Cement Chemistry

Cements:- used since historical times (Pyramids  3000 BC; Colosseum).

Ancient cements of varying types. Two main classes of constructional cements
are defined: non-hydraulic cements - do not set under water (see box), and
hydraulic cement.
Non-hydraulic cements were amongst
Non-hydraulic cements e.g.
(i) Plaster of Paris (CaSO4. /2 H2O)
1 the most common of the ancient
CaSO4. /2 H2O + 1 /2H2O  CaSO4.2H2O
1 1 cements. The relatively high
(gypsum) solubilities of portlandite (Ca(OH) 2)
and gypsum means that they
(ii) lime-based cement (CaO) deteriorate rapidly in moist or wet
CaO + H2O  Ca(OH)2 + CO2 CaCO3
environments. The early Romans
(calcite)
made good use of lime based
cements and mortars (cement + sand) by ramming the wet pastes to form a high
density surface layer which carbonates in contact with air to produce a low
permeability surface skin of calcite. This protected the underlying Ca(OH) 2 and
examples of Roman lime mortars can still be seen in Hadrians Wall. Lime
mortars were still used in domestic construction until relatively recently. Raw
(natural) materials required temperature treatment. Partial dehydration of
natural gypsum (200oC), and calcination of calcite (850oC). Hydraulic cements
- more durable. Hydration products are very insoluble - cements set under water.
Earliest systematic development of these, probably Roman - use of limestones
containing silica and alumina and also use of volcanic earths as an additive to
limestone prior to calcination. Forerunner of modern Portland cements.
Portland cement - patented by Joseph Aspdin in mid-1800’s. Made from finely
ground limestone and finely divided clay to give a burned product containing 65-
70% CaO, 18-24% SiO2, 3-8% Fe2O3, 3-8% Al2O3 plus smaller proportions of
minor oxides (e.g. Na2O, K2O, MgO, etc.). Modern plants permit much more
efficient processing and in addition, proportion raw mix compositions to produce
a cement from which a range of strength development and durability properties
can be expected.
 Raw materials for modern cement making Efficient grinding and blending of
raw materials is essential. Firing of
limestones argillaceous shales blends (raw meal) takes place in a
chalks schists
shells clays rotary kiln following drying and
calcerous muds other iron-bearing alumino- dehydration in cyclone preheaters
silicates and pre-calciners. Materials
additional iron may be required as a fluxing aid. undergo solid state reaction and
partial melting (clinkering) at temperatures of up to 1500 oC (in the hot zone of
the kiln). Cement clinker is recovered on the cooling grate and sent for grinding
and blending with gypsum.
Cement clinker composition : - main clinker minerals are alite, belite, aluminate
and ferrite. Proportions vary depending on raw meal composition and firing and
contribute to defining the hydration and strength development properties of the
cement product.
Alite- C3S, 3CaO.SiO2 (idealised): Minor - Al2O3, MgO, P2O5, Fe2O3, Na2O,
K2O
Belite- C2S, 2CaO.SiO2 (idealised): Minor - Al2O3, MgO, P2O5, Fe2O3, Na2O,
K2O
Aluminate - C3A, 3CaO.Al2O3 (idealised): Minor - Fe2O3, SiO2, MgO, Na2O, K2O
Ferrite - C4AF, 4CaO.Al2O3.Fe2O3 (idealised): Minor - SiO2, MgO, TiO2, Mn2O3.

Chemistry of clinker formation: - information on raw meal composition and

required kiln conditions may be obtained from equilibrium phase diagrams.
Minor components have a small influence on equilibria but approximations can
be made using the CaO-Al2O3-SiO2-Fe2O3 diagram although it is perhaps
preferable to restrict initial considerations to phase relations in the CaO-SiO 2 and
the CaO-Al2O3-SiO2 systems.

The CaO-Al2O3-SiO2 system

The CaO-SiO2 system
The CaO-SiO2 and CaO-Al2O3-SiO2 systems are binary and ternary systems
respectively. The ternary system shows the temperature and compositional
information of the binary system (CaO-SiO 2) but with the third component (Al 2O3)
also, viewed from above. The curved lines represent temperature ‘valleys’ as on
a map. Compositional information at a fixed temperature can be derived from an
isothermal section. The 1500oC section of the CaO-Al2O3-SiO2 system allows
some consideration of phase equilibria in cement making.
Approximate bulk
composition of raw meal is
represented by C which
means that C2S and C3S will
be in equilibrium with a liquid
phase of composition L c
(which contains CaO, Al2O3
and SiO2). It would expected
from this diagram that the
liquid would cool to crystallise
C3A. In practice, the final
1500 C isothermal section of the CaO-Al2O3-SiO2 system phase assemblage includes
o

C12A7, a phase relevant to a

lower temperature diagram.
This arises due to the non-equilibrium effect of fractionation; as cooling
occurs, slow reactions can cause high temperature assemblages to be frozen
in). The final properties of the cement strongly depend on its mineral
composition so that raw meal composition and firing conditions are adjusted
depending on the type of cement to be produced (see later notes on Cement
Type). The cement manufacturer expresses the product composition both as an
oxide analyses (chemical) or mineral composition. The latter is calculated using
the Bogue calculation.

HYDRATION - the term used to describe a range of reactions between cement

and water to produce a hardened product. A cement clinker particle is a
multiphase solid having massive calcium silicate grains (50 - 100 m) in a matrix
of interstitial aluminate and ferrite. They each have specific reactions with water
(see box) to produce a range of hydration products which intermesh and
interleave to produce a dense and strength developing solid. The rates of
reaction are important. The C3A reaction is fastest and also generates most heat
(cement hydration is exothermic) but little contribution to ultimate strength is
derived from this phase alone although it contributes significantly to early
strength. The principal contributers to longer term strength are the calcium
silicates. C3S is most reactive, giving early strength but C 2S has a better longer
term contribution. The C-S-H produced is the principal binding phase in Portland
cements and is quantitatively the most significant hydration product. The ferrite
reactions are intermediate in rate between the C 3S and C2S reactions but have
an important long term contribution to strength and durability.
 Reactions of Principal Clinker Phases
C3S + H2O  C-S-H* + Ca(OH)2
C2S + H2O  C-S-H* + Ca(OH)2
2C3A + 18H2O  C2AH8 + C4AH10
2C3A + 32H2O + 3(Ca2+(aq) + SO42-(aq))  C6AS3H32
C6AS3H32 + 2C3A  3C4ASH12
C4AF has analogous reactions to C3A,
i.e. produces e.g. C6(A,F)S3H32

*C-S-H is an amorphous hydrogel having variable

composition in terms of Ca/Si ratio and H2O/SiO2
ratios

Rates of hydration of individual clinker phases

Distribution of hydration products in Portland

cement pastes
Properties of Cement Hydration Products

Ca(OH)2 - crystalline, isostructural with the natural mineral Portlandite. Solubility

at 25oC of around 1g.l-1.
C-S-H - poorly crystalline product of variable composition. Considered to be
based on a crumpled layer structure (analogous to a distorted clay sequence)
which traps regions of porosity - pore size distribution from nm to m. Simplified
composition given by:
CaxH6-2xSi2O7.zCa(OH)2.nH2O where CaO/SiO2 = (x+z)/2 (Glasser et al, J.Am.
Ceram. Soc., 70, 481-5, (1987)). Variable CaO/SiO 2 ratio (approx. 0.8 to 1.8)
and variable H2O:SiO2 ratio (see CaO-SiO2-H2O phase diagram below). Variable
composition means variable solubility properties. Solution compositions above
C-S-H and the presence of other phases defines the C-S-H composition (see
lectures) so that cements containing siliceous blending agents will have
compositionally quite different C-S-H to that found in OPC pastes.
AFt - or ettringite, or aluminoferrite trisulphate (C 6AS3H32). Crystalline - trigonal.
Forms columnar type structure consisting of (Al,Fe)(OH) 6 octahedra alternating
with triangular groups of edge sharing CaO 8 polyhedra with which they share
OH- ions. Inter-column regions contain loosely bound SO 42- groups which are
exchangable. Responsible for retardation of C 3A hydration (due to coating of
C3A).
 The CaO-SiO2-H2O system

Crystal structure of ettringite

AFm - or monosulphate. Crystalline - layer structure derived from that of Ca(OH) 2
by the ordered replacement of one Ca 2+ ion in three with Al3+ or Fe3+. These
layers alternate with ones containing anions which balance the charge (e.g.
SO42-, OH-, etc.) and H2O. Composition is [Ca2(Al,Fe)(OH)6].X.xH2O, where X
represents the interlayer anion.
Hydrogarnet - nominally C3AH6, but in practice contains Fe and Si. Related to
the mineral grossular or garnet (Ca 3Al2Si3O12) which has a cubic structure. Not
normally a product of modern OPC hydration although present in blended
cements and older Portland cements.
Aqueous phase and pore structure - pore fluid permeates the microstructure
of the hardened cement paste via the pore system. It is highly alkaline (pH > 13)
due to rapid and almost quantitative dissolution of Na and K salts from the
cement clinker. The porosity of the paste comprises of interconnected and
isolated pores, the pore sizes of which are important to the strength and
dimensional stability of cement products.

Cement Types and Standards: provides some quality restrictions to cement

compositions and performance. Different types of cement are used to meet
different performance criteria. Properties can be estimated from compositions
Composition (wt%) and Properties of and fineness. Try to estimate
ASTM Types I to V Cements which cement types will be rapid
I II III IV V hardening, low heat ouput or
C3S 50 45 60 25 40
sulphate resistant Portland
C2S 25 30 15 50 40
C3A 12 7 10 5 4 cements.
C4AF 8 12 8 12 10
Fineness 350 350 450 300 350
(m2.g-1)
Compressive 7 6 14 3 6
Strength @ 1d
(MPa)
Heat of 330 250 500 210 250
hydration @ 7d
(J.g-1)

Blended Cements The use of cements in concrete which have not been
blended with some form of reactive additive will become less likely in the future.
There are now a range of additives commonly used to enhance the properties of
concretes and, in some cases, result in reduced materials costs. This is mainly
because they are industrial by-products. The most common of these are:
pulverised fly ash (PFA)- a coal combustion product; blastfurnace slag (BFS),
from iron making, and; condensed silica fume (CSF) from the ferrosilicon
industry. The suitability of such materials depends on: their reactivity, their cost
(availability) and their influence on the properties of the resulting concrete. All
influence the internal chemistry of
the cement system, i.e. pH,
mineral balances, and their
generally slower reaction leads to
a longer equilibration time as
reaction products of the additive
re-equilibrate with cement
hydration products. Reactivity, in
all cases, depends on glass
content, particle size, composition

Relative compositions of common blending agents

for Portland cements
(nature of impurities) and external influences such as temperature, humidity and
hydrating liquid composition.
Silica fume: quartz reduced in an electric arc furnace - some SiO volatilisation
and oxidation produces largely glassy SiO 2 particles of 100 nm diameter. Low
density material with 86-95% reactive SiO 2.
PFA: arises as a dust in chimney stacks above coal-burning power station
furnaces. Have widely variable compositions depending on furnace operating
conditions and coal source. Particle sizes may be low, with 50% < 10 m or
coarse with 50% < 40 m. Particles are generally spherical (formed by rapid
cooling from a melt) and may be hollow (cenospheres) with or without spheres
inside (plerospheres). Largely glassy (85 - 90%) with small crystallites of mullite
(A3S2) and quartz.
BFS: produced in the iron blastfurnace. Fluxes impurity oxides and sulphides.
Composition is monitored (defines iron quality). Best for iron maker when
(CaO+MgO)/(SiO2+Al2O3) is maximised. Mainly glassy (>95%) and has its own
CaO content (approx. 40%).

Influence of pfa addition on Ca(OH) 2 content

Hydration characteristics Silica fume reacts relatively fast in the cement

system. Pastes require a higher water content than silica fume-free ones unless
a superplasticiser is added. The silica is consumed in reaction with Ca(OH) 2 and
lime-rich C-S-H resulting in a paste with lower (or no) Ca(OH) 2 and a C-S-H of
low CaO:SiO2 ratio (maybe as low as 1.2). The nature of the CSF-cement
reaction process leads to efficient pore-filling and consequent enhancement of
mechanical performance (low porosity pastes are stronger than high porosity
ones). Silica fume-OPC blends are therefore used in the production of High
Strength Concrete (HSC) with compressive strengths routinely in excess of 100
MPa. PFA displays the same pozzolanic action as CSF (see plot above) but is
generally much slower in reactivity due to the coarser particle size. Also, the
alumina (around 30%) and iron (around 10%) content contribute to the formation
of products other than C-S-H but even so, general C/S ratios can be significantly
lower in PFA-OPC blends than in neat OPC. (Note that in all blended cements,
compositional gradients are common.) Other products include hydrogarnet, e.g.
C12A3FS4H16 was reported within a PFA cenosphere found in an aged paste
(Rogers and Groves, Adv. Cements Research, 1, 841, (1988)). BFS has different
hydration characteristics to CSF and PFA. Having a CaO content of its own, it is
not a pozzolan as such (i.e. it does not depend on external sources of CaO to
activate it - although its reactivity is accelerated by activators such as Ca(OH) 2,
Na2CO3, NaOH, etc). Typically, BFS exhibits an initial burst of activity in OPC-
BFS blends. This is followed by a relatively dormant period which may last six
months or more, depending on temperature, particle size and aqueous phase
composition, before continued hydration consumes remaining glassy grains.
Hydrotalcite (a magnesium aluminate hydroxide hydrate) and gehlenite hydrate
(C2ASH8) are commonly found in BFS-OPC pastes along with ettringite,
monosulphate and C-S-H but again, Ca(OH) 2 contents are substantially reduced
and C-S-H has lower Ca/Si ratios with respect to neat OPC. A unique
characteristic of BFS is its electrochemically reducing characteristics. E h values
of < -500 mV vs SHE (standard hydrogen electrode) have been measured in
pore fluids extracted from blends of 85% BFS - 15% OPC cured for 28 days.
This compares with around +100 mV measured for equivalent OPC pastes. This
feature has important implications for the use of BFS blends in waste
immobilisation and for passivation mechanisms for steel.

Effects of Blending Agents on Paste Microstructures. The durability of cement

pastes is strongly influenced by: (i) internal chemistry, and (ii) paste
microstructure. The industrial by-product additives above all influence the
development of paste microstructures. In neat OPC pastes, two types of porosity
contribute to the total pore volume. Isolated pores are completely enclosed by
hydration products so that material transport into and out of the pore is limited.
Connected porosity is that through which a continuous pathway between regions
of the microstructure exists. Continuous or interconnected porosity often
(although not always) links the interior of the paste to the outside world so that
aggressive chemical species can penetrate and degrade the paste internally
having consequences for paste durability. The effect of the blending agents
identified above on microstructure is to cause a reduction in the degree of
interconnected porosity. This is especially true in the case of BFS-containing
pastes. Although the overall porosity, as determined by neutron scatterring is still
significant, the interconnected porosity as measured by intrusion methods (e.g.
MIP) is low.
 DURABILITY - the ability of the
product to resist changes
imposed by its service
environment. Durability
includes influences of
mechanical damage, e.g.
abrasion, thermal expansion,
but is more commonly
associated with chemical
effects, e.g. sulphate attack,
chloride-induced or general
Microstructure in BFS-OPC blends corrosion of steel
reinforcement, alkali-aggregate
reaction, etc.
Sulphate attack: - expansion arising from the reaction between monosulphate
(4CaO.Al2O3.SO3.12H2O) and SO42- in the presence of aqueous Ca 2+ to give
ettringite. The conversion from the high density phase to the low density one can
cause expansion and cracking. The cracking opens up new connected porosity
which accelerates the transport of sulphate into the cement paste and the
deterioration of the paste. (Try writing out the equations for the monosulphate-
ettringite conversion).
Delayed Ettringite Formation: - a fairly recently discovered problem relating to
degradation in steam-cured products. A number of mechanisms for this have
been proposed (and at least one major legal conflict has arisen based on
assigning liability for failed concrete products). It is proposed that the
temperature cycle used in steam-curing produces a non-crystalline ettringite
precursor which, on cooling and after some extended time period, crystallises
having absorbed the required amount of moisture.
Carbonation: - lowering of matrix pH due to the reaction between dissolved CO 2
and the calcerous phases in the paste. Found at surfaces, a zone of carbonated
product penetrates towards the interior to a distance which is defined by the
porosity of the paste. Carbonation can ultimately consume Ca(OH) 2 and C-S-H,
the degradation of C-S-H leading to a progressive decalcification to very low
Ca/Si ratios and ultimately, silica gel. Degradation of the principal binding phase
therefore can lead to strength loss. A more immediate concern is the loss of high
pH in the vicinity of steel reinforcement. A pH of greater than about 10.5 is
thought to preserve a passive film on the steel, protecting it from corrosion. Loss
of pH therefore increases the corrosion risk. Engineers specify a minimum ‘cover
depth’ to attempt to deal with this problem but again, the depth of penetration is
porosity dependent.
Effect of Chloride: - used to be a common additive to cements to accelerate
setting but this use is now banned in structural concretes (Why do you think
CaCl2 would accelerated cement setting?). Chloride interactions with set
concrete are however common, e.g. de-icing salts, salt spray, etc. Penetration is
via connected porosity so that cover concrete may quickly become heavily
loaded with soluble chloride. Steel passivation films are rapidly de-stabilised by
chloride locally giving rise to pitting corrosion and rapid deterioration of the steel
(the corrosion is focused in series of a small areas). There are competing
influences of alkalinity and chloride effects so that a useful parameter to monitor
is the [Cl]/[OH] ratio.
Steel Reinforcement Corrosion: The oxidation of Fe(m) to Fe 2+. In addition,
further oxidation and cathodic reactions lead to production of oxides and
oxyhydroxides of Fe (III) which produces a low permeability ‘passive’ film which
slows the corrosion rate down considerably. Where corrosion can continue (by
depassivation), expansion of corrosion products at the cement-steel interface
and the subsequent spalling of cover concrete can occur. Many examples of this
can be seen in concrete structures. Spalling leads to exposure of previously
internal concrete as a fresh site for environmental damage.
Alkali -Aggregate Reaction (AAR): Certain rocks contain silica in a mildly reactive
form. Generally, flints, opals, cherts and strained quartz have a high degree of
reactivity in concretes. The reaction is driven by the high pH pore fluid and the
reactive silica and gives rise to a sodium silicate gel product which contains only
a small amount of calcium. The gel imbibes water causing swelling and this
gives rise to expansion cracks in affected concretes. The degree of expansion is
important with respect to the servicability of affected structures. A recent study
on a water inlet tower of a dam in Tasmania, Australia, showed that AAR
expansion had increased the diameter of the tower sufficiently so that the inlet
valves were unable to stem the flow of water when they were in the closed
position.
Glass-fibre Reinforcement Corrosion: Unlike steel reinforcement, glass fibres are
introduced in random orientation and throughout the paste. Typically, as filament
bundles (of around 50 filaments) the fibres will be of variable length (up to 2 cm
typically). As in the AAR, the highly alkaline cement pore fluid attacks the
siliceous glass to produce a gel which imbibes water. The result is loss of
effective fibre diameter as the gel continues to form. Occasionally, Ca(OH) 2
crystals attach themselves to the fibre and degrade the fibre locally (notching)
but the more general attack occurs even when pozzolans are added to minimise
notching. This degrading reaction prohibits the use of glass reinforced concrete
(GRC) as sole reinforcement in structural concrete.