Salahaddin University, Erbil, Iraq

College of Engineering
Civil Engineering Department

Hydration of Portland Cement

What is hydration of cement?
• It is a chemical reaction that occurs between the cement and water after
addition of water to the cement commonly to produce cement paste

• The chain of events that happen is that when combined with water the
individual cement compounds react with water each in a particular way and
produce hydration products also called hydrates which in turn form a
spongy mass known as gel

• It is a series of irreversible exothermic reactions. During this process a large

amount of heat is released

• The hydration produces the binding or “gluing” material that secures the
aggregates particles together in concrete

• The purpose is to achieve a firm, stiff and hard mass called the hardened
cement paste with the passing of time
Significance of hydration of cement
Understanding the hydration process is important for the following reasons;

• To achieve optimal strength and durability of cement paste

and thus concrete

• To alleviate formation of thermal stresses that can lead to

cracks

• To realize the importance of appropriate curing

Mechanisms of hydration of cement
• The are two ways in which the cement compounds may react with
water;

1. By addition of water the compounds present in cement are

dissolved to form a super saturated solution from which hydrated
products are precipitated. This is the true hydration

2. By the reaction of hydrolysis

❖ The term hydration is usually applied to both hydration & hydrolysis

Products of hydration of cement
• Under similar conditions, the products of hydration of the
individual cement compounds are chemically the same as that of
cement. This fact was observed for the first time by Le Chatelier
over a century ago
• The main hydrates are the calcium silicate hydrates and tricalcium
aluminate hydrate. The calcium silicate hydrates are the main
cementitious compounds in cement
• C4AF is considered to hydrate into tricalcium aluminate hydrate and
some of it becomes amorphous CaO.Fe2O3 in aqueous state

• Over a period of time, the products of hydration lead to stiffening,

setting and hardening of cement paste
Calcium silicate hydrates
• The C3S and C2S react with water to form calcium silicate hydrates known as the C-S-H
gel (once also called tobermorite gel) which constitutes the main binding substance in
concrete. They are also responsible for the final strength of the hardened cement
paste. C-S-H takes form in extreme small particles in the size range colloidal matter
• 70-80% of hydrated cement is comprised of calcium silicate hydrates

• As water added by a certain quantity, the C3S undergoes hydration first. Then the C2S
hydrates producing C3S2H3. (Both C3S & C2S is believed to approximately produce the
same final product C3S2H3, however there exists some uncertainty about whether they
both produce the same hydrate)
• The C-S-H formed by C3S and C2S has a typical Ca to Si ratio (~1.7 (1.5-2.0)) much lower
than that in C3S (3:1), so the excess Ca reacts to form Ca(OH)2 (CH) crystals. C2S also
forms CH which is an undesirable product of hydration having harmful effects on
concrete
• The C3S is much more reactive than C2S. The rate of reaction of C3S is moderately fast
while it is slow in C2S. Under standard temperature conditions, about half of C3S will be
hydrated by 3 days and 80% by 28 days. While C2S hydration takes longer by a great
deal. This is why C2S does not contribute to early strength
• Tricalcium silicate C3S
C-S-H and CH are generated
2(3CaO*SiO2) + 6H2O → 3CaO*2SiO2*3H2O +3Ca(OH)2
2C3S + 6H → C3S2H3 + 3CH
+ water → tobermorite + calcium hydr.
456.6 g + 108 g → 342.4 g + 222.2 g
1g + 0.24 g → 0.75 g + 0.49 g

• Dicalcium silicate C2S

2(2CaO*SiO2) + 4H2O → 3CaO*2SiO2*3H2O +Ca(OH)2
2C2S + 4H → C3S2H3 + CH
+ water → tobermorite + calcium hydr.
1g + 0.21 g → 0.99 g + 0.22 g

• From molecular weight basis both silicates require almost the same amount of
water for their hydration whereas the CH produced by C3S is more than twice the
amount of CH produced by C2S
Calcium silicate hydrates (cont.)
• By observation, it has been realized that the hydration of C3S does
not continue in a constant rate after the initial rapid reaction with
water on first mixing. This period is commonly called as dormant
period
• After some time (an hour or two), rate of hydration rises again.
Setting takes place afterwards
• The dormant period is practically significant since it is workable
during that period allowing concrete to be placed and compacted
before setting
• Considerable strength already developed before the hydration
process is finished and a small amount of hydrated cement
particles are believed to bind together the still remaining
unhydrated particles
• Further, it has been observed that strength development of
Portland cement is similar to that of the calcium silicate hydrates
Stages of hydration of C3S
• Stage 1: correlates to a period of somewhat rapid evolution of heat, which lasts for short time (about 15 min.)
• Stage 2: correlates to a period of dormancy (dormant period) lasting several hours. This is why concrete remains
plastic for several hours
• Stage 3: correlates to a period of acceleration when dormant period ends, lasting (about 4-8 hrs) during which the
rate of heat evolution reaches its maximum value. By the end of this period, the final set has passed and hardening
has begun
• Stage 4: correlates to period of deceleration during which the rate of heat evolution declines to a very low value
• Stage 5: after the rate of heat development reaches a very low value, it continues in a low steady rate

Rate of heat evolution during

Hydration of C3S
Effect of temperature on hydration of C3S
• The hydration of C3S is highly sensitive to temperature i.e. with increase
in temperature there is increase in the rate of hydration
• Once the hydration is in stage 5, it is much less temperature affected
• The effect of temperature on the hydration of C3S is shown below;
 Tri-calcium aluminate hydrate
• The amount of C3A is relatively small in cement but regardless it is the
behavior of C3A that is of immense significance to us when hydrated
• C3A in pure form (in absence of calcium sulfate, CaSO4) is wild when
reaction with water takes place causing almost immediate stiffening of the
resulting paste (flash set).
• If small amount of gypsum (dihydrate, CaSO4.2H2O) or hemihydrate
(CaSO4.0.5H2O) added to the cement, gypsum and C3A react to form
insoluble calcium sulfoaluminate i. e. formation of a protective layer called
ettringite on the surface of C3A crystals. But ultimately tricalcium
aluminate hydrate is formed.
• Initial peak rate of heat development shows that adding water to cement
causes formation of some calcium aluminate hydrate directly
• Hydration of C3A requires much more water than that of calcium silicates
• The high rate of heat development may also cause cracks in concrete which
we would like to avoid in all circumstances
• Tricalcium aluminate C3A
1. In reactions without gypsum CAH, CH, and AH3 are generated
AH3-gel
CAH10 AH3
C3A + H → C2AH8 → C3AH6
C4AH19 CH
(CH)
Meta stable Stable
hydrates end products
(fast) (slow)

3CaO*Al2O3 + 6 H2O → 3CaO*Al2O3*6H2O

C3A + 6H → C3AH6
+ water → tricalcium aluminate hydrate
1g + 0.40 g → 1.40 g
2(3CaO*Al2O3) + 27 H20 → 2CaO*Al2O3*8H2O +4CaO*Al2O3*19H2O
2C3A + 7H → C2AH8 + C4AH19
+ water → dicalcium aluminate hydrate + tetracalcium aluminate hydrate
1g + 0.90 g → 0.66 g + 1.25 g
• 2. Reactions with gypsum

Ettringite (trisulfate) and monosulfate are generated

C3A + 25 H + 3CSH2 → C3A*3CS*H31

2C3A + 5 H + C3A*3CS*H31 → 3C3ACS*H12

• 2–5 % gypsum retards C3A hydration reaction

• Ettringite is formed on the C3A patch of the cement grain and hinders its reaction.
Ettringite needles are stable as long as there is unreacted gypsum in mix water

• Thereafter ettringite reacts with C3A and monosulfate is generated

• When ettringite patch disintegrates hydration of C3A begins

3CaO*Al2O3 +3CaSO4*2H2O +25 H2O → 3CaO*Al2O3*3CaSO4*31H2O
C3A +3CSH2 +25 H → C3A*3CS*H31
Tricalcium alum. +gypsum +water → ettringite (trisulfate)
1g + 1.91 g + 1.67 g → 4.58 g

3CaO*Al2O3 +CaSO4*2H2O +10 H2O → 3CaO*Al2O3*CaSO4*12H2O

C3A + CSH2 +25 H → C3Al*3CS*H12
Tricalcium alum. +gypsum +water → monosulfate
1g + 0.63 g + 0.67 g → 2.30g
The rate of heat of hydration of C3A
• The hydration curve looks similar to that of C3S
• The first peak occurs within minutes of hydration then reduced to a lower value due to formation of
ettringite coat. The heat of hydration stays low until the ettringite breaks and converts into
monosulfoaluminate after all gypsum has been used to create ettringite
• The rate of heat evolution increases with the beginning of ettringite conversion to monosulfoaluminate and
reaches second peak and afterwards starts decreasing to a steady state

Rate of heat evolution during hydration of C3A

with gypsum
Hydration of C4AF
• Hydration of C4AF is comparable to that of C3A but proceeds
much slower and involves less heat
• C4AF does not hydrate fast enough to encourage flash set and
gypsum retards hydration of C4AF even more than C3A
• Gypsum doesn’t react with C3A only, it reacts with C4AF
forming calcium sulfoferrites and also calcium sulfoaluminate.
Its presence may also accelerate hydration of silicates
• Practical observation has shown that cement low in C3A and
higher in C4AF are more resistant to sulfate attack. This is
explained in the way that re-formation of ettringite from
monosulfoaluminate does not take place in case of C4AF due to
presence of iron in it
• The water bound chemically in C3A and C4AF are 40 and 37
respectively.
• Tetracalcium alumino ferrite C4AF
Similar reaction as with C3A but slower
4CaO*Al2O3Fe2O3 + 2Ca(OH)2+10H2O → 3CaO*Al2O3 + 3CaO*Fe2O3*6H2O
C4AF + 2CH +10 H → C3AH6 + C3FH6
tetracalcium + gypsum + water → tricalcium + tricalcium
aluminate aluminate ferrite
ferrite hydrate hydrate
1g + 0.30 g +0.37 g → 0.78 g + 0.90 g

Summary of the hydration reactions

Calcium Hydroxide, Ca(OH)2 or CH
• Created during hydration of calcium silicates
• It may compose nearly 25% of volume of solids in hydrated paste and causes the
concrete to become porous, weak and undurable
• Has the ability to react with sulfates present in water or soil to form calcium sulfates
further reacting with C3A and causes deterioration of concrete
• Its effect can be mitigated by use of pozzolans
• Its single benefit is that due to being alkaline, it keeps the pH value of water at around
13 in the concrete thus decreasing corrosion of steel reinforcement
• Takes form in crystalline material
• Most important hydration reactions and water demand in complete
hydration
 ❖ The hydration of cement compounds Hydration of calcium silicates
are summarized in the tables and rate
of hydration shown in the curve

Hydration of aluminates

Typical development of hydration of pure compounds

• With Time :
- The rate of hydration decreases continuously.
- The size of unhydrated cement particles decrease.
This is due to:
1) Accumulation of hydration products around the unhydrated
cement grains which lead to prevent water from channeling to
them.
2) Reduction of the amount of water either due to chemical reaction or
evaporation.
3) Reduction of the amount of cement due to reaction.
Water requirement of hydration of cement
• For full hydration of Portland cement, C3S needs 24% of water by weight of cement and
C2S needs 21%. On average PC needs 23% of water by weight of cement
• This 23% chemical combines with cement and can be called as bound water
• Aside from the bound water, a certain amount of water is found within the pores of the
gel called gel water
• The bound water and gel water are complementary to each other. If the amount of
water is insufficient to fill the gel pores, there is no question of the gel pores presence.
• It has been estimated that about 15% water by weight of cement is needed to fill the
gel pores. Thus for completion of hydration reaction a total of approximately
23%+15%=38% of water by weight of cement is estimated to be required so that no
excess water is left
• However, if more water is used than required for full hydration, then the excess water
may form undesirable capillary cavities
Structure of hydrated cement
• Fresh cement paste is plastic network of cement particles in
water but once it has set, its gross volume appears
approximately constant

• At any stage of hydration, the hardened paste consists

of poorly crystallized hydrates of compounds, referred
to as gel, of CH crystals, some minor components,
unhydrated cement and the residue of water-filled
spaces in fresh paste called capillary pores. Their
volume is reduced with the progress of hydration.
Water present in these pores is called capillary water Simplified model of cement paste structure.
Solid dots represent gel particles. The interstitial
Spaces are gel pores. Spaces marked by C
represent capillary pores
• Within the gel itself also exists interstitial voids called gel
pores
❖ The water added to cement
can be classified as:
1. Gel water
2. Combined water
3. Capillary water
Volume of products of hydration
• the space available for products of hydration
consists of volume of dry cement and the volume
of water added to the mix
• Non-evaporable water, determined under a
particular condition, is taken as 23% of mass of
anhydrous cement. The porosity is considered
about 28% i.e. about 28% of total volume of gel
occupied by gel pores
• The specific gravity of products of hydration of
cement is such that they take up a larger volume
than the absolute volume of unhydrated cement
but smaller than the sum of volumes of dry
cement and non-evaporable water by
approximately 0.254 of the volume of non-
evaporable water. Hence;
V(hydration products) = V(dry cement) +
V(non-evaporable water, 23%*mass of cement) –
0.254*V(non-evaporable water)
 Voids in Hydrated Cement
• Concrete strength, durability, and volume stability is greatly influenced by voids in the
hydrated cement paste
• Two types of voids are formed in hydrated cement paste
• interlayer hydration space (gel pores)
– capillary voids
• Concrete also commonly contains entrained air and entrapped air
• Interlayer Hydration Space
– Space between layers in C-S-H with thickness between 0.5 and 2.5 nm
– Can contribute 28% of paste porosity
– Little impact on strength, permeability, or shrinkage
– Depends on w/c ratio and progress of hydration
• Capillary Voids
– Depend on initial separation of cement particles, which is controlled by the ratio of water to cement
(w/c) and degree of hydration.
– On the order of 10 to 50 nm, although larger for higher w/c.
– Larger voids effect strength and permeability, whereas smaller voids impact shrinkage.
Cement paste at different stages of
hydration
w/c is 0.5 for (a)

a is 1.0 for (b)

 Heat of hydration
• It is the quantity of heat, joules per gram of unhydrated cement evolved upon complete hydration at a certain
temperature
• The actual value of heat of hydration depends on the chemical composition of cement and is nearly the same as the
sum of the heats of hydration of individual compounds when hydrated separately
• Because in early stages of hydration the different compounds hydrate at different rates, the rate of heat evolution as
well as the total heat evolved depends upon the compounds composition of cement. For this reason, lessening the
proportions of the compounds that hydrate most rapidly (C3A & C3S) the rate of heat evolution in early phase of
concrete can be lowered
• Fineness of cement also has an influence on the rate of heat release. Increase in fineness speeds up the hydration
reactions and therefore higher rate of heat evolution. Early rate of hydration of each compound in cement is
proportional to the surface area of cement. However, the effect of surface area is negligible in later stages of hydration
and total heat evolved is not affected by fineness of cement
• A controlled heat evolution is beneficial for many uses of concrete as suitable types of cement have been developed
such as low heat cement. It is thus advisable to understand heat of hydration of different cements in order to choose
the most suitable cement for a specific purpose
• The heat release is actually advantageous in cold weathers and in precast production where temp rise accelerates
strength development, in large-scale pours (mass concrete) the temperature difference between core of the concrete
and surroundings can create stresses leading to thermal cracking
• The temperature rise is dependent on: cement type (fineness, C3S & C3A contents), pouring temperature, pour
dimension, type of formwork, etc..
Heat of hydration (cont.)

Heat of hydration of compounds Influence of C3A on heat evolution (C3S

approximately constant)

Heat of hydration developed after 72 hrs at different temperatures Influence of C3S on heat evolution (C3A
Approximately constant)
 Heat of hydration (cont.)

❑ BS & ASTM describe method

of determining the heat of hydration by
measuring heats of solution of hydrated
and unhydrated cement in a mixture of
nitric and hydrofluoric acids (HNO3 & HF).
The difference between the two values
represents heat of hydration

Development of heat of hydration of different types of Portland cement

(cured at 21°C, w/c:0.4)
Heat evolution curve

Heat of hydration of cement paste (by conduction calorimetry at 20°C)

Setting and hardening of cement
• Setting is used to describe the stiffening phase of cement. This happens after adequate addition of water which leads
to formation of the paste which in turn gradually becomes less plastic with time
• Setting refers to change of cement paste from fluid to a rigid state
• The paste is said to have set when it becomes stiff enough to resist pressures
• The setting period is divided into two stages;
1. initial set 2. final set
• After the final set, the cement paste is believed further develop in strength and rigidity
• The initial set corresponds to rapid rise in temperature and final set corresponds to peak temperature
• The setting time decreases with rise in temperature. But at low temperature the reverse effect is observed (setting is
retarded).
• Setting of cement can be further divided into;
1. flash set 2. false set
• False set can occur due to added water reaction with anhydrate CaSO4 (gypsum) forming hydrate forms of gypsum
which can cause stiffening, presence of alkalis during storage can form alkali carbonates, these react with CH liberated
by hydration of C3S to form CaCO3 which precipitates and creates rigidity, and aeration of C3S at moderately high
temperature
Strength build-up
On adding water to the cement:
• C3A is the fastest to hydrate and contributes to immediate strength (1-3 days) but at advanced age it has little
to no contribution to strength development
• C4AF does not have any noticeable effect of strength development
• C3S hydrates almost immediately next to C3A and has an immense effect on early strength
• C2S has been found to be responsible to strength development 28 days onwards contributing to ultimate
strength

Development of strength in pure

compounds
 Factors affecting hydration
Main factors :
• Chemical composition of cement
The mineral composition of cement and their proportions are the main factors affecting the hydration of cement. Various mineral
components will reveal different characteristics when reacting with water. For example, the increase of C3A can speed up the hydration,
setting and hardening rate of cement, and the heat of hydration is high at the same time.
• Cement type
each type of cement has a particular chemical composition to serve the purpose for which it is to be used so increasing or decreasing some
of the compounds (esp. C3A & C3S) will lead to direct increase or decrease in rate of hydration i.e. type III cement has rapid hydration
characteristics with increased early-age hardening whereas type II & type IV have retarded hydration rates due to the fact that its purpose is
served when hydration proceeds slowly.
• Sulfate content
If the content of SO3 is too little, the retardation affect will be unobvious. Too much SO3 will accelerate the hydration of cement. The
appropriate amount of SO3 depends on the gypsum content and of C3A in the cement and it also related to the fineness of cement and the
content of SO3 in clinker. If the content of SO3 exceeds the limit, it will lower the strength of cement and it can even lead to poor soundness,
which will cause the expanded destruction of cement paste.
• Fineness
The finer the cement particles are, the larger the total surface area is and the bigger the area contacting with water is. Thus, the hydration
will be quick, the setting and hardening will be accelerated correspondingly, and the early strength will be high.
• Water/cement ratio
If the cement consumption is unchanged, the increase of the mixing water content will enhance the amount of capillary porosities, lower
the strength of cement paste, and extend the setting time. Therefore, in practical projects, the amount of water and cement will be changed
without modifying the water-cement ratio.
 Factors affecting hydration (cont.)
• Curing temperature
Usually, the temperature rises at the time of curing, and the hydration of cement and the development of early strength become
fast. If the hardening process occurs at a low temperature, the final strength won’t be affected though the development of the
strength is slow.

• Addition of supplementary cementing substances, additives and admixtures

Hydration, setting, and hardening of Portland cement are constrained by C3S, C3A. And all the admixtures that affect the hydration
of C3S, C3A can change the performance of the hydration, the setting and hardening of Portland cement. For example, the
accelerator agents (such as CaCl2, Na2S04) can accelerate the hydration and the hardening of cement and improve its strength. On
the contrary, the retarding agents (such as calcium lignosulphonate) can delay hydration and hardening of cement and affect the
development of the early strength.
Approaches used to study hydration of cement
Following methods are used to investigate cement hydration:
• Thermal analysis

• X-ray diffraction

• Scanning electron microscopy

References
• Properties of concrete, A. M. Neville

• Advanced concrete technology, John Newman & Ban Seng Choo

• Concrete technology, B. L. Gupta & Amit Gupta

• Hydration of cement, Rizwan Riaz, Muhammad Safdar & Fatima Mehvish

https://www2.slideshare.net/rizwansamor/hydration-of-
cement?qid=179af270-64dc-4673-bb4d-dfab983e3b54&v=&b=&from_search=5
• Concrete technology, Hydration of cement, Sukhvinder Singh
https://www2.slideshare.net/SukhvinderSingh89/hydration-of-cement-
73655061?qid=179af270-64dc-4673-bb4d-dfab983e3b54&v=&b=&from_search=2

• Concrete technology, A. M. Neville & J. J. Brooks

Thank You