superconducting magnets of high-resolution NMR instruments.6 In 1988, a MRI technique known as stray field
imaging (STRAFI) was developed (38). In this experiment a

width ~

1
T2

= Gz dz
Figure 11. Schematic of conventional MRI experiment. (A) Two nuclei situated in a magnetic field gradient, Gz, are separated by
dz. (B) A 90 RF pulse is used to obtain an interferogram of the
nuclei in the sample. (C) Fourier transformation of (B) gives two
peaks separated by a frequency proportional to their separation
in the sample (21).

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631

Chemistry for Everyone

penetrating to about 23 mm. The untreated sample shows

little surface water but significant water penetration to 89
mm after 24 hours (22).
While STRAFI is a powerful technique for examining
the water content of a cement paste, it is limited to relatively
small sample sizes ( 2-cm diameter) because of magnetic
field constraints. Studies of concrete are limited to those with
very small aggregates such as fine gravels and sands (28).
Another way of alleviating the problem of short T2 while
avoiding enormous field gradients is through the use of single
point imaging (SPI; ref 21, 39). SPI is an MRI technique
that uses an oscillating field gradient in which signals are measured at a constant encoding time, tp, following a radio frequency (RF) pulse. A recent variation on SPI developed by
Balcom et al. (40) has proven useful in the examination of
water in cement samples. This technique, called SPRITE
(single point ramped imaging with T1 enhancement), uses a

ramped magnetic field gradient that is much easier to control than the oscillating gradients used in conventional SPI
(28, 29, 40). While conventional MRI, including STRAFI,
measures all resonance frequencies simultaneously and
deconvolutes using a Fourier transform, SPRITE uses a process called position encoding where only one frequency, corresponding to a particular encoding time, tp, is measured. The
spatial position, z, of the analyte nucleus is encoded in reciprocal space such that the signal, S(k), is proportional to k
(40):
1
2 Gz,max tp

k =

(19)

With a constant encoding time, k is inversely proportional

to the maximum field gradient, Gz,max. A schematic SPRITE
imaging sequence and resulting image are shown in Figure
14. Following an RF pulse a single frequency is measured
after a desired encoding time, tp. Next, the field gradient is
ramped and the sequence is repeated. Each sequence gives
the nuclear density at a particular point in the sample.
Through repetition of the sequences at varying Gz,max an im-

A
RF

RF
tp

z1

RF
tp

RF
tp

z2

RF
tp

z3

z4

tp

z5

Time

B
Figure 12. One-dimensional STRAFI image of a Portland cement
sample coated with methyltrialkoxysilane. The coating is applied
every 30 minutes during the analysis. The signals show the ingress
of the polymer coating into the cement to a depth of about 2.5 mm
after 24 hours (22).

Gz

Time

Signal

z1

z2

z3

z4

z5

Figure 13. One-dimensional STRAFI of Portland cement samples in

contact with water for 24 hours. Sample A was treated with methyltrialkoxysilane. Sample B was untreated and shows deep penetration of water into the cement surface (22).

632

Figure 14. Schematic of the SPRITE imaging sequence: (A) the signal is measured after a time, tp, has elapsed from an RF pulse; (B)
the ramping of the field gradient that accompanies the measurement of signal; (C) each successive sequence will show the density
of the analyte nucleus at a particular position, dictated by the gradient used during that sequence (40).

Journal of Chemical Education Vol. 80 No. 6 June 2003 JChemEd.chem.wisc.edu

Chemistry for Everyone

2 MT0
r H

A
RF

RF
tp

T1

RF
tp

RF
tp

T2

RF
tp

T3

tp

T4

T5

Time

Gz

Time

(20)

where T is the freezing-point depression, is the surface

tension of the liquid, M is the molecular weight, T0 is the
normal freezing point, r is the pore radius, is the density
of the absorbate, and H is the molar enthalpy of fusion (41).
Information on the freezing-point depression of water in a
cement sample is valuable for the determination of pore distributions in these materials.
As ice forms in a cement sample the internal pressure of
the closed system increases owing to the volume expansion
of water. The resulting pressure increase once freezing begins
in the gel pores forces the migration of water from the gel
pores to larger pore regions where ice will form immediately.
This results in a secondary freezing point at about 40 to 45
C (29). Figure 16 shows a measurement of these two freezing phenomena for a cement sample measured using an SPI
technique (29), in which the evaporable water content of a
concrete sample is measured as a function of temperature as
the sample is slowly cooled (2 Khr). The first freezing event
is seen between 0 and 1.6 C. As the sample temperature is
lowered the amount of evaporable water decreases slowly at
freezing temperatures corresponding to the respective pore
sizes present. The large change at 0 to 1.6 C shows that the
majority of evaporable water present is contained in large
pores. The second major freezing event, associated with the
desorption and freezing of water from the gel pores, is shown
at 45 C. Other studies have shown that evaporable water
can still exist in cement samples at temperatures as low as
90 C (29).

T1

T2

T3

T4

T5

Temperature
Figure 15. Schematic of SPRITE used for temperature dependent
measurements. (A) The normal SPRITE sequence from Figure 14 is
used again, but (B) the field gradient is kept constant. (C) This allows for a repeated measurement of the signal density for analyte
nuclei at a particular position in the sample as a function of temperature (40).

1.0

Magnetization (arb. u)

T =

Corrosion of Steel Reinforcement

Reinforced concrete is often used in bridge decks, roads,
and sidewalks. One of the most serious threats to concrete
in cold climates is the use of deicing salts in the winter to
ensure safe conditions for motor vehicles and pedestrians

Signal
at z 1

age is produced. SPRITE and other SPI techniques take

longer than conventional MRI techniques, but are less susceptible to noise and magnetic inhomogeneities in the sample
because only one frequency is analyzed at a time (21, 28, 29,
39, 40). SPRITE is also useful because signal resolution depends only on the size of Gz,max and the ramping sequence
used, not on the T2 of the analyte nucleus (40).
SPRITE can be used to examine the behavior of protons in a concrete sample as a function of physical parameters such as temperature. From eq 19 it can be shown that
keeping Gz,max and tp constant results in repeated measurements of protons in a defined position, z. The intensity of
the signal can be observed as a function of temperature,
shown in Figure 15. Through an adjustment of parameters
such as Gz,max, RF flip angles, and tp, the experiment can be
tailored to be sensitive to a nucleus of defined T2. This allows the ability to differentiate between the protons of free
liquid water (T2 200 s) and ice (T2 10 s) in a cement
sample. By following the appearance and disappearance of
free water at various regions of a cement sample in the freeze
thaw cycle, characteristics of the material can be examined
(29, 40).
In cement gels, MRI has shown that water freezes in two
steps. The first step occurs between 0 and 2 C, where free
bulk water and water in the capillary pores freeze (29). This
freezing-point variation is due to a freezing-point depression
phenomenon caused by vapor pressure lowering in the capillaries and related to the pore size of the capillaries by the
Kelvin equation (29),

0.8

0.6

0.4

- center
- drying face

0.2

0.0
-50

-40

-30

-20

-10

10

T / C
Figure 16. Magnetization signal for evaporable water in a sample
of Portland cement mixed with 14-mm diameter graded quartz aggregate measured using SPRITE as a function of temperature. Freezing of water is associated with a decrease in signal intensity (29).

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633

Chemistry for Everyone

(6, 15, 26, 42, 43). Chloride ions, when transported by water, attack steel reinforcement (rebar) of these structures causing them to weaken from within. High pH is important for
minimizing the rate of steel rebar corrosion because it allows
the formation of a passive oxide layer on the surface of the
metal (6, 30). Low pH aqueous states caused by the leaching
of calcium hydroxide from the cement, combined with chloride ion ingress, causes extensive rebar corrosion in short periods of time. Chloride ions set up redox reactions along the
rebar, as shown by the following equations (26):

2 Fe(s)
O2(g) + 2 H2O(l) + 4e
2 Fe2(aq) + 4 Cl(aq)


2 FeCl2(aq) + 4 OH (aq)
2 Fe(OH)2 +

2 Fe(s) +

/2 O2(g)

/2O2(g)

2 Fe2(aq) + 4 e

(21)

4 OH(aq)

(22)

2 FeCl2 (aq)

(23)


2 Fe(OH)2 + 4 Cl (aq)

(24)

Fe2O3(s) + 2 H2O(l)

(25)

Fe2O3(s)

(26)

Chemical attack of chloride ions is destructive because it not

only reduces the amount of hydroxide ion and iron, but it
also acts in a catalytic manner. Transport of chloride ions
throughout the system is also increased as cracks form as a
result of the other decay processes. Furthermore, patching
can create localized corrosion cells between the rebar in the

existing chloride-contaminated concrete and in the new

chloride-free patch, accelerating the concrete corrosion (43).
Waterproof coatings will stop the introduction of new
chloride ions, but will not remove the chloride ions already
present in the system. Coatings also become ineffective if the
concrete surface is cracked or damaged (26, 43).
A particularly interesting approach to treating chloride
ion ingress is electrochemical chloride extraction (ECE), in
which chloride ions are effectively pulled from the concrete.
A dc circuit, shown in Figure 17, is set up using rebar as the
anode and an electrolyte gel packed on the concrete surface
as the cathode. When a dc potential of 10,00030,000 V is
applied, water hydrolyzes at the anode, replenishing the hydroxide content of the system. The negatively charged steel
rebar repels chloride ions to the surface of the concrete and
into the electrolyte gel. After 48 weeks the process is complete, at a fraction of the cost of replacement (43). After sealing with a waterproof coating, the concrete is effectively
protected against further rebar corrosion.
Structures with extremely problematic chloride ion problems, such as ocean piers, can be cathodically protected by
constant maintenance of the rebar at a negative potential of
about 10,00030,000 V (43).
Concluding Remarks
The study of cement offers an opportunity to explore
the chemistry of earth materials, their preparation, and resulting properties. Furthermore, examination of cement degradation comprises an extensive part of modern cement
chemistry. Recent innovations in research techniques have
made the study of cement preparation and degradation behavior more accessible. Improvement of corrosion resistance
in cement and concrete structures would significantly
lengthen the lifetime of applications using these materials,
potentially saving billions of dollars worldwide.
Acknowledgments

DC power supply

steel rebar

Cl

H2O

H + OH

H2O

H + OH

Cl

Notes

electrolyte gel

concrete sample
Figure 17. Schematic of electrochemical chloride extraction (ECE).
A dc voltage of 1030 000 V is applied between the steel rebar
(anode) and an electrolyte gel (cathode) on the surface of the concrete. Hydrolysis of water takes place at the rebar and chloride
ions are repelled from the concrete into the electrolyte gel (43).

634

This work was supported by the Natural Sciences and

Engineering Research Council of Canada and the Izaak
Walton Killam Trusts.

1. Portland stone, a gray stone quarried from the Dorset

region of England, was a commonly used building material in
Europe in the 16th19th centuries (2, 7).
2. Founded in 1898, ASTM International is a nonprofit organization that provides a global forum for the development and publication of voluntary consensus standards for materials, products,
systems, and services. See http://www.astm.org (accessed Mar 2003).
3. Fluxing is a process that promotes fusing of materials, in
this case by lowering of the melting point of a mixture by adding
another component (7).
4. Ettringite is a collective term referring to the various aluminate and sulfoaluminate phases present in the clinker material.
5. Efflorescence is the blossoming to a powdery substance
on exposure to air.
6. The stray field near a 9.4 T (400 MHz) NMR magnet is
on the order of 60 Tm.

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Chemistry for Everyone

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