Hydration of Pure Cement Compounds

Hydration - reaction with water

Reaction products formed hydration products
Calcium silicates








100 + 21 99 22
Note: Difference in mass of water for hydration, products C-S-H and CH
100 + 24 75 49
Tricalcium Aluminate (C
3
A)
Primary initial reaction


(AFt)
Ettringite (Aft) is a stable hydration product only while
there is an ample supply of sulfate
(Intergrind gypsum with clinker to avoid flash set)
(No measured expansion after 2 days max. SO
3
)
(Unstable at temperatures > 70
O
C potential DEF)
If the sulfate is consumed before C
3
A has completely
hydrated

monosulphoaluminate
(Afm)

H
S C A
C
32 3
3
H
S C A
C
12 3

Hydration of Pure Compounds
Ferrite Phase C
4
AF
Forms similar hydration products to C
3
A, but less
reactive
Reactions are slower and involves less heat
Changes in the composition of ferrite phase affect the
rate of hydration
Fe |, hydration becomes slower
Reactions
Hydration Products
Precipitation of
CH and ettringite
at early time
after ~2 hrs, CSH
formed
6 hrs 1 day,
rapid increase of
CH, CSH, and
ettringite
After ~2 days,
ettringite
monosulpho-
aluminate

(Locher & Richartz 1976)
Hydration Rate
Example of relative rate
of hydration of main
potential compounds

C
3
A fast early hydration
(within 1st minute) but
small amount of hydrates
High heat generation over
next few days (< 100 h)

Hydration of C
3
S
generates Ca(OH)
2

(potential for pozzolanic
reaction with SCMs, e.g.
fly ash, ggbs, silica fume)
Hewlett , Ed., 1998
Notes
Gypsum is important to avoid flash set; but if it is too
much, affect setting and hardening, also affect long-
term volume stability as ettringite has high volume that
can cause expansion and cracking if formed at later
age.
The amount required increases with C
3
A content.
Limit: specified in standards, e.g. SS EN 197-1, Table 3

C
3
A is undesirable as it contributes
little to strength except at early
stage; but it is useful to reduce
production temperature of cement
clinker.

(Mindess et al 2003)
Hydration of Portland Cement
Assumption: the cement compounds hydrate
independently

Compound interactions
C
3
A & C
4
AF both compete for sulfate ions
It is suggested that gypsum accelerates C
3
S hydration
Increasing SO
3
may reduce rate of heat evolution and
total hear evolved at early age, but not after 28 days
(Lawrence in Hewlett, 1998)

Kinetics
The rate of hydration during the first few days
C
3
A > C
3
S > C
4
AF > C
2
S

Rate of heat evolution


(Mindess et al. 2003)
Stage 1 dissolution Stage 2 induction (dormant)
Stage 3 Acceleration Stage 4 Deceleration
Stage 5 - Steady
Determine
initial setting
Determine final setting
& initial hardening
Hydration Heat Evolution
Stage 6 onwards hydration rate depends diffusion rate of
water and ions of hydration product (solid state diffusion)

Hewlett, Ed., 1998
Heat of Hydration
Heat of hydration in J/g of a typical cement
H
3 days
= 240 C
3
S + 50 C
2
S + 880 C
3
A + 290 C
4
AF
H
1 year
= 490 C
3
S + 225 C
2
S + 1160 C
3
A + 375 C
4
AF
Quantities of C
3
S, C
2
S, and so on are expressed as weight fraction
of the cement (potential compounds)
C
3
S (502 J/g), C
2
S (260 J/g), C
3
A (1160 J/g), C
4
AF (420 J/g)
Temperature rise due to heat of hydration under
adiabatic condition is ~12-14
o
C per 100 kg of OPC
AT = (M
c
. H) / (M
c
. S
c
+ M
a
. S
a
+ M
w
. S
w
)
Where
H = heat of hydration (increases with degree of hydration -time)
M = mass ( c-cement, a-aggregate, w-water)
S = specific heat (c = 0.88 J/g
o
C, a = 0.75 J/g
o
C, w = 4.18 J/g
o
C)
Concrete: c = 300-500, w = 140-180 , aggregate = 1600-1800 (kg/m
3
)
Heat of Hydration
ASTM Type l = CEM l (strength class 42.5)
ASTM Type III ~ CEM l (strength class 52.5)
ASTM Type IV ~ CEM l (strength class 32.5)


Peak temperature in thick sections , e.g. Pile caps and
raft foundations with least dimension 2 m occurs at
around 3 days (one dimension heat lost)
Neville, 1995, Ref. 1.30, Lerch & Ford, 1948)
(Note: Temperature Effect)
C-S-H
Compositional variation
C/S = 1.5 - 2.0, depends on age of the paste, curing
temperature, w/c, impurities
Varying water content, water in C-S-H exists in several different
states

Physical behavior
Amorphous, poor crystalline materials
Extremely small irregular particles in the size range of colloidal
matter (< 1m)
High surface area ~400 m
2
/g

Develop at the surface of calcium silicate, forms a coating
covering the grain, thickness of the hydrate layer increases
and forms a barrier further hydration is controlled by
diffusion of water in and ions out through the barrier

Model of C S - H structure
Layered structure
C-S-H
bread calcium silicate
sheets
filling Ca
++
, H
2
O
- Sheets are distorted
and randomly arranged.
- Space between the
calcium silicate sheets
is the intrinsic porosity:
I interlayer pores
M- micro pores
P isolated capillary pores
Clay C-S-H
(Mindess 2003)
Model of C S - H structure
Source: Young et al, 1998
Estimated Properties & Influence of C-S-H
Source: Young et al, 1998
C-S-H
Model of CS-H structure and water held in C-S-H
In capillary pores (P), menisci are created as the pores
are filled or emptied (high mass loss, low shrinkage)
In micropores (M), the adjoining surfaces are so close
together that water cannot form menisci, and
consequently has different behavior from bulk water.
Water in M acts to keep the layers apart by exerting
disjoining pressure.
The disjoining pressure depends on RH and disappear
below 50% RH (high shrinkage)
In interlayer pores (I), water are structurally associated
with solid
Hydroxyl water in solid lattice
No sharp distinction between different forms of water
As water is removed from C-S-H, rearrangement of
particles is possible.
Calcium Hydroxide (CH)
Well crystallized material with definite stoichiometry
In voids or cracks: Hexagonal tabular morphology
Strong alkaline, in solution gives a pH>12, responsible for the
protection of steel from corrosion in reinforced concrete

Calcium Sulphoaluminates
Ettringite
Hexagonal crystals in the form of needles, typically 10x0.5
m
Often found in voids or cracks in mature concrete
Monosulphoaluminate
Clusters or rosettes of irregular plates when first
formed
Grow into well-developed, but very thin, hexagonal plates
Degree of crystallinity is decreased to some extent due to
impurities
monosulphoaluminate
CH (striated)
ettringite
(Mindess 2003)
Note: For Information ONLY
Properties of the Hydration Products (Mindess 2003)

Microstructure of Hydrated Cement Paste
(a) Water separates
cement grains
(b-d) solid hydration
products form a
continuous matrix
and bind the
residual cement
grains together.
This happens
because the
hydration products
occupy a greater
volume than the
original cement
compounds due to
their lower specific
gravity (~2.0 vs 3.2)
CH
(Mindess 2003)
Microstructure of Hydrated Cement Paste
C-S-H
Occupy > 50% volume of hydrated paste
Two forms of C-S-H
Early product C-S-H (groundmass & undesignated product)
Grows out from the particle surface into the surrounding
water-filled space in the form of low density arrangement of
thin sheets (outer product from surface of cement grain)
Higher micro porosity
Contains a high level of impurities (Al, SO
4
, K, Na)
Later product C-S-H (inner product)
Denser coating around the hydrating cement grains
The coating forms diffusion barrier during later hydration,
thicken with time, growing inwards & outwards
The coating maintains the shape of original grains
Less impurities, more resistant to physical change on drying
The proportion | as hydration | or the w/c +
Fractured surface
< 3 days
Polished surface
28-day old paste
High degree of complexity
Unhydrated
cement particle
Later CSH
product
Early CSH
product
(Darwin 1994)
Ettringite needles
Interface between early & later CSH
indicate cement grain boundary
Microstructure of Hydrated Cement Paste
Calcium hydroxide
Occupy ~20-25% of the pastes solid volume
In Stage 3 of C
3
S hydration, many CH crystals nucleate
and grow within the capillary pore space
CH will only grow where free space is available
Morphology vary, particularly affected by admixtures and
by temperature of hydration

Calcium sulphoaluminates
Occupy only ~10-15% by solid volume
Play a minor role in the microstructure (although not
necessarily in properties)
Both ettringite and monosulphoaluminate are well
dispersed throughout the paste

Microstructure of Hydrated Cement Paste
Unhydrated residue of cement grains
may persist even in well hydrated cements
Porosity
Classification (Mindess 2003)









Enormous range of pore sizes
Water that occupies the pores plays many different roles
Microstructure of Hydrated Cement Paste
Mehta & Monteiro, 1997
Note: Fine aggregates (> 150 m and < 4 mm)
Coarse aggregates (> 4 mm and < 150 mm)
Microstructure of Hydrated Cement Paste
Porosity - Classification
Capillary pores remnants of water filled space that exists
between the partially hydrated cement grains
Gel pores regarded as an intrinsic part of the C-S-H (cannot
be resolved by SEM), (include small capillary pores)
Capillary pore system is the interconnected network of pores
through which bulk water flow & ion diffusion occur easily
Porosity - Measurements
Mercury intrusion porosimetry
Forcing mercury into pore system by applying external
pressure, pressure required is inversely proportional to
the pore radius
Give better appreciation of capillary pore system
Physical adsorption of gases
Pores are filled by a condensed vapor (gas) through
capillary condensation
Give better measure of gel-pore system
(Medium capillary pores)
(small capillary pores)

{
{
Capillary
pores
Gel pores
Mindess ,2003
Note: Shrinkage and creep both lead to change in surface energy of CSH,
fundamentally related to thermodynamics of gel water
Microstructure of Hydrated Cement Paste (HCP)
Pore solution
Fluid contained in capillary pores is not pure water, but
an ionic solution that is in equilibrium with hydrated paste



inde





In low alkali cement, pH ~ 13
In high alkali cements, pH > 13.5
(S. Diamond, Figure 4.11,
Mindess et al, 2003 )
Note: Role of alkalis in ASR & corrosion passivation in concrete
Note:
Time (> 3 days) for
sufficient amount
of CH to activate
pozzolans
Interfacial Transition Zone
Microstructure of HCP is highly modified in the vicinity of
embedded materials: aggregates, fibers, and reinforcing steel
The modified volume is called interfacial transition zone (ITZ)
Common features of ITZ
Increased porosity
Reduction of unhydrated cement
Higher w/c due to the wall effect and localized bleeding
Within the free space close to the surface, crystals of CH or
ettringite can readily form, CH predominates and often highly
oriented
Thickness of ITZ: ~20-40 m
vary depends on the size, shape, and volume of aggregate, w/c,
mixing and placing procedures
due to wall effect
Interfacial transition zone
ITZ plays an important role
in mechanical properties
and permeability

Recent views:
Potential weakness for crack
initiation in concrete
May be modified by pozzolanic
reaction products and/or nano
particles
Difficulties in determining ITZ
properties due to its small
thickness and changing with
distance from particle surface

Mindess et al. 2003
Volume changes during hydration
All cement hydration products have lower specific
gravities than the cement compounds
Hydration reaction is accompanied by an increase in
solid volume and decrease in porosity.
Expansive reactions
CH grows around solid particles or stops growing when it
meets obstacles. The same is true of C-S-H. Thus, the
hydration of calcium silicates is not accompanied by increase
in the total volume of paste. If original water occupied space is
filled, hydration will cease.
Bulk expansion occurs when ettringite is formed after cement
paste is hardened. If space is limited, ettringite crystals may
develop crystal growth pressures.
Early age, plenty space for ettringite to grow, no problem
Calculation of volume change
Equations are empirical, derived from experimental data
The hydrated cement includes all hydration products, CH, C-S-H, and
sulphoaluminates
Evaporable water lost under D-drying or oven drying condition
(include water in capillary and gel pores, and water in sulphaluminates)
Non-evaporable water - lost from D-drying to 1000
o
C (measures water
chemically combined in hydration products)
Non-evaporable water
, o = degree of hydration
Evaporable water associated with hydration products
w
g
: gel water (C-S-H) + water
in in calcium sulphoaluminates

Total volume of hydration products

Gel porosity
constant for all normally
hydrated cements
Calculation of volume change
Capillary pore volume


Volume occupied by unhydrated cement

v
c
specific volume of cement, (1/specific gravity) = 0.32
Original volume of the paste

Capillary porosity


Gel/space ratio
Volume relationships among constituents of hydrated cement pastes
w/c = 0.5
o = 1.0
Mindess et al. 2003
Full Hydration
POSSIBLE in practice?
Calculation of Volume Change
Minimum w/c ratio
At low w/c ratios, there is insufficient space for the
hydration products to form so that complete hydration is
not possible. The minimum w/c that can be used and still
ensure complete hydration can be determined from


Set V
c
= 0, and o=1, the minimum w/c = 0.36
However, the hydration products must be formed with
the gel pores saturated. Thus, water required for
complete hydration is



For complete hydration (o=1), the w/c should not be <0.42
0.24o 0.18o
Volume Relationship
For example 100 g of cement at o = 1 (fully hydrated)
V
hc
= 100/3.15 = 32 cm
3
(density 1 g/cm
3
= 1000 kg/m
3
)

w
n
= 0.24 o g/g of cement, V
wn
= 24 cm
3
w
g
= 0.18o g/g of cement, V
wg
= 18 cm
3
V
hp
= 0.68o cm
3
/g of cement = 68 cm
3


V
hc
+ V
wn
< V
hp
< V
hc
+ V
wn
+ V
wg
32 + 24 68 32 + 24 + 18
(56) (74)
[vol. of reactants]< [vol. of product] < [vol. of components]

Note: V
hc
, space for inner product. Outer product in space
provided by water (w/c 0.42 for full hydration)

Volume Relationship
For example 100 g of cement at o = 1 (fully hydrated)
V
hc
= 100/3.15 = 32 cm
3
(density 1 g/cm
3
= 1000 kg/m
3
)

w
n
= 0.24 o g/g of cement, V
wn
= 24 cm
3
w
g
= 0.18o g/g of cement, V
wg
= 18 cm
3
V
hp
= 0.68o cm
3
/g of cement = 68 cm
3


V
hc
+ V
wn
< V
hp
< V
hc
+ V
wn
+ V
wg
32 + 24 68 32 + 24 + 18
(56) < (74)
[vol. of reactants]< [vol. of product] < [vol. of components]

Note: V
hp
< volume of components , difference in volume to
be filled from ingress of external water (curing) otherwise by
some capillary water forms vapour (vapour pressure < 1, RH
< 100%) e.g. sealed specimen or external RH < 100%
Volume Relationship
Non-evaporable water
Evaporable water in hydrated products
Volume of hydrated products
Capillary porosity
Gel/space ratio
Except for X, all are linearly proportional to degree of hydration, o
Consider the cases at o = 0.5 (50% hydration) for w/c of 0.36, 0.42 and 0.50
Factors Leading to Cessation of Hydration
Environmental factors:
Temperature lower than ( 10
O
C) freezing of pore fluid
Lack of water for hydration, e.g. w/c < 0.42, o < 1.0
Lowing vapour pressure in capillary pores, e.g. sealed
specimen, no ingress of water (curing)
Vapour pressure < 0.8: hydration rate is low
Vapour pressure < 0.3: hydration rate is negligible
[Powers, 1947 Ref. 7.36 in Neville, 1995, Fig. 7.1]

Physical factors:
Lack of space for hydration products, e.g. w/c < 0.36
Large grain size cement particles (> 40 m in diameter)

In practice, common curing period is 7 days, o < 0.6 to 0.7
w/c 0.2 to 0.3 for high strength concrete [What value is o?]

Environmental Factor
Hydration rate highest when capillary
pores are saturated, i.e. vapour
pressure of 1.0 (RH 100%)

Below vapour pressure of 0.8 (RH 80%)
hydration is low

Below vapour pressure of 0.3 (RH 30%)
hydration is negligible

Note: Tropical hot wet climate, range
of ambient RH between 60% (afternoon)
and over 80% (night)

Air-conditioning may bring RH to 30%
Source: Properties of Concrete, A.M. Neville, 4
th
Ed. 1995, Pitman
Powers, T.C., A discussion of cement hydration in relation to curing of concrete, Proc. Highw. Res. Bd, 27, 1947
Fig. 7.1
Schematic Representation of Single Cement Grain
Modified from Williamson, 1970
Comparison of ASTM and BS-EN Standards
ASTM BS-EN
Portland
cement
C 150 Spec for Portland
cements
197-1: 2000 (SS EN 197-1: 2008)
CEM I Portland cement
[197-1: 2011]
Blended
cements
C 595 Spec for blended
hydraulic cements
197-1: 2000 (SS EN 197-1: 2008)
CEM II Portland comp. cem
CEM III blastfurnace cem
CEM IV pozzolanic cem
CEM V composite cem
C 1157 Performance Spec
for blended hydraulic
cements
Mineral
admixtures
C 618 Spec for coal fly ash
and raw or calcined natural
pozzolans for use in concrete
450-1: 2005
Fly ash for concrete Definition,
spec, and conformity criteria
C 989 Spec for GGBFS for
use in concrete and mortars
15167-1: 2006 (SS EN 15167: 2008)
Ground granulated blast furnace
slag for use in concrete, mortars,
and grouts
C 1240 Spec for silica fume
used in cementitious
mixtures
13263-1: 2005
Silica fume for concrete
Portland cement
CEM I K = 95 to 100%, MAC = 0 to 5%
Portland-fly ash cement (MAC = 0 to 5%)
CEM II/A-V: K = 80 to 94%, V = 6 to 20%
CEM II/B-V: K = 65 to 79%, V = 21 to 35%
Portland-silica fume (MAC = 0 to 5%)
CEM II/A-D: K = 90 to 94%, D = 6 to 10%
Clinker: K, Blastfurnace slag: S
Silica fume: D, Fly ash: V (siliceous)
Blastfurnace cement (MAC = 0 to 5%)
CEM III/A: K = 35 to 64%, S = 36 to 65%
CEM III/B: K = 20 to 34%, S = 66 to 80%
CEM III/C: K = 5 to 19%, S = 81 to 90%
No change in Table 1 of BS EN 197-1: 2011
Specification for Constituent Materials Cement
Revision of BS EN 197-1: 2011
Combining EN 197-1 and EN 197-4 and addition of sulfate resisting
classes of cement (superseding EN 197-1 and EN 197-4)
SS EN 197-1: 2008 to be revised as per BS EN 197-1: 2011

Sulfate resisting cements 3 main groups:

Sulfate resisting Portland cement
CEM I-SR 0, sulfate resisting Portland cement (C
3
A content of clinker = 0%)
CEM I-SR 3, sulfate resisting Portland cement (C
3
A content of clinker 3%)
CEM I-SR 5, sulfate resisting Portland cement (C
3
A content of clinker 5%)

Sulfate resisting blast furnace cement (no requirement on C
3
A content of clinker)
CEM III/B-SR, sulfate resisting blast furnace cement
CEM III/C-SR, sulfate resisting blast furnace cement

Sulfate resisting pozzolanic cement (C
3
A content of clinker 9%)
CEM IV/B-SR, sulfate resisting blast furnace cement
CEM IV/C-SR, sulfate resisting blast furnace cement


Specification for Constituent Materials Cement
Revision of BS EN 197-1: 2011
Table 2 Seven products in sulfate resisting common cements
Main
types
Notation of the seven
products
(types of common
sulfate resisting
cements)
Composition (percentage by mass)
Main constituents Minor
additional
constituents
Clinker
K
Blast
furnace
slag
S
Pozzolana
natural
P
Siliceous
fly ash
V
CEM
I
Sulfate
resisting
Portland
cement
CEM I-SR 0
CEM I-SR 3
CEM I-SR 5
95 - 100 - - - 0 - 5
CEM
III
Sulfate
resisting
blast
furnace
cement
CEM III/B
- SR
20 - 34 66 - 80 - - 0 - 5
CEM III/C
- SR
5 -19 81 - 95 - - 0 - 5
CEM
IV
Sulfate
resisting
pozzolanic
cement*
CEM IV/A
- SR
65 - 79 21 - 35 0 - 5
CEM IV/B
- SR
45 -64 36 - 65 0 - 5
* Main constituents other than clinker shall be declared by designation of cement (P or V)
Specification for Constituent Materials Cement
Revision of BS EN 197-1: 2011
Table 3 Mechanical and physical properties as characteristic values

Strength
class
Compressive strength (MPa) Initial setting
time
Soundness
(expansion
Early strength Standard strength
2 days 7 days 28 days min mm
32,5 L
a
- 12
32,5 52,5 75
10
32,5 N - 16
32,5 R 10 -
42,5 L
a
- 16
42,5 62,5 60 42,5 N 10
42,5 R 20
52,5 L
a
10
52,5 - 45 52,5 N 20
52,5 R 30
a
Strength only defined for CEM III cements

NOTE: CEM III cements are distinct low early strength blastfurnace cements
VICAT APPARATUS EN 196-3: 2005
Standard Consistence:
Water content for 500 kg cement when
distance between plunger (Figure 1 c)
and base-plate is (6 2) mm (to the
nearest 0,5%)

Initial Setting Time:
The elapsed time, measured from zero to
time at which distance between needle
(Figure 1 d) and the base-plate is (6 3)
mm (to the nearest 5 min.)

Final Setting Time:
The elapsed time, measured from zero to
that at which the needle (Figure 1 e) first
penetrates only 0,5 mm into the
specimen (to the nearest 15 min.)
Note: No requirement in BS EN 197-1

Chemical Requirements (BS-EN 197-1: 2000)
Note:
SO
3
limit for
different
strength class
Note:
Higher limit
for CEM II/B-T
& CEM lll/C
Identical with
Table 4 of BS
EN 197-1:
2010
Compressive Strength Determination

Cartoon on Concrete
Source: IEM Bulleting