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Concrete Technology

Prof. Dr. Zena K. Abbas


[email protected] Second class

Concrete technology
Lec. 2
limestone or chalk
Chemical Composition:

The raw materials used for the manufacture of cement consist


mainly of:
1-Lime - CaO
2-Silica – SiO2
3-Alumina- Al2O3
4-Iron oxide- Fe2O3
These oxides interact with one another in the kiln at high temperature to
form more complex compounds.
** The relative proportions of these oxide compositions are responsible for: shale or clay
1. influencing the various properties of cement
2. the rate of cooling
3. fineness of grinding

It is to be noted that for simplicity’s sake abbreviated notations


are used.
C stands for CaO,
S stands for SiO2,
A for Al2O3,
F for Fe2O3 , and H for H2O.
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The equations suggested by Bogue for calculating the percentages of major
compounds are given below.
C3S= 4.07 (CaO) – 7.60 (SiO2) – 6.72 (Al2O3) – 1.43 (Fe2O3) – 2.85 (SO3)
C2S = 2.87 (SiO2) – 0.754 (3CaO.SiO2)
C3A = 2.65 (Al2O3) – 1.69 (Fe2O3)
C4AF= 3.04 (Fe2O3)
The oxide shown within the brackets represents the percentage of the same in the raw
materials.

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Hydration of Cement
The chemical reactions that take place between cement and
water is referred as hydration of cement

1. Anhydrous cement does not bind fine and coarse aggregate.


It acquires adhesive property only when mixed with water.
2. The chemistry of concrete is essentially the chemistry of the
reaction between cement and water
3. The products of hydration are important because they have
cementing or adhesive value.
4. The quality, quantity, continuity, stability and the rate of
formation of the hydration products are important
*** Anhydrous cement compounds when mixed with water
react with each other to form hydrated compounds of very
low solubility.

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Hydration of Cement

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The hydration of cement can be visualized in
two ways:-
1. Through solution: in this way , the cement compounds
dissolve to produce a supersaturated solution from which
different hydrated products get precipitated
2. Solid state: - is that water attacks cement compounds in
the solid state converting the compounds into hydrated
products starting from the surface and proceeding to the
interior of the compounds with time.
**** It is probable that both “through solution” and
“solid state” types of mechanism may occur during the
course of reactions between cement and water
**** The former mechanism may predominate in the
early stages of hydration in view of large quantities of
water being available, and the latter mechanism may
operate during the later stages of hydration.
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Heat of Hydration:

The reaction of cement with water is exothermic. The


reaction liberates a considerable quantity of heat. This liberation
of heat is called heat of hydration.

** This is clearly seen if freshly mixed cement is put in a


vacuum flask and the temperature of the mass is read at
intervals.

The study and control of the heat of hydration becomes


important in:
1. The construction of concrete dams
2. The mass concrete constructions.

It has been observed that the temperature in the interior of large mass concrete is
50°C above the original temperature of the concrete mass at the time of placing and
this high temperature is found to persist for a prolonged period.

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The Figure shows the pattern of liberation
of heat from setting cement and during early
hardening period. On mixing cement with
water, a rapid heat evolution, lasting a few
minutes, occurs.
--This heat evolution is probably due to the
reaction of solution of aluminates and
sulphates (stage I).
-- This initial heat evolution ceases quickly
when the solubility of aluminate is
depressed by gypsum. (Stage II).
-- Next heat evolution is on account of
formation of ettringite and also may be due
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 Since gypsum are added to control the flash setting
properties of C3A,
 Actually the early heat of hydration is mainly
contributed from the hydration of C3A.
 Fineness of cement also influences the rate of
development of heat but not the total heat.
 The total quantity of heat generated in the complete
hydration will depend upon the relative quantities of
the major compounds present in cement.

Thank you

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Concrete Technology
Prof. Dr. Zena K. Abbas
[email protected] Second class

Concrete technology
Lec. 3
Tricalcium aluminate hydrate and the action of gypsum

The amount of C3A present in most cements is


comparatively small but its behavior and
structural relationship with the other phases in
cement make it of interest.

The tricalcium aluminate hydrate forms a prismatic dark


interstitial material in the form of flat plates individually
surrounded by the calcium silicate hydrate.

The reaction of pure C3A with water is very violent


with evolution of large amount of heat, forming
calcium aluminates hydrate in the form of leaf
hexagonal crystals. In Portland cement, this reaction
leads to immediate stiffening known as "flash
setting".

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Gypsum, added to the clinker through grinding process
cause delaying the reaction of C3A with water by its
reaction with C3A to form insoluble calcium
sulfoaluminate (3CaO.Al2 O3.3CaSO.30-32H2O) -
ettringite - around C3A particles, which permits enough
time for the hydration of C3S that its reaction is slower
than C3A and permits the occurring of natural setting.
But eventually tri-calcium aluminate hydrate is formed,
although this is preceded by a metastable
3CaO.A12O3.CaSO4.12H2O, produced at the expense of
the original high-sulfate calcium sulfo-aluminate.

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The reaction of gypsum with C3A continues until one of them exhausted, while C3S continue in hydration.

 If C3A exhausted before gypsum


The surplus gypsum  expand  become an agent assist the disruption
and deterioration of cement paste.

 If gypsum exhausted before C3A


The remaining C3A begins in hydration:
C3A + 6H  C3AH6
C3AH6is stable --cubical crystals- with high sulfate resistance.

Calcium aluminate hydrate - Be at many forms before


transforming to the stable state (C3AH6). It is probably
forming hexagonal crystals (C4AH8, C4AH10, C4AH12) before
the cubical crystals.

When the hexagonal crystals expose to sulfates (inside concrete from sand or external from soil or
ground water)  react with it forming calcium-suloaluminate  with increase in volume,
depending on the amount of remaining aluminates and the concentration of sulfates  crack and
deteriorate of the hardened concrete.

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The transformation of calcium aluminates hydrate from the metastable hexagonal
form to the stable cubical form is accompanied with — change in the density and
size of the crystals — leading to decrease in the late ages strength of the cement
paste due to:

1. Lose the adhesion and cohesion in the microstructure.


2. Increase the porosity of the hardened cement paste.

The presence of C3A in cement is undesirable:


1. It contributes little to the strength of cement except at early ages (1-3 days)
2. and, when hardened cement paste is attacked by sulfates; expansion due to the
formation of calcium sulfoaluminate from C3A may result in a disruption of the
hardened paste.
But it is useful in the cement industry
1. works as flux material
2. reduce the temperature needed to form the clinker.
3. Also, it facilitates the combination of lime with silica.

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Using the optimum percentage of gypsum is very important
because:
1. It regulates the speed of the chemical reactions in the early ages.
2. Prevent the local concentration of the hydration products.
The necessary gypsum content increase with the increase of:
-C3A content in the cement.
-Alkalis content in the cement.
- Fineness of the cement.

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Calcium silicates hydrate
C3 S:
C3S which is normally present in the largest amount. '
Hydration of C3S — take about one year or more
This initial gel form an external layer over C3S causing the
delay of the reaction. After few hours, this initial C-S-H
undergo hydrolysis to form the second product of the gel CSH
The full hydration of C3S can be expressed approximately
following equation:
2(3CaO.SiO2) + 6H2 O  3CaO.2SiO2. 3H2O + 3Ca (OH) 2
For C3S hydration
2 C3S + 6H  C3S2H3 + 3Ca (OH)2
The corresponding masses involved are:
100 +24  75 +49

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C2 S:
 Its reaction is slower than C3S.
 The amount of Ca (OH)2 from its hydration is less. Its formed gel is similar to
that produced from C3 S, but there is difference in the route of the chemical
reactions between the two compounds — the lime: silica during the hydration
of C2S differs than that formed during the hydration of C3S. Hydration of C2S
— takes more than 4 years.
The gel formed after the completion of hydration of the two compounds
C3S and C2S — require approximately the same amount of water for hydration,
but C3S produces more than twice as much Ca (OH)2 is formed by the hydration
of C2S , as shown in the equations below:
For C2S hydration
2 C2S + 4H  C3S2H3+ Ca (OH)2
The corresponding masses involved are:
100 +21  99 +22
C2S β- C2S form at about 1450.

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you

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