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Cement Composition

How is composition determined?

Chemical analysis
•X-ray diffraction
•Optical microscopy
•Scanning electron microscopy
with energy dispersive X-ray
analysis
•Electron microprobe analysis
•Selective dissolution
•Thermal analysis
Oxide composition

•CaO(C)
•SiO2(S)
•Al2O3(A)
•Fe2O3(F)
•MgO, SO3, Na2O, K2O
•Minor oxides
Using Bogue equations, oxide compositions
are converted into approximate compound
compositions

•% C3S = 4.071C –7.700S –6.718A –1.430F –


2.852 SO3
•% C2S = 2.867S –0.7544 (% C3S)
•% C3A = 2.650A –1.692F
•% C4AF = 3.043F
Assumptions in Bogue equations

No secondary minerals present –inaccurate!!


•A/F > 0.64
•All alumino ferrites are present in the form of
C4AF –not true! Many solid solutions exist
•System is in equilibrium

Do not account for the presence of free lime


Typical composition

•CaO: 60 –67% •C3S: 45 –60%


•SiO2: 17 –25% •C2S: 15 –30%
•Al2O3: 3 –8% •C3A: 6 –12%
•Fe2O3: 0.5 –6% •C4AF: 6 –8%
•MgO: 0.5 –4% •Gypsum ~ 4%
•Alkalis (as Na2O): •Additives –up to 5%
0.3 –1.2%
•SO3: 2.0 –3.5%
Cement Chemistry

Cement hydration

Reaction of cement with water


•Exothermic; heat released is called ‘Heat of
Hydration’
•Rate of heat evolution is faster if the reaction is
quicker
•Heat evolved depends on heat of hydration of
individual compounds, and also on the clinker
morphology!
Heat evolution

Heat of hydration of pure


cement compounds
Compound HOH (J/g)
C3S 502
C2S 260
C3A 867
C4AF 419

Bogue: ½of total heat is evolved between 1 and 3 days,


about ¾in 7 days, and 83 –91% in 6 months
Typical pattern of heat evolution
Heat peaks

Peak I: ‘Heat of wetting’+ some early C-S-H formation


•Dormant period: Very slow rate of heat evolution

•Peak II: Main peak; associated with the rapid dissolution


of C3S to form CSH and CH, and formation of ettringite
(AFt) from C3A.

•A slowdown of the hydration process beyond the main


peak leads to lower rates of heat evolution.

A broader peak (III) is associated with the conversion of


ettringite to mono sulphate(AFm).
Hydration reactions
Silicates (C3S and C2S) hydrate to produce Calcium-silicate-hydrate
(C-S-H) gel and calcium hydroxide (CH)

•3 times as much CH produced by C3S hydration compared to C2S


•C-S-H does not have a well-defined composition; C/S varies from
1.5 to 2
•Aluminates (C3A and C4AF), in the absence of gypsum, hydrate
rapidly to produce Calcium-aluminate-hydrates (C-A-H)
•In the presence of gypsum, ettringite (AFt) and mono sulphate
(AFm) are produced (depending on the C3A to SO3ratio)
•Ettringite formation is known to be expansive (numerous
mechanisms suggested)
Reactions -Specifics

2 C3S + 6 H C3S2H3+ 3 CH
•2 C2S + 4 H C3S2H3+ CH
•2 C3A + 21 H C4AH13+ C2AH8
Flash set reaction!
• C2AH8 is a meta stable phase that deposits as
hexagonal platelets (similar to CH). Above 30 oC, it is
converted to cubic hydro garnet (C3AH6).
• In the presence of gypsum,

C3A + 3 CSH2+ 26 H C6AS3H32


Aluminate-sulphate reactions
Nearly all the SO42-gets combined to form ettringite in an
ordinary Portland cement.
•If there is still C3A left after this reaction, it can combine with
ettringite to form mono sulphate(or Afm phase) which has a
stoichiometry of C4ASH12-18.
•If there is sufficient excess C3A, then C4AH13can also form as a
hydration product, and can exist in a solid solution with AFm.
•C4AF produces similar hydration products as C3A, with the
Al3+being partly replaced by Fe3+. The final hydration product
depends on the availability of lime in the system. In the presence
of gypsum, C4AF produces an iron-substituted ettringite.
•Higher the ratio C4AF/C3A, lower is the conversion of ettringite
to mono sulphate.
Kinetics of hydration

The progress of cement hydration depends on:

•Rate of dissolution of the involved phases (in the initial


stages), and at later stages,

•Rate of nucleation and crystal growth of hydrates

•Rate of diffusion of water and dissolved ions through


the hydrated materials already formed
Factors affecting hydration rate
1. The phase composition of cement
2. The amount and form of gypsum in the cement: Whether
gypsum is present in the dihydrate, hemihydrate, or the
anhydrite form.
3. Fineness of cement: Higher the fineness, higher the rate of
reaction due to availability of a larger surface area.
4. w/c of mix: At high w/c, hydration may progress till all of the
cement is consumed, while at low w/c the reaction may stop
altogether due to lack of water.
5.Curing conditions: The relative humidity can have major effects
on the progress of hydration.
6. Hydration temperature: Increase in temperature generally
causes an increase in the rate of the reaction, although the
hydrated structure can be different at different temperatures.
7. Presence of chemical admixtures: For example, set
controllers, and plasticizers.
Hydrated cement paste

Hydrated cement paste is composed of capillary pores


and the hydration product.
•The pores within the structure of the hydration product
are termed ‘gel’pores. This hydration product includes C-
S-H, CH, AFt, AFm, etc.
•Gel pores are included within the structure of hydrated
cement.
•According to Powers, 1/3 of the pore space is
comprised of gel pores, and the rest are capillary pores.
Water within cement paste
1. Capillary water: Present in voids larger than 50 Ao. Further
classified into: (a) free water, the removal of which does not cause
any shrinkage strains, and (b) water held by capillary tension in
small pores,which causes shrinkage strains on drying.
2. Adsorbed water: Water adsorbed on the surface of hydration
products, primarily C-S-H. Water can be physically adsorbed in many
layers, but the drying of farther surfaces can occur at about 30 %
relative humidity. Drying of this water is responsible for a lot of
shrinkage.
3. Interlayer water: Water held in between layers of C-S-H. The drying
of this water leads to a lot of shrinkage due to the collapse of the C-S-
H structure.
4. Bound water: This is chemically bound to the hydration product,
and can only be removed on ignition. Also called ‘non-
evaporable’water.

2 and 3 are together called ‘gel’water


SE micrograph of paste
CSH Structure –Feldman Sereda model
CSH Properties

The Feldman Sereda model suggests a high surface area for CSH
•Using water sorption and N2sorption measurements, a surface
area of 200000 m2/kg is reported (ordinary PC has a fineness in
the order of 225 –325 m2/kg). Small angle X-ray scattering
measurements show results in the range of 600000 m2/kg.
•The corresponding figure for high pressure steam-cured cement
paste is 7000 m2/kg, which suggests that hydration at different
temperatures leads to different gel structures.
•The structure of C-S-H is compared to the crystal structure of
Jennite and Tobermorite. A combination of the two minerals is
supposed to be the closest to C-S-H.
•High covalent/ionic and Vander Waalsforces
•Occupies a volumeof50-65% of the paste
Calcium Hydroxide

Mehta and Monteiro, 1993

•Hexagonal crystals, generally oriented tangentially to


pore spaces and aggregates along the longitudinal axis

•Low surface area(0.5 m2/g)

•Low Van der Waals forces


•Volume–20-25%
Calcium sulpho aluminates

Ettringite: Acicular, columnar, hexagonal crystals


(seen as prismatic needles).
The presence of tubular channels in between the
columns can lead to high water absorption and
swelling by ettringite.
This is one of the theories explaining the expansion
caused by ettringite formation.
•Mono sulphate–plain hexagonal
•Volume occupied is 15 –20%
Ettringite and mono sulphate