KALMATRON Corporation

Dr. Alex V. Rusinoff, PhD, S.P., Founder & Chairman

KALMATRON KF-A FOR HIGH

PERFORMANCE CONCRETE

Author: Dr. Alex V. Rusinoff

Date: March 26, 2004

KALMATRON CORPORATION
276 Michelle Court,
South San Francisco, CA 94080 USA
Phone: +1 (415) 385-3290
website: www.kalmatron.com
e-mail: KalmatronWorld@aol.com
Fax: (650_872-2555
 Alexander V. Rusinoff
Concrete batch with KALMATRON
KF-A where W/C = .41; slump 2
This concrete is applicable with
shotcrete providing high adhesion and
waterproofing advantages.
Unique application of KF-A to repair a
clinker kiln foundation: the concrete
mix with KF-A admixture was applied
in an environment with a temperature
of 185F (85 C) with perfect adhesion
and zero cracks.
2 slump Kalmatron KF-A
concrete 32 MPa delivered to a
40 (m) height. No bleeding of water,
no cracks, with 25% higher
compressive strength.
Concrete with KF-A is applied by
shotcrete for waterproofing
underground structures.
Kalmatron for High Performance Concrete Page 1 2004
KALMATRON KF-A FOR HIGH PERFORMANCE CONCRETE
High Strength/High Performance Concrete (HPC) is characterized as a concrete
mix design that sustains controlled batch workability with further adequate
resistance to climatic and urban environments after application, i.e., performance
durability. There is a multitude of admixtures on the market to achieve HPC
features with the functions of densifiers, thinners, retarders, stabilizers, and
agitators. All of them are functional substitutes for the natural cementitious gel
performance.
KALMATRON KF-A admixture is a conceptually new product patented in the
USA (#5,728,428). This is an inorganic oxidizer of micro/macro metal elements
contained in cementitious materials providing electro-chemical decay of cement
grain by electrolysis between inversely charged particles of electrolyte and
cement grain. Decay-hydration reactions result in maximum volume of
cementitious paste as a continuous solid phase in which the aggregates are
embedded.
Extension of the gel surface classifies KALMATRON KF-A with admixtures
known as Type C accelerating admixtures, and Type F water-reducing, high
range admixtures (See ASTM C 494).
RHEOLOGICAL ADVANTAGES OF CONCRETE WITH KALMATRON KF-A
Reduces shrinkage, 200300 micro-strains is a typical result. Just no cracks
Increases compressive strength by 20 to 35%
Exothermic heat is lower 30% to 50%
No flakes, efflorescence, dusty spots, or slid areas
Water impermeability is 100% starting at 50 mm or 2 concrete thickness
Highest resistance to chemical and climate corrosions
Increases frost-resistance up to 35%
Tensile Resistance is higher up to 40%
Contains approximately 3% macro and 97% micro pores
CONCRETE APPLICATION ADVANTAGES WITH KALMATRON KF-A
Accelerates cure without affecting working time
Less heat build up when cured in mass. No bleed water
Mixing up to 5 hours keeps batch revived with insignificant slump reduction
Mixes are more cohesive and will not separate if vibrated, yet flow better
Twice lower material loss on shotcrete application with build in one pass
rd th
Early strengthening on 3 to 7 day with higher compressive strength at 25%
Metal parts of equipment are cleaner than usual
Highest adhesion to most known porous materials
Allows application from -5 C to 40 C without affecting the set time
The need for concrete curing membranes is virtually eliminated
Yield of concrete mix is higher by 3% to 6%
Reliable raw compaction of concrete mix
Pumpable concrete mix flow with slump at 2 to 3
ECONOMICAL ADVANTAGES OF CONCRETE WITH KALMATRON KF-A
Eliminates the use of any known admixtures and supplementary materials
Do not apply polymers, fibers, Pozzolana, water-reducers, silica fume, fly ash,
strength agitators, retarders, plasticizers or any other materials
Setting-Accelerators and Air-Entrainers are applicable due to application
Does not require curing compounds and heat/cold insulations
th
Ready to use on 7 day of natural hardening for any structures except bending
structural elements. They have to be aged with project request
Doesnt need to be isolated for liquid containing structures. KF-A itself
waterproofs concrete 24 hours after application
Yield of batch is higher by 3% to 6% which is significant for precast industry
Reduces labor time on vibrating and flattening by 15% to 20%
One pass application for precast and stucco industry
HOW KALMATRON KF-A WORKS
KALMATRON KF- A as an admixture transforms the most conventional
concrete mix designs to concrete with stable High Performance features, while
the cost is much lower.
Alexander V. Rusinoff Kalmatron for High Performance Concrete Page 2 2004

A concrete mix contains a lot of structurally useful minerals, which are not used at all since the active agent is water
only. Water is not active enough to involve them in hydration and hardening processes. KALMATRON
KF-A admixture provides agitation of cementitious mixes in chain reactions. The gradated solubility of
KALMATRON KF-A components sets up a sequence from first reaction to fourth, if the initial dosage of water is
reduced enough and mixing done completely. Otherwise, as practice shows, the whole chain of reactions will be
delayed by 30 days. But the final performance of this product will be the same as described below.

1. Dissolution of cement grain by speeded hydration. The stage when standard hydration speed increases due to
weakening of molecular tensions of water with electrolytes formed by KF-A. The standard reactive bawl of a
concrete batch has some potential energy which should be spent on hydration and structure formation. With KF-A
part of this energy goes to the electrochemical decay of cement grains and after that on to hydration itself. The
results of this reaction are:

The chemical heat of hydration is lower. The tensional heat of water absorption subsides proportionally as the
area of the cement gel surface increases. That means much lower exothermic reaction heat.
Prolonged equalization of solution concentrations during the mixing and transportation of the concrete mix give
the best compaction, which results in low slump with high workability.
Also, this retards the shrinkage dynamic in the first 60 days.
Provides natural increase in structural strength by enhanced compaction.

Similarity to known: This type of reaction may be recognizable in the application of salts with some plasticizer.
On the first 28 days it gives a huge increase in strength. But the consequences of such an application after 45 days
are recognizable also since concrete gets dusty, cracked, and fragile because the ion-kation exchange is out of
control. It means that concentrations of inter porous solutions are really high with immediate ability for self-
crystallization before the concrete hardening process begins. That creates opposing tensions in the concrete body.
Early crystallization means aging of concrete before maturing.

2. Oxidation of metal containing elements. Involvement of negatively charged artificial minerals provides magnetic
reorientation of water dipole molecules and particles of cement grain. Weakening of their relations by reorientation
causes ordered rotation with considerable freedom to be involved in the hydration reaction with a greater amount of
cement particles. Thats why KF-A has higher effectiveness with lower quality cements. This reaction results in:

Darker color of concrete because there is no lime emission during drying;

Up to two times lower exothermic heat emission, since that energy is taken for oxidation;
As a result of the above, porosity becomes milder in size of development from depth to surface of concrete;
Shrinkage is 1 to 2 times lower than conventional;
Electric conductivity increases because of metal oxidation. In concrete maturity stage it becomes normal;
KALMATRON Concrete behaves as a High Alumina Concrete in respect to corrosion resistance, compressive
strength, impermeability, and abrasion resistance, i.e., an ironed concrete.
Cementitious paste volume increases by 10% and higher which depends on cement quality. Thats why it worse
cement is better KF-A performance.

Similarity to known: Actually, this reaction is similar to the function of magnetized water. The distinguishing part is
that the KALMATRON KF-A admixture provides a more stable residual polarizing effect. The followers of
KALMATRON KF-A created an admixture which only functions like this with well-ground magnetic materials. Test
results are not stable and have never been applied in the field because natural concrete magnetic conductivity is
random enough.

3. Colloidation of free molecules of water the thickening of water by solutions with high concentrations. Since
most cement grains are hydrated and the inter porous liquid-vapor part is represented by natural mineralogical
cementitious solutions, then:

superficial vapor emission is slower; that reduces shrinkage;

concentration of solutions on the surface and inside the concrete body changes almost simultaneously;
osmotic pressure is very low and thats why hydrothermal deformations are not significant;
number of pores is lower and different types of pores are fewer, i.e., ordered porosity.

Numerous mineralogical sediments become natural centers of cementitious solutions and densify until
crystallization. Solutions with lower concentrations stay diffuse to the close of the colloid phase in accordance with
gradated concentrations. The speed of colloidation is slow and the whole process may take decades.
 Alexander V. Rusinoff Kalmatron for High Performance Concrete Page 3 2004

This reaction results in:

Homogeneity of concrete structure with considerable compaction of concrete aggregates;
Increase in macro-structural density from 3 to 5%;
Early strength on third or seventh day;
Liquid impermeability is 100% in respect to initially targeted type of concrete;
Oxide film resists rebar corrosion; that is observable by any detector pulled out from a batch;
Physical resistance to freeze-thaw cycles and cycling drying-saturation types of corrosions because of better
compacted structure and ordered porous structure.

Similarity to known: This reaction is recognizable in natural hardening. The difference is that the KF-A admixture
provides structural formation by hardening much faster and relatively more simultaneously from surface to depth.

4. Stabilization of the gel of the cement paste. Obviously, this is a result of naturally growing viscosity of
solutions in cement paste. The approximate time of this process is from 7 hours to fourteen months, which is much
longer than for conventional cement paste. The longer term of the gel phases presence in the concrete body
results in:
Growth of micro-structural density;
Dynamic growth of liquid impermeability;
Increase of crystalline containing part by natural drying of cement gel;
Stable and predictable growth dynamic of compressive strength;
Dominant type of continuous porous system up to 97%;
Lower pore suction ability, below 5%, with reduced superficial tensions of saturation;
Creep of concrete is stable and indicative after 91 days.

A similar mechanism of concrete improvement can be observed

when water treated in a magnetic field is added to concrete. In a
magnetic field water molecules loose their attractive-repulsive
forces and become oriented on a magnetic pole or electric charge.
Neutralized molecules of water are much more easily attracted to
numerous electrostatic fields naturally contained by cement grains.
Hydration of cement is faster and more complete than with
untreated water. However, on an industrial scale magnetic water
treatment facilities would create environmental and economical
disadvantages.

When the hydration reaction is entirely complete, the highest

Figure1. Concrete specimen
KALMATRON shows completed cement hydration.
performing concrete rheological features are measurable simply
by the density which results from the ingredients structural
compaction. The petrography analyses in this case show the
unusually high contents of a densely integrated cementitious
paste.
treated with
Fig. 1 shows a hardened cementitious paste with areas like
melted and opened shells, which are the hydrated cement grains.
The combination of hydration and electro-chemical decay of
cement grain results in a maximally densified concrete structure.
We never found an intact cement grain but still call it an almost
completed process.

The maturation of a concrete batch begins from simple

evaporation of excessive water from the surface. For conventional
concrete it is the first step for superficial cracking and aging. KF-A
added to the concrete mostly contains liquid electrolytes, which
have a very slow evaporation speed that helps to prevent not only
shrinkage, but allows the formation of macro pores.

THE MODEL OF CONCRETE MATURING

Figure 2. Unhydrated cement grain in
standard concrete structure. X60
Fig. 3 Model Of Concrete Maturing shows the principle of
Page 4
concrete structure formation in the distribution of cementitious
phases during hardening time. Obviously, the dominance of the
cement gel is preferable there to increase the ratio of micro pores
and reduce the self destructive nature of concrete. This is the
function of KALMATRON KF-A.
Alexander V. Rusinoff Kalmatron for High Performance Concrete Page 4 2004

Below is a description of concrete maturing stages from the surface

of evaporation to the depth of gel crystallization. Remarkably, the
diameters of capillaries of every phase comprise 4 of a water
molecule, which means that physically densifying the concrete
structure alone doesnt improve water resistance.

1- inter crystalline containing liquids of mineral solutions.

2- matrix of cement gel (paste) with of porous 15 ;
3- area of primary ettringite formation 30;
4- area of maturing of allite-belite and micro-capillary system 30;
5- ordered crystalline structure 500;
6- regular capillary and porous structure with 500 to 10,000.

Inversely oriented boundary osmotic pressures between

areas of concrete maturity cause the self-destructive
nature of the concrete structure. We have measured
those tensions, moisture, and temperatures with a
combined indicator, shown at right. Most tensions are
higher than concrete resistance to rupture.

Figure 3. The model of concrete maturing

CONSUMPTION OF WATER AND CEMENT HYDRATION

Modern admixtures and supplementary materials for the concrete mix are dedicated to improving applicability and
concrete rheology. Hydration of cement relies on the amount of water and mixing time only. Relative to cement
hydration, all this amount of water and admixtures work as thickeners or thinners of the water-cement solution,
which creates concrete structure independently from compaction of aggregates within the cement dough.
No enhancing chemical reactions occur with the hydration of cement grains in this case.

It is known that unhydrated cement grains present a major problem in new concrete structures (Fig. 2). Even the
final product of the cement clinker has a lot of foreign inclusions in the frame of the cement structure. During
hydration of Portland cement, approximately 25% to 30% of the hydration products form calcium hydroxide, which
is also known as free lime. This has no cementitious value by itself. It is soluble in water and is the cause of the
powerful conduction of liquids through the concrete body. However, 30% of cement in a concrete mix becomes not
only useless, but also harmful for the durability of the concrete structure.

What it takes to hydrate a cement grain is described in the source [1],

page 14. For instance, after 28 days in contact with water, grains
of cement have been found to have hydrated to a depth of only 4
m, and 8 m after a year. Dr. Powers calculated that complete
hydration under normal conditions is possible only for cement
particles smaller than 50 m, but full hydration has been
obtained by grinding cement in water continuously for five days.
The size of a regular cement grain is over 90 m.

Figure 4. Shotcrete Technologies Inc. did an
emergency repair project for the CO D.O.T. on
I-70 with KALMATRON KF-A. The shotcrete
was applied with slump 2 or 64 mm, the
temperature of concrete mix in the hopper was
lower than outside temperature by 8 F or
4.5C.
Concrete mix with KF-A needs 10% to 30% less water than the
standard concrete mix design. Nevertheless, workability is even
better with lower slump. KALMATRON KF-A hydrates almost all of
the cement grains, which effectively produces good workability at a
lower slump of only 2 3 (65mm90mm). The entire reduced
amount of water is used to hydrate all of the cement grains, leading to
complete compaction of concrete structure. There is no extra water
added to provide workability and there is no bleed water because all
of the water is effectively utilized.
Alexander V. Rusinoff Kalmatron for High Performance Concrete Page 5 2004

SLUMP AND WORKABILITY

Modern concrete technology controls concrete batch performance by major parameters

such as water to cement ratio, properly entrained air by admixtures, and high-range
water-reducing admixtures to increase slump. The Slump Test by ASTM C 143-78 does
not measure the workability of concrete, but is very useful in detecting variations in the
uniformity of a mix of given nominal proportions [1, p. 208]. However, over 30% of water
from the weight of cement that is poured into a concrete mix is aimed at providing
moveability for the concrete batch, where compaction of concrete ingredients is a
missing feature.

Workability can be defined as the amount of useful internal work necessary to produce
full compaction (of concrete mix) [1]. The test, known as the compacting factor test, was
developed at the Road Research Laboratory and is described in BS 1881: Part 2: 1970
and ACI Standard 211.3-75. Therefore, the Workability Test lets us recognize the
Slump 2
suitability of the present concrete mix for a particular job, but the Slump Test can only
show the complete list of ingredients for the targeted concrete mix design. There are two
main distinctive groups for slump recognition

STANDARD CONCRETE MIX

LOW SLUMP The application of a standard concrete mix with low slump from 1 to 2 (25-
50 mm) needs less cement fine aggregates and simpler curing because the slump is
stable. But it also needs more labor time for vibration and flattening because the
workability is very low.
Field of application: roads vibrated by power-operated machines, floors and light-loaded
shallow foundations.

MEDIUM SLUMP The application of the same standard concrete mix with medium slump
2 to 4 (50-100 mm) needs less labor time for vibration and flattening because the Slump 3
workability is really good. But it needs more cement and fine aggregates and takes time to
get full slump, which causes insufficient volumes for casting, additional concrete batches,
and another extension of labor time for targeted filling of mold and curing to avoid heating,
shrinkage, bubbling, cracking, etc. as prescribed for the standard concrete mix.
Field of application: roads vibrated by hand-operated machines; mass concrete
foundations; vibrated reinforced concrete slabs, beams etc.

CONCRETE MIX ENHANCED BY KF-A

WORKABLE SLUMP The application of the same concrete mix with 8.5 to 17 Lbs/cu. yd.
3
(5 to 10 Kg/m ) of KF-A varies with slump, needs less water and does not depend on
cement quality and fineness of aggregates. With slump ranging from 2 to 3 it has the
same workability, casting sufficiency and pumpability. It needs less labor time for vibration
and flattening, reduces time for equipment cleaning and eliminates labor time for curing.
Field of application: limitations not known due to the stable nature of HPC performance.
Slump 5
Therefore the most economically effective High Performance Concrete mix with the widest
field of application and the best combination of features should provide:

1. Low slump for one step technology of application (precast, stucco, etc.)
2. Workability with stable viscosity of concrete mix until hardening will begin.
th th
3. Early strength that matches targeted compressive strength appears on 7 to 10 day.
4. Liquid impermeability in 24 hours and growth during another 90 days.
5. Slowly growing flexibility during the first 45 days.

The dynamic performance of a conventional concrete mix

with KALMATRON KF-A provides:
Batch pumpability equals that of a mix containing high cement with medium slump
Hardening of concrete is dynamically close to that of Cement Type IV concrete mix
Because of high early strength, concrete performs like a concrete batch with Cement
Type III
In maturity stage, high resistance to chemical and climate corrosions with high liquid SLUMP IS ZERO.
impermeability, performing as a High Performance Concrete. And this batch is workable
and pumpable with KF-A.
 Alexander V. Rusinoff Kalmatron for High Performance Concrete Page 6 2004

TRANSFORMATION OF CONCRETE BY KALMATRON KF-A

Concrete specimens with The most widely known way to improve concrete quality is
Silica Fume increasing the cement content or applying fine-grained
cement in an attempt to achieve a higher volume of cement
gel. Increasing the cementitious volume of cement paste
with KALMATRON KF-A results in some specific
performances of the concrete mix.

Tests were conducted to evaluate concrete specimens with

Silica Fume and KF-A for resistance to chloride permeability
[2]. We found that the standard test procedure wasnt
suitable because even with water-saturated concrete
specimens, the electric conductivity of specimens with KF-A
was much higher. What occurred was a functional change
of concrete class from low content alumina cement
concrete to high content alumina cement concrete without
changing the initial amount of alumina content.

The chloride permeability test procedure is based on the

electric conductivity of concrete specimens saturated with
Concrete specimens with water and salt-water solutions. On the diagrams of present
KALMATRON KF-A
tests readings we can see that specimens with KF-A have
higher electric conductivity even in a water test, up to 40
times. Even without any salt saturation, concrete with KF-A
is more electrically conductive during concrete structure
formation, as shown by the given electrochemical activity.
Figure 5. Comparative testing of concrete electric
conductivity. The current in KF-A dosed specimens is For testing KF-A, were asking to keep both control and trail
higher. specimens in different baths. Otherwise, test results would
be very close for both groups of specimens because even a
light water solution of KF-A chemicals improves control
specimens significantly by exchange through the curing
water in the same bath.

During present testing, researchers [2] noted that some blue

film appeared on the surface of concrete specimens with
KF-A (Fig. 6). That blue film has a very high electric
conductivity due to its metallic nature. Obviously, after
complete oxidation of metal-containing elements in
concrete, the dominant remainder of metal oxides was
dispatched to the surfaces of pores and capillaries with
visible sediments appearing on the outside surface.

According to the source [1], measurements of Portland

Cement paste in water show higher electric conductivity, up
1
to 2 /2 times greater than ordinary Portland Cement
concrete. The difference in conductivity between Portland
Cement concrete and both Rapid Hardening concrete and
Figure 6. Chloride penetration test specimen after
completion of test. The blue colored substance High Alumina concrete is 10 to 15 times.
appeared after specimens dried. This is a solid film of
Tetracalcium Aluminoferrite crystals [2]. p. 20; 29.
The cementitious value of concrete is clearly measurable by electric conductivity, based on which quality control and
even the field of application can be established. As proven by many applications of conventional concrete with KF-A
for corrosion resistance, this is very important for evaluating further concrete durability.

It can also be regarded as a measure of a materials homogeneity [1]. Obviously, the bigger the volume of the
cementitious paste, the higher the homogeneity of the concrete batch. Cementitious paste has the highest electric
conductivity and contains moisture longer than other concrete ingredients. In a post maturing concrete age, the gel
and liquid phases are responsible for concrete resistance to industrial and climate corrosions.

The present test demonstrates that KALMATRON KF-A is a concrete class-upgrading admixture for conventional
and High Performance Concrete that was proven in numerous practical applications.
Alexander V. Rusinoff Kalmatron for High Performance Concrete Page 7 2004

LIQUID IMPERMEABILITY OF CONCRETE WITH KALMATRON KF-A

Pore blockers are very popular and people use this term for concrete impermeability. But the problem with concrete
is that it is not a homogeneous material and to add something else into its body means to multiply those problems.
Some product applied on or mixed with concrete has the ability to clog pores by growing into them like foreign
crystals. Nobody knows about the speed and volume of crystallization of those crystals and what the rheology of
these crystals is and how it will work for linear extension under cycling hydro-thermal conditions. The thickness and
mass of the concrete structure are crucial factors for a foreign pore blocker.

Impermeability of the Concrete Microstructure

Since the smallest diameter of a pore even in cement paste is 500 to 10,000 and a molecule of water has a
diameter of 4 only, concrete leaks like a sieve. So, what kind of pore blocker should be used to fill up pores from
at least 500 to 4 , which is 125 times? Therefore, a pores diameter is not a parameter for liquid impermeability
but a function of pore gradation and viscosity of inter porous solutions, wherein:
the pore gradation should be as low as possible to reduce hydraulic thresholds and tensile tensions;
the viscosity of inter porous solutions should be high enough for water thickening but not for conductivity.

Impermeability of the Concrete Macrostructure

The liquid impermeability of concrete structures is evaluated by measuring hydraulic pressure applied to a concrete
specimen until resistance is lost. After that we can mark water resistance as W2; W4; W6, etc. in accordance with
manometer gradation. Therefore, the indication of any improvement relates to a specified level of impermeability.
For example, if water resistance of concrete achieves 100% for a specimen with W2, it is not impermeable to a
higher hydraulic pressure as opposed to a specimen with W4 resistance. Waterproofing concrete results in its
ability to keep constant the mass of water contained under hydraulic pressure with stable indications of density and
compressive strength. Obviously, the surface of this concrete will have different capillary suction depth owing to the
degree of wetting as described by the Juren formula:
2U Cos
h = (1)
r g
Wherein: r is the radius of capillary, is the density of liquid, g is the acceleration of gravity, Cos is degree
of wetting, and U is a rate of evaporation. Suppose that the radius of the capillary is changed from the depths of
the concrete mix to the surface of evaporation:

ri 2U Cos 2UCos rI
h = d r = Ln 0;
(2)
ro r g g ro

which simply and encouragingly shows that minimizing the difference between the radii of capillaries in the center
and at the surface of the concrete structure (dominantly continuous porosity) increases water impermeability.

Capillary-porous forming process

The maturing concrete mix develops a capillary-porous system during cement hydration and gel hardening.
Actually, these voids are trace-ways of gas-bubbles from the exothermic reaction of cement hydration. The longer
the time of hardening, the longer it takes a bubble to escape from inside the cement dough up to the surface. That
is why slump and shrinkage are so high there. Of course the diameter of capillary-porous voids will be bigger when
the exothermic reaction is longer. This is one of the reasons why retardation of concrete hardening causes
structures to crumble and have low resistance to liquid permeability.

The same results occur with fast hardening and high speed
strengthening concretes, where bubbles are captured in the
cement paste and create inter structural tensions that are generally
directed from inside to outside of the concrete body. Further
development of tensions causes an increase of micro cracks, with
consequent reduction of compressive strength. Resistance to liquid
permeability is unstable, resulting in unpredictable and abrupt
leakage.

Concrete with KF-A admixture has advanced resistance to liquid

permeability 2 to 4 times greater in comparison with control
specimens because of its dominantly continuous porosity. It
prevents the formation of hydraulic thresholds in the structure and
forced migrations of inter porous moisture that increase the Figure 7. Waterproofing of water tanks by shotcrete
sorption ability of water from outside. with KALMATRON KF-A.
Alexander V. Rusinoff Kalmatron for High Performance Concrete Page 8 2004

The pressure of inter porous gases might be as low as possible, as described by equation (3), which is integrated
by three independent functions n, V, and t.

Rtn ni VI tI
2 2 2 2
P = = - R ndn dV/V tdt = 0.5R (n o - n i ) (t i - t i ) Ln [VI / Vo ], (3)
V no Vo to
Wherein:

no; nI number of cement grains at the beginning and after hydration, respectively; since nI <<no the integral will
get a negative sign and finally no 0;
Vo; VI volume of cement gel produced from cement grains at the beginning and after hydration;
tI; to - final and initial temperatures of exothermic reaction, respectively;
R Gas Constant;
______
2 2
= t i - t I entropy of cement hardening, where the volume of cement gel has been represented by equation (4):
R
2
R 0.5 n o
2 P
Ln VI = 0.5 n o ; or : VI = e ; (4)
P
i.e., the volume of cement gel has an exponential relationship with the complex of straightly and inversely related
parameters. This is the answer to how to increase the volume of cementitious paste. Since the number of cement
grains no and the entropy of cement hardening are constants in equation (4), we have to reduce the inter
porous pressure of exothermic gases P. KALMATRON KF-A was developed for this.
Further integration of equation (4) will show a factorial growth of no! which in thermodynamic terms means that
active surfaces increase during the decay-hydration process. But it will not affect previously accomplished
processes.

The mechanism of concrete waterproofing by KF-A

Hydrothermical and barometrical balance between outside humidity and moisture in the concrete subsurface is the
best hydroseal, as it works in natural rock. In regular concrete, the free molecules of water are involved in
hydrothermical and barometrical migrations in the capillary-porous system of concrete and passively depend on
outside changes. Because of this, even the sorption ability has a slowly growing dynamic through time.

During the hydration of cement gases are produced, and as the gases are released they create pores that mark
their passage through the still plastic concrete. In normal Portland cement the gas produced is carbon dioxide; this
gas must build up a bubble of a certain critical mass before it is able to rise to the surface. As a result, the pores
formed are large and are known as macro pores. The exothermic reaction provides enough heat for macro pores to
be produced and may even be dominant in the porosity forming process.
In concrete containing KF-A and the same cement the gas produced is
Acetylene (15) and it is released as soon as it is formed. The result is that the
gas bubble is very much smaller and so is the resulting pore diameter, hence
the pores are known as micro pores. Due to lower exothermic heat, the
process of pore formation goes much slower. The smaller pore diameter
means higher gas/vapor inter porous pressure, which prevents water from
penetrating the concrete.

Conventional concrete contains approximately 70% macro and 30% micro

pores. Concrete with KF-A contains approximately 3% macro and 97% micro
pores, making concrete far more resistant to water ingress.

We can hypothesize also the dominating presence of dead-ends and closed

pores. According to the test results, water resistance of specimens with KF-A Figure 8. Concrete mold made with
grows after repetitive cycles of hydraulic pressure, but the structural content KALMATRON KF-A passed a 15-day
of moisture is the same and stable. This is proof of the structural hydraulic test under 70 PSI hydraulic pressure, or
lock which is a usual property of natural rock characterized by superficial 5 At. The most simple and convincing
moistening only. test that was ever done.

Further development of equations (2) and (4) results in the marvelous

mathematical picture of a perfect concrete structure matrix. KALMATRON
KF-A makes that picture closer to reality.
Alexander V. Rusinoff Kalmatron for High Performance Concrete Page 9 2004

REDUCTION OF CONCRETE CORE TEMPERATURES WITH KALMATRON KF-A

The temperature of concrete delivered to a site in hot weather should not exceed 29C (85F). Cements with a limited
rate of heat evolution are known as Portland Cement Type IV, Portland blast furnace Cement Type P and IP with a
2
specific surface of about 320 m /Kg and heat of hydration of 300 Joules per gram (80 cal/g). These cements,
developed for massive concrete structures such as dams, have low initial cracking. Early strength of concrete with
these cements is very low but the ultimate strength is unaffected.

According to research [2] of core temperatures for a hardening concrete mix, KALMATRON KF-A provides a
noticeably lower concrete core temperature of cement hydration in concrete mix. The conclusion is based on a
reduction of exothermic temperature in the concrete mix with KF-A shown in Fig. 9.
th
At 1000 minute we can see the drop of tempe-
rature to 5.25C (41.9F) relative to the control
specimen. This is about 25% from the highest
exothermic peak. For the trial specimen itself the
readings range from 31.5C (88.7 F) to 27.75C
(81.95 F). For the control specimens these figu-
res range from 33C (92F) to 30.5C (86.9 F).
This is significant entropy for such a process as
the hydration of cement in a sampling volume.

Compared with control specimens in the same

time frame, the temperature of specimens
containing KF-A is more than twice as low.

The low heat feature is achieved by limiting lime

content after correction for lime combined with
SO3. The limit is:
CaO
1 (6)
2x4(SiO2) + 1x2(Al2O3) + 0.65(Fe2O3) Figure 9.

The heat of hydration consists of the chemical heat of reactions and the heat of water absorption on the surface of the
cement gel formed during the hydration process. These processes are consequent. In the first hours of hydration
regular cements give high heat indication, up to 500 joules per gram (120 cal/g). The heat of absorption is
approximately 25% of the summary heat indication, which is relevant to the current measurements mentioned above.

With some delay, the heat of absorption will dominate until the final setting time. The delay is explained by the
difference between hydration and absorption speeds. The faster the speed of hydration the sooner the absorption
process starts. The bigger the volume of gel forming, the less free water is left for other processes and that is why the
heat of absorption is lower. The difference between the high heat energy of cement hydration and the low heat energy
of absorption is the entropy of concrete structure formation. Obviously, KALMATRON KF-A reduces entropy by
reducing hydration heat emission that equalizes both reactions speeds.

FORMATION OF CONCRETE STRUCTURE WITH KALMATRON KF-A

The next equations are examples of the most probable reactions of KALMATRON KF-A with a concrete mix during
different stages of structure formation. However, abundance of water will cause discontinuance of (11), (12) and (17)
reactions with apparent retardation of effectiveness until the concrete batch naturally desiccates after 30 days. That is
why for KF-A application we recommend less water to produce a workable concrete mix.

Free calcium oxide in cement forms calcium hydroxide when mixed with water (7). Calcium hydroxide then
takes part in exchange reactions with sodium nitrate and calcium carbonate and sulfate and with calcium
chloride to form low-soluble and hardly-soluble acicular crystals of hydroxonitrates Ca(OH)NO3 (9) that will
continue to grow well after the complete formation of the cement stone structure by using free pore water
and Ca ions released from the cement stone gel.
Alexander V. Rusinoff Kalmatron for High Performance Concrete Page 10 2004

CaO + H2O Ca(OH)2 (7)

2NaNO3 + Ca(OH)2 Ca(NO3)2 +2NaOH; (8)
Ca (NO3)2 + Ca(OH)2 2Ca(OH)NO3 ; (9)
CaCl2 + Ca(OH)2 Ca(OH)Cl2 + CaOH (10)
CaOHNO3 + ag CaOHNO3 ag; (11)
CaOHCL + ag CaOHCl ag ; (12)
3Ca(OH)2 + 3Na2SO4 + 31H2O + Ca3(AlO3)2 3(CaO Al2 O3 CaSO4) 31H2O + 6NaOH; (13)
Ca(OH)2 + Na2CO3 CaCO3 + 2 NaOH; (14)
CaC2 + 2H2O Ca(OH)2 + C2 H2; (15)
3Ca(OH)2 + 6NaCl + [3CaO Al2O3] + 30H2O 3 [CaOAl2O 3 CaCl2] 30H2O + 6NaOH; (16)
3Ca(OH)2 + 6NaNO3 + [3CaO Al2O3] + 32H2O 3[CaOAl2O3 Ca(NO3)2] 32H2O + 6NaOH (17)

These crystals have a micro-reinforcing effect on segregation within voids under the effects of temperature, shrinkage
and corrosion. Therefore, a primary structure reinforcement framework is formed within the concrete mix as early as
the setting stage. This framework is built up in the direction of mass transfer of a diffusion flow.

Hardly soluble double salts of calcium sulfoaluminate 3CaAl2O3CaSO4 31H20 are

crystallized at the same stage. The crystals are in the form of hexagonal
syngonite-like structures or a package of parallel laminate with interstices filled
with inters crystalline solutions. The density, volume and strength of the entire
package depend on the density of such solutions. When moisture gets into the
interstices, the solutions are diluted, and the package volume increases. Given
the conditions in the pore spaces of concrete, this explains the exponential
decrease in permeability with time during tests. If temperature decreases, the
intercrystalline solutions break into crystalline hydrates and solutions of residual
concentration. The volume of the interstices decreases while the density and
strength of the structure as a whole increase to ensure high frost resistance.

During a further maturing stage, low-soluble double salts of calcium

nitrochloroaluminate 2CaOAl2O3Ca(OH)Cl2 10H2O are formed on the primary
framework in the form of the same hexagonal syngonite-like structures. However, Figure 10. The magnified crystals of
the concentration of inter crystalline solutions is so high that their density does Tetraculcium Aluminoferrite deposited
not change with an inflow of moisture from outside. The great number of into concrete after 3 months.
molecular bonds is explained by the effect of chlorine ions upon dipolar water Formed by KF-A, new grows of crystals
molecules. This phenomenon is similar to when water is magnetically treated provides highest protection from
before mixing concrete components to improve concrete strength. chemical corrosions [10].

Adding metal oxide ions to compounds dissolved in water has a polarizing effect on dipolar water molecules to lower
the number of molecular bonds of water. Owing to weak bonds in the presence of calcium hydroxide, an alkali group is
released into the water to protect calcium against dissolution at the maturing stage:

3Ca(OH)2 + 6NaCl2 + 30H20 + [3CaOAl2O3] 3[CaOAl2O3 CaCl2 10H2O] + 6NaOH; (18)

- -
Cl Na OH +

Tricalciumalumochloride formed as a result of reaction (13) forms hardly soluble solid phases when water is released
for simultaneous hydration reactions. The alkali and the internal pore moisture form solutions inhibiting metal corrosion
that also have a low eutectic temperature of -126 F (-70 C) when the cement stone is in a stable phase stage.

At a stage when phases are unstable, owing to the weak bonds of water molecules that are depolarized with chlorine
ions and weak bonds of the reaction products (8), nitrate ions react, and the sequence of these reactions is determined
by their inherent chemical activity, the alkali levels of the solution, and the intermediate reaction product - calcium
aluminate - with which the following dissociation reaction is most likely:

3Ca(OH)2 + 6NaNO3 + 32H20 + Ca3(AlO3)2 3Ca3(AlO3)23Ca(NO3)2 32H2O] + 6NaOH; (19)

-
Na OH +
Alexander V. Rusinoff Kalmatron for High Performance Concrete Page 11 2004

This reaction yields a low-soluble double salt of calcium hydro-nitro-aluminate with an increase in pore fluid pH. The
stability of the reaction (16) is insured by an almost simultaneous reaction of sodium sulfate. The consumption of
starting components for another reaction (10) results in their shortage and in a one-way character of dissociation:

3Ca(OH)2 + 3Na2SO4 + 31H20 + Ca3(AlO3)2 3Ca0 Al2O3 CaSO431H2O + 6NaOH , yielding calcium hydrosulfoaluminate. (20)

Therefore, if such an electrolyte is added at a concentration that insures a change in solubility of mineral binders
without reacting with them, with a subsequent formation of hardly soluble complex compounds - calcium
hydrosulfoaluminate, calcium chloroaluminate and tricalcium chloroaluminate from the resulting solution, the overall
volume of the crystalline component of the structure increases all at once parallel with normal concrete cure.

The advantage of complex additives is explained by the fact that although the rate of formation of double salts is lower
than in the case of a single additive (which is due to the consumption of calcium aluminate of the liquid phase for
hydration), cement components can react at a lower reaction constant. Moreover, a protracted reaction allows the ion
force of free water (which later becomes the pore fluid) to become stronger so as to form saturated solutions from
additional double hydrate salts.

Calcium electrolytes containing calcium accelerate hydration and hardening of silicate phases of cement owing to a
higher probability of formation of three-dimensional germs of a new phase. These electrolytes also disperse the
products of hydration through dissociation with anion-kation groups:
+ -
Ca(OH)2 + Na2CO3 CaCO3 + 2Na + 2OH (21)

The above-described processes insure a high hardening rate and a fast rise of concrete strength. The use of KF-A
additive insures a better use of the potential of alite 3CaOSiO2C3S. Ions of electrolyte that are still in the liquid phase
are products of displacement. They form salvation shells at the boundaries of kation fields, thereby preventing free
calcium from leaving the structure-forming reactions. At the same time, nitrate ions accumulate in the free water
polarized with chlorine ions to form solutions of increasing ion strength. These solutions will, in turn, accelerate the
hydration of alite. The manifest relay-like character of these processes allows alite to develop to a greater extent into a
symmetrical three-dimensional conglomeration with isotropic properties.
+ -
Involved Na and SO also participate in exchange reactions
similar to (13). However, it should be noted that these
components used as herein disclosed decelerate dissociation
of ions because of accumulation of alkali in the aqueous
solution in the presence of calcium hydroxide. Silica Fume
This allows the group of belites 2CaOSiO2 (-C2S) that are
lagging in their development in comparison with alite to cause
an exponential increase in the group of calcites and silicates
that failed to be attached in previous hydration reactions.

As the components causing the formation of calcium

sulfoaluminate are well soluble, and sulfate ions are present
in the solution at a high concentration after displacement, the KF-A
aluminate available in the system is fully bound into
sulfoaluminate during the setting of the structure. With further
curing of the concrete mix, no sulfoaluminate is formed, and
this results in an improved sulfate resistance of concrete,
lower shrinkage, a better strength and frost resistance.

Fig. 11 shows comparative test result for shrinkage evaluation

for concrete with KF-A and Silica Fume. The difference in
shrinkage development was lower for concrete with KF-A by
almost two times.
Figure 11. Development of shrinkage for KALMATRON
KF-A concrete and concrete with Silica Fume.

Adding electrolytes results in the intensification of chemical reactions and a better solubility of cement clinker minerals
with water. They also accelerate the exchange reactions. The resulting products of hydrolysis and hydration, which are
Alexander V. Rusinoff Kalmatron for High Performance Concrete Page 12 2004

in the form of crystals and gel, actively coagulate. It should be noted that gel expands due to the absorption of a large
amount of water. This enhances adhesion of the aggregate of the mix and results in the clogging of pores and
compaction of the concrete stone.

It should be noted that the presence of lime-based elements in cement improves the isotropy of a concrete structure. It
is known that a scatter of test results is mainly associated with, and depends on, ambient temperature and mixing
water temperature. These temperatures affect the rate and completeness of the above-described reactions. Also, it
stabilizes the local temperature field of the mix during the lime based elements quenching. A stable quenching reaction
is insured by making a specific choice of particle size and moisture content of those elements and also of the
water/cement ratio. Therefore, the relay-like character of the reactions results in the rapid formation of a primary
framework of acicular crystals of calcium hydroxo-salts at the stage of concrete setting. This framework is overgrown
with lamellar crystals of calcium sulfoaluminate, calcium nitrochloroaluminate and calcium hydrosilicate. The formation
of hardly-soluble crystalline structures raises the density of the cement stone and acts like a micro-reinforcement.
These structures reduce the permeability of concrete and preserve its plastic properties.

RESISTANCE OF CONCRETE WITH KALMATRON KF-A TO CORROSION

Resistance of concrete to chemical corrosion depends on its liquid and gas conductivity and dynamic wetting ability.
Liquid-gas conductivity can be determined by evaluation of macro and micro pores, where a domination of micro pores
is preferable. The dominance of micro pores in the cement stone gel with diameters of 15 provides absolute liquid-
gas impermeability by high inter porous pressures of gases and vapors as the products of concrete batch hydrothermic
reactions.

KALMATRON KF-A as an admixture to concrete mixes

provides stable resistance to the chemical corrosion of
aggressive liquids and gases. Due to increased cementitious
gel because of KF-A reactivity, the concrete body obtains 97%
micro pores, which are the best hydraulic lock in itself. Almost
complete hydration of the cement grains before concrete
application gives no chance for wetting conductivity.

Therefore, the most chemically resistant part of the concrete

structure is the cementitious stone gel. We have excellent
results of KF-A application on the floor of a zinc plant, where
the cementitious part of the concrete was intact after one year
but the aggregate was eaten up by the sulfuric acid, and that
floor looked like a honeycombed surface (Figure 12). Figure 12. Acid drip area where the aggregate corroded
down under the KF-A concrete cement matrix.
It was recommended to change the porous aggregate to a
more durable type.

We have also the results of comparative applications of

concrete with KALMATRON KF-A and concrete made with
Sika 51 High Aluminum Cement, where after a few months
the aggregate above the deteriorated Sika 51 cement is
exposed (Fig. 13).

Products were applied to the floor of an acid room where

electrolysis occurred with solutions of 30% sulfuric acid and
copper sulfate. This photo was taken after 9 months. There is
the intact surface of concrete with KF-A (above) and the
deteriorated surface of concrete with Sika 51, the filler
appearing.

Application of KALMATRON KF-A to concrete structures in

chemically complicated environments is an entirely different
Figure 13. The comparative application of regular concrete
field. We found a few technologies to prevent concrete from 3
with 5 Kg/m of KALMATRON KF-A next to high alumina
these solutions. One of them is implanting acids and salt concrete based on cement Sika 51.
solutions into the concrete batch and has been the most
successful.
Alexander V. Rusinoff Kalmatron for High Performance Concrete Page 13 2004

HP CONCRETE AS IT IS

What happens if we pour some oil into the concrete batch? Obviously, slump
and workability will be great, and even the initial properties of concrete will
exceed expectations, but retardation of hydration will occur and the final
concrete structure will be fragile, or became fragile under cycling temperature/
moisture or chemical corrosion.

We can observe the same effect with other hydration retarders such as:

Super fine fillers (fly ash, sandy dust, volcanic dust, etc.). a). Trial and control (from left to right)
Soluble organic fillers (kaolin, lignite, etc.). specimens are after 90 days into 25%
Plasticizers based on organic soluble minerals. of sulfuric acid solution.
Premixed accelerators for hardening, which need much less time than
required for hydration.
Organic retarders of hardening which prevent hydration itself.
Any crystal growers based on fast blowing minerals.

On the pictures shown at right are the comparative tests results of traditionally
enhanced concrete mix designs with regular concrete mixes transformed to
High Performance Concrete by KALMATRON KF-A. Twice bigger looses of
aggregates are obvious with control specimens.
b).Control Quartzite concrete specimen
Most concrete features depend on the volume and speed of hydration of the
had weight loss of 2.5% after 90 days in
cement grain. High Performance Concrete must be designed with a maximum sewage tank.
of rheologically uniformed ingredients to allow the performance of natural
materials properties. The cementitious part should act like glue among natural
aggregates. KALMATRON KF-A is designed to enhance the natural
performance of cementitious paste, its volume and original properties.

KALMATRON KF-A was tested, specified, and applied for structures that
come in contact with aggressive media, such as ammonia, alkalis, sugar,
sulfates, chlorides, sea-water, and distillate petroleum products. Other fields of
successful application are sewage systems, zinc plants, uranium mines, food
processing plants, wineries, sea structures, airports, roads, etc.
c).Trial Quartzite concrete specimen
3
with premixed 7.5 Kg/m KF-A had
Controlled setting time, high compressive strength, absence of cracks, high
weight loss of 1.4% after 90 days in
tensile and flexural strength, impermeability, sulfate and alkali resistance, frost sewage tank.
resistance and low labor efforts for preparation and use --- those are the main
characteristics of the concrete mix with KALMATRONKF-A. Figure 14. a, b, c.

It is proven that KALMATRON KF-A as an admixture to concrete mix provides stable high-cementitious effects on
different stages of the forming concrete structure; it cant be identified otherwise than the performance of cured High
Performance Concrete.

Dr. Alex V. Rusinoff

President and Chairman of KALMATRON Corporation
Alexander V. Rusinoff Kalmatron for High Performance Concrete Page 14 2004

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