Materials and Structures/Matbriaux et Constructions, 1991, 24, 143-157

RILEMTECHNICALCOMMITTEES
COMMISSIONSTECHNIQUES DE LA RILEM
68-MMH: MATHEMATICALMODEI.I1NG
OF CEMENT HYDRATION
TASK GROUP 1

Strength of cement (final report)

I. O D L E R
Institut fiir Nichmetallisehe Werkstoffe, Technisehe Universitdt Clausthal, 3392 Clausthal-Zellerfeld, Germany

1. INTRODUCTION
In this report, data on the effect of cement structure and
hydration conditions on strength and strength development are reviewed and analysed. Emphasis is put on a
critical analysis of models that describe the relationship
between strength and other relevant parameters, and that
may be useful for predicting the strength development
and ultimate strength of the binder. Data on the progress
of hydration and on cement paste structure are discussed
only in as much as they are related to cement strength.
This report deals mainly with the strength development of
ordinary Portland cement and with hydration at room
temperature; however, data on strength and strength
development of blended cements, on the effect of chemical
admixtures and on the effect of temperature are also
discussed, though to a more limited extent.
In cement research, different types o'f strength (compressive, flexural, tensile etc.) may be determined. Moreover,
additional parameters may be employed to be used as
indicators of the strength characteristics of hydrated
cement (E-modulus, hardness etc.). In this report, compressive strength will be considered unless otherwise
stated. It has also to be taken into consideration that the
strength of a given binder depends - in addition to its
quality - on other factors such as composition of the paste
or mortar employed for testing, geometry of the test
specimens, its curing, etc. Thus, this has to be considered
in comparing data published by different investigators.
In this report, first the available data on the strength
development of pure clinker minerals and on their
interaction will be analysed. In subsequent sections, data
on the effect of clinker composition, calcium sulphate
addition and fineness will be surveyed. Subsequently, the
effect of hydration time, hydration temperature, total
porosity, pore structure and some other factors on
strength will be analysed. Finally, based on these data, the
0025-5432/91 q') RILEM

possibility of expressing the strength by means of

mathematical equations will be analysed.

2. STRENGTH OF PURE CLINKER MINERALS

The rate of strength development and the ultimate

strength differ significantly for different clinker minerals.
From data published by Bogue and Lerch [1] and shown
in Fig. 1 it appears that C3 S exhibits both the fastest
strength development and highest ultimate strength. The
strength of C2S grows significantly slower; however, the
ultimate strength of this phase is similar to that of C3S.
Contrary to this, the strengths obtained by both C3 A and
C4AF are very low even after a long hydration time.
Table 1 contains data published by Mironov and
Malinina [2]. According to their findings, C4AF produced
the highest ultimate strength of all compounds, followed
closely by C3 S. C2S exhibited a significant strength only
after long hydration times, while the strength of C3A

,-"1"

olO

o,g
0 2B

90

180

360

Age,doys
Fig. 1 Compressive strength development of pure clinker
minerals [1]

144

68-MMH: Mathematical modelling of cement hydration

Table 1 Compressive strength of specimens made from pure

clinker minerals according to Mironov and Malinina [2]
Mineral

100

E
E

Compressive strength (MPa)

7 days

28 days

365 days

32.2
2.4
11.8
30,0

46.6
4.2
12.4
38.4

58.4
32.5
0
59.5

80

CX~

C3S

/~-C28
C3A
C4AF

Table 2 Compressive strength of specimens made from pure

clinker minerals according to Butt et al. [3]
Mineral

L_

.>-

60

l+O

bq
c~J
~=

E
o

20

Compressive strength (N m m 2)
7 days

28 days

30.0
5.5
--

52.0
32.0
6.5
38.0

3~
C3S
#-C2S
C3A
C4AF

--

C3S 100%
C3S 95%, CSH2 5%
C3A 100%
C3S 75%, C3A 25%

Tensile strength (MPa)

3 days

28 days

0.8
1.1
0
1.5

1.9
2.3
0.3
1.9

Table 4 Compressive strength of clinker mineral blends

according to Bogue and Lerch [1] (mortars)
Material

C3S 85%, #-C2S 15%

C38 85%,C3A 15%
C3S 85%, C4AF 15%

36

38

~0

~2

4~

~6

~B

SO

w/c- r a t i o x 100
Fig. 2 Compressive strength of fully hydrated pure clinker
minerals at different w/c ratios /-4]: (A) C3S, (r C3A, ([])
CgAF.

Table 3 Tensile strengths of clinker minerals and their

blends according to Haegermann [15] (mortars)
Material

Compressive strength (MPa)

3 days

28 days

14.6
12.3
11.4

29.3
27.5
20.7

dropped to zero after reaching low, yet measurable, values

within the first 28 days.
Data reported by Butt e t al. [3] are shown in Table 2.
According to their results C3S yielded the highest and
C3A the lowest strength after 28 days of hydration.
Compressive strength values found on fully hydrated
C3S, C3A and Cr
pastes made with different starting
water/solid ratios/-4] are shown in Fig. 2. The strength of
fully hydrated C3A and CgAF were similar and significantly lower than those of C3S.
Introduction of foreign ions into the crystalline lattice
of C3S may distinctly affect the resultant strength. This

effect may be either a direct or an indirect one brought

about by a simultaneous modification change of the
tricalcium silicate produced [5-11]. Also the type and
quantity of ions used for stabilizing #-C2S may affect the
reactivity and thus the strength development of the
resultant material [12-14]. The strength development
may be altered if more than one clinker phase is present in
the system or if the clinker phase hydrates in the presence
of gypsum. Table 3 shows pertinent data of Haegermann
[15] and Table 4 those of Bogue and Lerch [I].
According to Haegermanra's findings the strength of
C3S became increased by the presence of gypsum or CaA.
According to Bogue and Lerch the presence of#-Ca S has
a more favourable effect on C3S strength than that of
C3A or C4AF.
Data on the strength development of pure C3S and its
blends with C3A and CeAF found recently by Locher and
Odler [16] are summarized in Fig. 3. A partial replacement of C3S by C3A resulted in an increase of strength at
small additions and after shorter hydration times, yet in a
subsequent strength decline at high C3A additions.
Blends of C3S and CgAF exhibited lower strengths after
all hydration times than pure C3S.
The effect of gypsum additions on the strength of C3S
has been studied by Bentur [17]. Up to a degree of
hydration of 40% the strength remained constant for
gypsum additions between 0 and 9%. At a hydration
degree of 60% the strength declined sharply up to 2%
SO 3 and remained constant afterwards. From all this it
appears that data on the strength of hydrated clinker
minerals are rather scarce and contradictory. It appears
that significant differences exist between them. Moreover,
the bonding properties of any of them may be influenced
by the incorporation of foreig~n ions into their crystalline
lattice.

Materials and Structures

145

5O

t,0

30

C3S
o 100
o
70
<~ 50

20

10

28

70

50

50

C3A

CI.AF C~H2

30

50
30
50
100
25

25

90 f (d)

Fig. 3 Strength development of blends of clinker minerals [-16].

3. E F F E C T OF P O R T L A N D C E M E N T CLINKER
PHASE C O M P O S I T I O N ON S T R E N G T H
It may be assumed that each of the phases of Portland
clinker contributes either directly or indirectly to the
strength development and ultimate strength of the
resultant cement. It is conceivable that this effect may be
an additive one, in which case each of the phases present
acts individually, or a cumulative one in which case an
interaction between the individual phases takes place,
enhancing or weakening their effect.

3.1 Regression equations

Several researchers have investigated the relationship between clinker phase composition and strength after a
preset hydration time, using multiple linear regression
analysis and thus assuming an additive action of the
phases involved. In such a case the relationship between
strength and cement composition may be expressed by an
equation of the type
0"t = a 0 -k- a l c 2 --I-a 2 c 2 + a3c 3

(1)

where at = strength after hydration time t; a o, a 1, a 2 ,

a 3 ----regression coefficients (constants); and c l , c 2, c 3 =
contents of phases 1, 2, 3 in clinker.
Blaine e t aL [18] proposed a series of equations obtained
by evaluating cement strength against a number of clinker
parameters (such as phase composition, ignition loss,
insoluble fraction, air content, alkali content), using
multiple linear regression analysis. They found that all the
above parameters may be related to strength.
Alexander e t a L [19] studied the relationship between
strength and cement composition on 30 Australian
cements containing between 46 and 62% C3 S and
between 1 and 11%0 C 3 A . They concluded that the most

significant association between strength and compound

composition lies in the regression involving C3A alone.
C4AF was found to have little or no effect on strength.
This may, however, be related to the difficulties in
analysing quantitatively C4AF in industrial cements. In
subsequent work by Alexander [20] it was found that the
correlation of strength with C3 S passes through a
maximum at 7 days and that with C3 A is highest at 28
days.
Kn6fel [21] found that the 28-day strength is linearly
proportional to the sum 3C3S + 2C2 S + C3 A + C4AF.
SchrS.mli [22] in analysing his own data and data from
the literature concluded that C3 A affects positively the
initial and moderately negatively the ultimate strength.
Osbaeck [23] found a negative effect of C3A on 7- and
28-day strength as determined by multiple regression
analysis (31 cements), while the effect of C3 S is expectedly - a positive one. The correlation coefficient
between strength and C3S or C3 A content was not
significant for 1- and 3-day strengths. This finding may,
however, be explained by the simultaneous existence of a
correlation between the amounts of alkali and C3 A in the
specific set of data studied.
Aldridge [24] studied the relationship between
strength and phase composition on 114 cements from
New Zealand. He concluded that an equation of the type
a c = ao + alC3S +az(C3S + C2S) +a3C3 A + a4SA

(2)

yielded better fits than a simpler equation of the type

a c = a o + a l C 3 S + a z C 3 A + a3SA

(3)

where SA = specific surface area. C4AF was found not to

be influential as to its effect on strength development.
Alexander and Ivanusec [25] established recently that

146

68-MMH: Mathematical modelling of cement hydration

Table 5 Equations expressing the effect of clinker phase composition as proposed by different investigators
Equation

Ref.

a28 = K(3C3S + 2C2S + C3A + C4AF)

Kn6fel [21]

MPa

0 3 = - 3 0 + 0.28 C3S + 0.64 C3A + 0.073 SA

0"z8= 2.5 + 0.45 C3S + 1.14 C3A + 0.045 SA

MPa

Aldridge [24]

MPa

0"3 = - 5 5 +0.34C3S +0.36(C3S + C2S) +0.64C3A +0.73 SA

0"28= - 8 3 + 0.32 C3S + 1.2(C3S + CzS)+ 1.14C3A +0.49 SA
a28 = 200 C3S + 90 C2S + 405 C3A

(W/C= 0.35)

p.s.i.

0"28 = 90C3S+0C2S +450C3A

0"28 =40C3S+0C2S + 80C3 A

(w/c = 0.50)
(w/c = 0.80)

p.s.i.
p.s.i.

MPa
MPa

Aldridge [24]

Alexander et aL [19]

0"28 = 5.14 + 0.386 C3S - 0.087 C2S + 2.980 C3A -q-0.64 C4AF + 0.0617 SA
0"3 = 10-19 +0.170C3S+ 0-279 C3A +0.0485 SA
0"28 = 1-97 +0.188 C3S +0.279C3A +0.0385 SA

MPa
MPa

MPa

Alexander [20]
Alexander [20]

SA = surface area (cm 2 g- t); K = constant.

the relationship between strength and the C3S content of
cement does vary greatly with the SO 3 content of cement.
On the other hand, variations of SO 3 at a constant C3A
content have little effect on strength. In Table5 linear
equations expressing the relationship between compressive strength and clinker phase composition published by different investigators are summarized. They
were all determined by multiple regression analysis,
evaluating experimental data from different sets of
cements studied. In comparing these data one has to
consider the different methods of testing employed as well
as different units in which the strengths are expressed.
Expectedly, the regression coefficient associated with C3S
was consistently positive, indicating a positive effect of
C3S on strength. The coefficient associated with C3A was
also positive. Its magnitude was always greater than the
one associated with C3S. Its value was always greater in
the equation expressing 28-day rather than 3-day
strength. The coefficient for the effect of C2 S after 28 days
was found to be either positive, negative or equal to zero.
This discrepancy may probably be explained by the
difficulties associated with the determination of this phase
in the cements studied. Finally, the coefficient associated
with C4AF was positive; however, its magnitude was
significantly lower than that of the coefficient associated
with C3 A.
Even though multiple linear analysis yielded reasonably good data on the relationship between strength and
clinker composition, it may be questioned whether the
effect of the single clinker phases is indeed a linear and
additive one, even when a wide range of cement
compositions is considered.
Alexander and co-workers [19,20] obtained best fits
for their data at 3, 7 and 28 days when using an equation
of the type
a = ao + al(1 + b C 3 A ) C 3 S q- a 2

(4)

where ao, al, az = experimental constants, rather than an

equation of the type of equation 1. Alexander [20] also

found that the cement strength at a given hydration time

increases linearly with the C3A content to a m a x i m u m of
14% C3A.
Egorov et al. [26] investigated a large number of
experimentally made clinkers varying widely in their
phase composition. These clinkers were ground with
constant amounts of gypsum (SO 3 = 2.5%) to an identical
fineness (3000cm 2 g - l ) a n d tested under identical
conditions. They reached the following conclusions:
1. The existing relationship between clinker phase
composition and cement strength is never a linear one.
2. All the phases present contribute to strength
development; however, the magnitudes of their effects
vary in a wide range.
3. The effect of silicates a n d particularly that of CaS is
the most pronounced at all ages. Nevertheless, the
strength starts to decline when the C3S content in clinker
exceeds 70%.
4. The contribution of C3A and C4AF to strength
development is a relatively small but complex one. The
strength increases with increasing C3A content only to a
certain value, and decreases with even higher C3 A
contents. The optimum p r o p o r t i o n of CaA is not constant
and changes with the a m o u n t of C3S and C4AF present.
From the experimental d a t a obtained the following
equations were derived to express the relationship
between compressive strength (in kg cm-Z) and clinker
phase composition:
0.1 = 97 + 12.9 C3S + 5.1 C3 A - 3.2 C4AF
+ 4.0 C3S x C4AF -+ 3.8 C3A x C4AF
a 3 = 215 + 22.6 C3S + 14.9 C3S + 14.8 C4AF
+ 9.3 CaS x C4AF + 6C3A x CgAF
av = 302 + 40.6 Ca S + 20.6 C3 A
+ 17.0 C 4 A F - 14.3 C3 A x C4AF
o'28 = 450 -+-25.3 C3S + 17.9 C3A
+ 24.7 C4AF + 21.8 C3S x CaA
- 33.0 C3A x C 4 A F - 23.9 (CaA) 2

Materials and Structures

147
texture, presence of minor components, the particle size
distribution of the cement and the amount of gypsum in
cement may have a significant effect on the strength
development, making the analysis of the effect of phase
composition difficult. The effect of theses factors will be
analysed below.

-Z 90

4. E F F E C T O F M I N O R C L I N K E R
CONSTITUENTS ON CEMENT STRENGTH
5
10
15
20
composition- bogue % C,AF
Fig. 4 Effect of clinker composition variation on compressive
strength of cements C3S: 70%, C2S: 10% [27].
Abdul-Maula and Odler [27] found on a series of
laboratory-made cements a non-linear effect of the
individual clinker phases on cement strength, and
evidence of an interaction between the phases present
(Figs 4 and 5). The resultant strength increased at all ages
ifC3S was replaced by C3A, though only up to an amount
of 10% and it declined at higher degrees of substitution. A
substitution of C3S by C4AF up to 30% had little effect on
l-day strength; at longer hydration times, however, the
resultant strength increased significantly with an increasing amount of C4AF in the clinker over the whole range of
observations. At a constant C 3 S + C 2 S content the
strength in the presence of both C3 A and C4AF was
higher than in the presence & a n y of the two phases alone.
On a series of laboratory-made cements with constant
C3S + C2S yet variable C3A and C~AF contents it was
found that with optimum gypsum additions the final
strength increased with increasing C4AF and declining
C3A content [I t].
It may be concluded that the published data on the
effect of clinker phase composition on cement strength
are rather contradictory. Nevertheless it appears that this
effect is a rather complex one. Even though equations
obtained by multiple regression analysis reflect fairly well
the strength/composition relationship for narrow ranges
of clinker composition, it appears likely that an interaction among the single clinker phases in producing
cement strength does exist. In analysing the effect of phase
composition on strength it has to be taken also into
consideration that additional factors such as clinker

CaA
Z

C4AF

CaA + C4AF

80

A,',,
e-..

~9 ~0
,>- 20
E

0 1020 30 0 10 20 30 0 10 20 30 40
composifion bogue %

Fig. 5 Effect of clinker composition variation on compressive

strength of cements 1-27].

It has been recognized that cement strength may be

affected also by the presence o f minor constituents in
clinker. Such constituents may be present only in amounts
of a few per cent or a few tenths of a per cent, and yet
distinctly affect the resultant properties of the binder.
Of the various minor constituents the effect of alkalis,
i.e. of Na20 and K 2 0 , has been studied most extensively.
A review on the action of alkalis in cement has been
published by Jawed and Skalny [28]. According to them,
high contents of alkalis in clinker generally result in a
decrease of final strength while early strength is usually
increased. Some authors, however, have reported an
overall positive effect of strength development.
In a more detailed study o f the subject it has been
recognized that the action of alkalis depends to a great
extent on the form in which they are present in clinker: in
the absence o f SO3, alkali oxides are incorporated into the
crystalline lattice of clinker minerals while, in the presence
of SO> alkali sulphates (designated also as 'soluble
alkalis') are formed.
Kn6fel [29] reported a decrease of both early and late
strength due to the presence of high amounts ( = 1.6%) of
either Na20 or K 2 0 , present either in the form of
sulphates or incorporated into the crystalline lattice of
clinker minerals. Schmitt-Henco [30] reported an increase of strength due to alkali sulphates. Osbaeck [31]
studied the effect of alkalis on 31 industrial cements. He
reported a decrease of 7- and 28-day strength due to
soluble K 2 0 in clinker, while the effect of this form of
potassium oxide on I- and 3-day strength was not
significant. At the same time no significant effect of K / O
bound in clinker minerals on strength was observed. In a
subsequent study on laboratory-made cements Osbaeck
and Joens [32] observed an increase of early strength and
a decrease of late strength values due to soluble K20.
Parallel to that the hydration of the phases C3S, C3A and
C4AF was distinctly accelerated. Joens [33] also reported
an increase of early strength and a decline of late strength
due to soluble alkalis. The hydration of C3S was
accelerated up to 36 h and reduced afterwards.
Abdul-Maula and Odler [-27] found only minor
strength changes due to the presence of N a 2 0 or K 2 0 in
the crystalline lattice of laboratory-made clinkers. Jawed
and Skalny [34] found a decrease of 7- and 28-day
strength due to KzSO4, while data on 1-day strength were
inconclusive. The C3S hydration was accelerated while
that of C3A was retarded. Odler and Wonnemann [7]
reported a decrease of both early and late strength due to
NazSO 4 in cements. The rate of C3S hydration was not

148

68-MMH: Mathematical modelling of cement hydration

altered. In parallel work on alkalis incorporated into the

clinker minerals [6] they found no significant effect of
either Na20 or K20 on strength. Strunge et al. [35]
reported a negative effect of NazO and K20 on cement
strength; this decline can be partly eliminated by an
increase of the silicate modulus of the clinker. Finally,
Gouda [36] and Richartz [37] reported an increase of
strength in the early stages (I to 3 days) and a decrease
later on due to high alkali content in clinker.
From the above it appears that even though a
significant effect of alkalis on strength is generally
recognized, data on the character and magnitude of this
effect are not uniform. Alkalis bound within the
crystalline lattice of clinker minerals appear to act
differently to those present in the form of soluble
sulphates.
The effect of MgO on cement strength has been studied
by several investigators and has been found not to be very
significant [-27,31,38,39].
Free lime affects the cement strength mainly by
inducing unsoundness, volume instability and cracking.
According to Alexander [19] a negative effect of free lime
on strength begins to appear at about 2days, reaching
significance at between 28 and 90days. Schmitt-Henco
[31] also found a negative effect of free lime on 28-day
strength. Contrary to this, a positive effect of free lime on
strength was reported by Aldridge [24].
In industrial clinkers the clinker phases present are
doped simultaneously by several foreign ions [40]. Thus
an interaction between them as to their effect on strength
is conceivable.
5. EFFECT OF CLINKER TEXTURE ON
CEMENT STRENGTH
It has been recognized that, in addition to oxidic and
phase composition, the texture of the clinker may have an
effect on cement strength. The parameters to be considered are: the size, shape and orientation of individual
grains, distribution of grain sizes, distinctness of their
boundaries, clustering, colour, birefringence, etc.
5.1 Effect of size and shape of alite crystals on cement
strength

Even though the effect of alite size on strength has been

generally recognized, opinions differ as to the existing
relationship between these parameters.
According to most investigators the initial as well as
final strength increase with decreasing size of alite
crystals 1-41-46]. Contrary to this, Butt and Timashev
[47] reported an improvement of strength properties with
increasing alite size. Suzukawa et al. [48] and Locher [49]
reported no significant effect on strength due to differences in alite crystal size. Butt and Timashev 1-50]
reported best strengths for alite crystals with sizes
35-45 #m for strengths between 3 days and 3 months,
while after one year the strength declined or became
unchanged with increasing alite size.

5.2 Effect of overall clinker structure on cement strength

It has been recognized that, in addition to clinker mineral

size, the overall clinker structure may also have an effect
on cement strength. It is generally believed that clinkers
with relatively large, well-developed crystals with distinct
grain boundaries lead to higher strengths than those with
indistinct crystallization, indistinct grain boundaries and
aggregates of ill-formed minerals ]-3,51-55].
According to Volcovsky et al. [56] the following four
types of clinker structure can be distinguished:
Type I: Monadoblastic, distinctly crystalline, coarsegrained with grain size above 30 #m.
Type II: Monadoblastic, distinctly crystalline, finegrained with grain sizes below 30/~m.
Type III: Glomeroblastic, medium-grained with relatively indistinct crystallization and formation of belite
aggregates.
Type IV: Glomeroblastic, poorly crystalline with large
aggregates of ill-formed minerals.
The strength obtained (at constant phase composition)
declines from Type I to Type IV, whereby the difference
in strength after 28 days may amount to 20 MPa.
Ono [55,57] studied the relationship between clinker
structure and cement strength. He proposed a set of multiregressive linear equations (for 7- and 28-day strengths) in
which the following parameters were considered: hydraulic modulus, free lime, Blaine specific surface area, size
of alite, birefringence of alite, size of belite, birefringence of
belite, colour of belite. Using these parameters the 28-day
strength could be estimated with a standard deviation of
+ 1.5 to 3 MPa.
As the described variations of the clinker texture are
brought about mainly by variations in the thermal history
of the clinker it is obvious that, in addition to its oxidic
composition, the conditions of clinker burning are
another important factor that determine the strength
development of the resultant clinker [-49,54,55,58,59].
6. EFFECT OF SULPHATES ON STRENGTH
The amount of SO 3 in clinker is generally low. Here the
SO 3 is present predominantly in the form of alkali
sulphates. Its effect on cement strength is discussed in
section 4.
A larger fraction of SO 3 is added to cement in the form
of calcium sulphate, either as gypsum CaSO4" 2H20 or
anhydrite CaSO4. During cement grinding a fraction of
gypsum may decompose to hemihydrate CaSO4"89
The main role of calcium sulphate is to control cement
setting; however, the strength may be affected as well.
Data on the effect of calcium sulphate on the progress
of hydration and on cement strength are not uniform,
though it is generally believed that optimum strength
values are obtained at an 'optimum gypsum' value
depending on the clinker quality, cement fineness and
hydration time.
Frigione and Murra [60] studied the effect of gypsum
on compressive strength of cements with different particle
size distributions. They found a strength maximum at

Materials and Structures

about 6% gypsum added, regardless of particle size
distribution and hydration time (1, 3 and 7 days). Jelenic et
al. [61] also found a strength maximum with increasing
gypsum in clinker. This maximum shifted to higher SO 3
values with increasing hydration time.
Nakagawa et al. [62] studied the effect of anhydrite
added to ordinary Portland cement and found a strength
maximum at about 5% CaSO4 added (at room temperature). This maximum shifted to higher values at 65~
At optimum anhydrite additions the early hydration of
C3S was retarded and the degrees of hydration at later
ages increased. The strength development was accelerated. Khalid and Ward [63] found that the optimum
gypsum value may depend, in addition to clinker
composition and fineness, also on the hydration temperature, and it increases with increasing temperature.
Le Jean [64] found a strength optimum shifting to higher
gypsum values with increasing hydration time.
Alexander and Ivanusec [25] studied the effect on
strength on six cement brands manufactured in full-scale
plants at four SO 3 contents. They found that the strength
was usually independent of, or linearly related to, the SO 3
content of cement. They also found that at greater ages
the relationship between strength and C3A content varied
considerably with the content of SO3.
Abdul-Maula and Odler [11,27] studied the effect of
gypsum on strength on laboratory-made cements with
variable C3A/C4AF ratios. In all instances the amount of
SO 3 had a considerable effect on strength. This effect and
the optimum SO3 depended on the C3A/C4AF ratio in
the clinker employed. Frigione [65] found little differences
in strength by varying the content of gypsum in both
Portland and Portland-blast-furnace-slag cements. At
the same time Jawed and Skalny [34] reported data of
Mills, according to which a distinct optimum, shifting
gradually to higher SO 3 values, exists if either hemihydrate or gypsum are used as set regulators.
Finally, Soroka and Relis [66] compared the strength
development of compacts made from identical ground
clinkers without and with gypsum added (2.93% SO3).
The effect of gypsum on strength was most beneficial after
one day and exhibited a minimum after 7 days. The degree
of hydration was decreased except after one day. It was
shown that the higher strength was associated neither
with a higher degree of hydration nor with lower porosity,
but was due to an improved quality of the hydrates
formed.
It has also been found that the resultant compressive
strength may be affected by the rate of sulphate
dissolution, which in turn depends on the kind of calcium
sulphate used and its fineness: Blombled [67] found
differences in both 1- and 28-day strengths when adding
identical amounts of different forms of calcium sulphate
(gypsum, natural anhydrite, hemihydrate, phosphogypsum) to the clinker. It appears that the effect of
calcium sulphate on strength is a rather complex one, as
calcium sulphate may affect both the kinetics of cement
hydration as well as the quality and the structure of the
hydrates formed.

149
In gypsum-free cements (low-porosity cements) the
setting is controlled by an addition of a lignosulphonate
and an alkali carbonate rather than by gypsum. The high
strength of these cements is due to their extremely low
water requirement and thus the low water/cement ratio
used [68-77].
7. STRENGTH OF BLENDED CEMENTS
Blended cements contain - in addition to Portland clinker
and calcium sulphate- a latent hydraulic component such
as granulated blast-furnace slag, or a pozzolanic component such as natural pozzolana, low-lime fly ash, burnt
clay or an indifferent component such as limestone.
The strength development and ultimate strength of
Portland-blast-furnace-slag cements depends - in addition to clinker quality and fineness - mainly on the
quality (i.e. hydraulic reactivity) and amount of slag
added. The effect of slag composition on reactivity has
been extensively studied [78-84]. It is generally accepted
that the cementing properties of slag are linked to the
presence of a glass phase in the material, even though a
perfect vitrification is not desired [81]. The reactivity of
the glass phase is not constant and depends to a great
extent on its composition. In general the more basic the
slag is, the greater is its hydraulic activity in the presence
of alkaline activators including clinker. On the other
hand, the response to sulphate activators depends mainly
on the alumina content of the slag. At a constant basicity
the strength of the resultant cement increases with
increasing content ofAl20 3 in the slag. MgO contents up
to 8-10% may have little influence on strength, while
Fe20 3 and MnO affect the reactivity and thus the strength
adversely.
Several formulas have been put forward to quantitatively express the slag reactivity. Smolczyk [80] found
that a good l{near correlation exists between strength and
the hydraulicity index:
m-

CaO + 0.5 MgO - A1203

SiOz + FeO + (MnO2) 2

Demoulian et aL [81] tested the reliability of various

indexes proposed and concluded that those indexes that
give too much importance to alumina as a networkformer are the least reliable ones.
Another factor affecting slag reactivity is the structure
of its glass, which in turn is also determined by its thermal
history. It has been reported that optimum strength
properties are reached at MeO6/MeO4 = 0.4.
The structure of natural pozzolanas and fly ashes varies
in a wide range and in line with it also their reactivity
[82-84]. Numerous papers have been published on the
effect of pozzolanic components on cement strength
development, e.g. [85,86]. It is generally believed that the
initial rate of strength development is slowed down in
cements containing natural pozzolanas or fly ash, though
significant differences exist as to the reactivity of different
materials. On the other hand the uItimate strength is in
most cases above that of the control, pozzolana free

150

6 8 - M M H : M a t h e m a t i c a l modelling o f c e m e n t h y d r a t i o n

---_..

gz
=Ego
c-.oa

r'l(l a

y-

o-~ 60
-4-t '- I_.

,~ oZ,0

c_lX.
.4--

30
2 ~00

80 Porttond cement

t+O

20Pozzolano

60

Composition of cement %
Fig. 6 Effect of added pozzolanas on cement strength
development.
binder. At higher pozzolana contents, however, even the
ultimate strength may be below that of the pozzolana-free
cement. Fig. 6 shows the effect o f a pozzolanic component
on strength for different additions and hydration times.
8. E F F E C T O F C E M E N T FINENESS O N
STRENGTH
It is generally believed that the ultimate strength, i.e. the
strength of fully hydrated cement paste, is virtually
independent & t h e fineness of the original cement. On the
other hand the fineness of cement determines significantly
the progress of hydration and thus the strength
development.
It has been well recognized that the progress of
hydration, especially that after short hydration times, is
significantly enhanced by increasing fineness. In line with
this, the compressive strength was found to increase too.
Locher et aL 1-87-1 published data of this kind for two
series of cements made out of two clinkers ground to
different surface areas. Table 6 shows the data obtained.
It has also been recognized that, in addition to the
surface area, the progress of hydration depends also on
the particle size distribution of the particular cement
[60,87-90]. As a measure of particle size distribution the
position and inclination of the line characterizing the size
distribution in a granulometric grid according to Rosin,
Rammler and Bennet (RRB) may be employed. Locher et
aL [87] studied the effect of n = tan a on cement strength.
Table 6 Effect of specific surface area on cement strength [87]
Cement

Surface
area
(cm2 g- 1)

Compressive strength (N mm- 2)

18h

2days

7days

28 days

2610
3430
4530
2600
3670
4740

6.4
14.2
22.2
13.2
14.7
22.7

18.8
36.9
45.8
28.0
36.7
43.2

46.3
59.8
62.4
45.5
53.5
55.9

70.6
78.5
78.0
56.7
65.5
61.4

2000

t,000 cm2/0

6000

Fig. 7 Effect of the n-value (slope of the particle size distribution line in the RRB grid) on cement strength [90].
They found that all strengths between 18 h and 28 days
increased with an increasing n-value (at a constant specific
surface area) regardless of the fineness of the cement. In
other words, at an equal specific surface area the strength
increases as the granulometric distribution becomes
narrower. This increase of strength was found to be
predominantly the effect of a faster hydration under these
conditions.
In an independent study Frigione and Murra [60]
confirmed the data of Locher et al. [87]. They found that
the rate of hydration, and thus the cement strength,
increase distinctly with increasing n up to about n = 2.
In a recent paper [90] the accelerated hydration with
increasing n and the positive effect of the increasing nvalue were again confirmed. From Fig. 7 it is apparent
that the compressive strength after 28 days increases with
increasing n at any specific surface area.
9 S T R E N G T H AS F U N C T I O N O F H Y D R A T I O N
TIME, H Y D R A T I O N T E M P E R A T U R E AND
DEGREE OF HYDRATION
An increase of cement strength with increasing hydration
time has been generally recognized. Obviously this
strength increase is a consequence of increasing amounts
of hydration products as the time progresses.
Immediately after mixing with water, different constituents of Portland cement hydrate with different rates
due to the existing differences in reactivity. Only later do
the degrees of hydration o f different clinker phases
become gradually almost identical.
A minimum amount of cement must be hydrated
before a measurable strength of the paste can be detected.
Only after this does a linearity between the degree of
hydration and strength appear to exist [87]. The
minimum amount of cement needed to produce a firm
structure within the paste and thus yield measurable
strength may depend on the quality of the binder.
Another important factor is also the initial water/cement
ratio, as with an increasing water content a greater
amount of hydrated material is needed to produce a firm,
three-dimensional solid structure.
Also the slope of the plot o f strength against degree of
hydration may not be constant and may depend on

Materials and Structures

various factors such as cement quality, hydration time, or
starting water/cement ratio. All these factors have to be
considered in estimating strength from the degree of
hydration or from parameters related to it. In earlier work
it has been suggested [91] that cement strength is related to
the existing gel/space ratio which in turn depends again
on the amount of hydrates formed. The get/space ratio X
was defined as follows:
X-

gel volume
gel volume + volume of capillary

The following equation was suggested to express the

relationship between the cement strength ~ and the
gel/space ratio:
-= ~0 X n

where % = strength at zero capillary porosity and n =

constant depending on the type of cement. Numerous
investigators have used this equation to express their
experimental data in the form of a mathematical function
[91-96].
Berger et al. [93] derived for the strength of C3S
hydrated for different times the equation
~v = 2.250 x 3
where ~v = tensile strength (p.s.i.), X = gel/space ratio =
[0.63 m / ( m + (w/s))], m = degree of hydration and w/s =
water/solid ratio. The increase of strength with increasing
degree of hydration appears to be due to two separate
factors:
(a) to an increase of the amount of hydrate phases in
the system at the expense of non-hydrated material and
water, and
(b) to a simultaneous decrease of the overall porosity
due to progressive hydration.
In considering the effect of the amount of hydrates on
strength it has to be stressed that the bonding capacity of
different hydration products may vary considerably, thus
producing significant differences in strength obtained at
equal porosity. As to the effect of the CSH phase formed
in Portland cement hydration, it was found that its bond
capacity increases with increasing degree of silicate
polymerization [97]. On the other hand, the present
Portlandite was reported to lack the capability to take
up stresses, causing a collapse of the material [98].
Osbaeck and Joens [99] proposed a model according to
which single clinker phases contribute independently and
additively to strength by filling the space by their
hydration products, thus lowering the porosity of the
system.
As to the unhydrated material present in the cement
paste, it was suggested that its capacity to take up the
existing stresses may be distinct though limited [98].
Contrary to this, an equal capacity of hydrated and nonhydrated materials as to their contribution to strength was
postulated by Lawrence [t00]. In evaluating statistically
the data obtained on a series of cement pastes mixed at

151
different w/c ratios and hydrated at different temperatures
for different times, R6Bler and Odler [96] concluded that
the (negative) effect of porosity on strength is significantly
greater than the (positive) effect of the amount of hydrates
present. Thus, the increase of strength with increasing
degree of hydration appears to be more a consequence of
the decreasing overall porosity of the system than that of
an increasing amount of hydrates present.
10 EFFECT OF POROSITY A N D PORE
STRUCTURE ON STRENGTH

All cement pastes are porous bodies with porosities

ranging between about 5 and 40% [94,101-105]. This
porosity mainly originates from the fraction of mixing
water that remains unreacted in the hydration process
and gets accommodated in the pore space. These pores are
originally filled with the pore liquid. They may be
emptied, however, as the paste dries out. Another fraction
of voids may be due to the air which remained entrapped
in the paste. The volume of the latter is rather small,
however, in pastes that were well compacted and made
without air-entraining agents.
In fully hydrated pastes the existing porosity depends
only on the original water/cement ratio and the amount
of water needed for complete hydration of the pastes. The
latter value depends on the phase composition of the
cement and, to a lesser extent, also on the starting
water/cement ratio. In partially hydrated pastes the
porosity depends on the degree of hydration and declines
as the hydration progresses. In such pastes the existing
volume is filled either with the original non-hydrated
material, or with the hydration products formed, or with
pores, and each of these volume fractions affects the
resultant strength differently. It is generally recognized
that the existing pores affect the resultant strength
adversely whereby pores of different geometry may be
differently effective. Nevertheless, efforts have been made
to express the cement paste strength just as a function of
total porosity, without taking into consideration other
factors.
Balshin [106] suggested the following equation to
express the strength-porosity relationship:
a = no(1 - P)"
where ~ = strength, a o = strength at zero porosity, p =
porosity and n-empirical constant. Functions of this
type were employed by numerous investigators to express
the strength-porosity relationship of various non-metallic
materials [49,88,107-111].
The following equation was suggested by Ryshkewitch
[112] and Duckworth [113]:
O" ~--- O"0 e - kP

where ~ = strength, ao = strength at zero porosity, k =

constant and P--porosity. According to this equation a
linear relationship does exist between porosity and the
logarithm of strength. Functions of this type were
employed by numerous investigators to express the

152

6 8 - M M H : M a t h e m a t i c a l modelling o f cement h y d r a t i o n

strength-porosity relationship of various non-metallic

materials [88,94,100,104,114-122].
Schiller [123] suggested the following equation for
gypsum pastes:

been made to express the ultimate strength as function of

this ratio. Several empirical equations of this kind have
been suggested to predict concrete strength, namely that
of Feret [133]:
C

a = k In ( P o / P )
where a = strength, k = constant, P = porosity and Po =
porosity at zero strength. According to this equation a
linear relationship exists if strength is plotted as a
function of the logarithm of porosity. Functions of this
type were employed by several investigators to express the
effect of porosity on cement paste or concrete strength
[49,104,123-127].
Finally Hasselmann [128,129] suggested the existence
of a linear relationship between strength and porosity that
can be expressed by the equation
a = ao(1

-kP)

where a = strength, % = strength at zero porosity, k =

constant and P = porosity. A good fit of experimental
data with this equation was recently reported by Atzeni
[130] and Indelicato [131].
To test the above equations R681er and Odler [96]
studied a series of cement pastes made from a single
cement with different w/c ratios and hydrated for different
times. The porosity of these pastes varied between 5 and
28%. They concluded that the existing relationship
between strength and porosity in the above porosity
range can be expressed with sufficient accuracy with any of
the above equations, even though Hasselmann's equation
yielded slightly more accurate results than the other
ones. A relatively good fit of most strength-porosity
expressions with experimental data was also reported by
Relis and Soroka [102].
In addition to the above equations several additional
ones have been suggested to express the strength-porosity
relationship. According to Watson [132] a linear
relationship exists between the strength and the solid/
pore volume ratio:
a = k(s/p)

where s = volume of solids, p = volume of pores and k =

constant.
Jambor [101] suggested the following relationship for
expressing the strength-porosity relationship:
a = k (Po - p ) i / 2
(w/c)P

where P = porosity, Po = original porosity, w / c = water/

cement ratio and k = constant.
The following equation was suggested by Relis and
Soroka [102]:
a = wG/P

where w = amount of hydrated material, G = amount of

non-hydrated cement and P = porosity.
For a given cement and hydration temperature, the
porosity of a fully hydrated cement paste is only a
function of the initial water/cement ratio, and efforts have

O-~ K

c+w

Abrams [ 134]:
K 1

K2(w/c)
and Bolomey [135]:

where a = strength, w = a m o u n t of mixing water, c =

amount of cement, and K, K1, K2--empirical constants
depending on cement quality and testing method used.
It has to be noted that the constants in any of the
equations expressing the relation between strength and
porosity vary, depending on the intrinsic bonding
properties of the hydrated material present and the testing
procedure employed. The former may depend on the
oxidic and phase composition of the clinker (see sections 2
to 4), on the conditions of burning and thus on the texture
of the present clinker (see section 5), on the amount of
calcium sulphate and the quality and amount of other
components interground with the cement (see sections 6
and 7), and on the conditions of hydration, especially on
the hydration temperature (see section 9).
Even though equations in which the strength is
expressed as a function of total porosity agree fairly well
with experimental data, it has been suggested that pores of
different sizes affect the resultant strength differently.
Generally it has been suggested that the detrimental effect
of porosity on strength increases with increasing pore size
[96,101,122,126]. R6131er and Odler [96] and Odler and
Abdul-Maula [11] found a linear relationship between
strength and both the total porosity and just the volume
of pores with radii above 10 nm. The existence of a fair
relationship between the strength and both the volume of
all pores and the volume o f only larger pores may be
explained by the relatively small volume of very small
pores (gel pores) present in ordinary cement pastes, as well
as by the fact that variations in the water/cement ratio
(and thus in total porosity) are accompanied mainly by
changes in the volume of larger pores [96], whereas the
volume of small (gel) pores remains virtually unchanged.
High-strength materials have been obtained by special
processing (extrusion, twin-roll mill processing) of blends
of Portland or high-alumina cements with organic
polymers [136]. Their favourabte mechanical properties
were originally attributed to the absence of larger pores
which may act as macro-defects. According to Eden and
Bailey [137], however, the high strength reported by
Birchal et al. [136] is only in part related to the absence of
large voids and must be due also to other effects (presence
of polymers in the system). Recently, evidence of a
chemical interaction between the hydrated cement and
the polymer present was found, and thus the favourable

Materials and Structures

strength properties obtained may be attributed to the
reaction products formed.
In addition to porosity and pore size, other structural
features of hydrated cement pastes may also exhibit an
effect on cement strength. The view has been forwarded
[105,119] according to which there exists an optimum
ratio for crystalline and poorly crystallized products at
which the highest strength is obtained. The required
optimum proportion of poorly crystallized material
declines with decreasing total porosity. Finally it has been
stressed [138] that certain types of pores such as
discontinuities at phase boundaries and slit-shaped
cracks may be detrimental to strength, although their
contribution to total porosity may be very small.
11. O T H E R FACTORS I N F L U E N C I N G C E M E N T
STRENGTH
Some other factors affecting cement strength are just to
be mentioned without being further discussed:
1. It has been recognized that cement additives such as
set accelerators and retarders or plastifying agents may
alter the strength of the set material. This subject will not
be discussed in more detail in this report.
2. Combination with organic polymer or sulphur may
affect the strength properties ofcementitious systems very
significantly. The discussion of these factors is beyond the
scope of this report.
12. T H E POSSIBILITIES O F DERIVING A
C O M P R E H E N S I V E E Q U A T I O N FOR
ESTIMATION OF CEMENT STRENGTH
After the various factors that may determine cement
strength have been presented, the possibility o f expressing
the existing relationship by means of a mathematical
expression (or a set of expressions) is to be discussed.
First, one has to consider that the numerical value of
strength depends on the kind of strength to be studied
(compressive, tensile, flexural) and on the method
employed for determining this strength parameter (kind
of aggregate if any, cement aggregate ratio, test specimen
size, method of compacting, method of curing (in water or
in humid air), curing temperature, etc.). Thus, any
expression derived can refer only to a particular kind of
strength and to a particular method of strength determination. For the present discussion it appears meaningful to
assume either an absence of an aggregate or a constant
aggregate quality and a constant cement/aggregate ratio,
a constant method and degree of compacting, constant
test specimen geometry and a constant method of
strength determination. On the other hand the cement
quality, water/cement ratio, hydration time and hydration temperature will be assumed to be variable and their
effect on strength is to be expressed quantitatively.
Before discussing the development of strength as a
function of time, the possibility of estimating the final
strength of the material is to be discussed first. Two
factors seem to determine the final cement strength: (a)

153
cement quality, i.e. its 'binding capacity', and (b) the
porosity and pore structure of the system.

12.1 Cement binding capacity

It appears beyond doubt that the phase composition of
the clinker employed is one of the factors that determines
the resultant cement strength. The contribution of the
single phases does not appear to be additive, however, and
thus it may be difficult to express this effect quantitatively.
If, however, only a narrow range Of variation in clinker
phase compositions is considered, an additivity in the
effects of the single phases may possibly be assumed,
without affecting the accuracy of such estimation too
much. In such a case the effect of phase composition could
possibly be expressed in the form of a single equation.
In addition to the mutual ratio of the single clinker
phases the presence of minor oxides in clinker may have
also a distinct effect on ultimate strength. Thus it may
become necessary to introduce into the above-mentioned
equation corrections that take into account this effect.
At this time it is not clear whether the burning
conditions, which affect the clinker 'reactivity' (i.e. its rate
of hydration), have an effect only on strength development or also on the ultimate strength of the hydrated
cement. In the latter case this effect would have to be
considered too, and it is apparent that it would be very
difficult to express such an effect in a quantitative way.
Another factor that determines cement strength is the
gypsum content in cement. If taking this effect into
account one has to consider that (a) the effect of gypsum
on strength is not necessarily a linear one and (b) the plot
of strength against content of gypsum depends also on the
composition of clinker.
In cements that contain, in addition to clinker and
gypsum, a third component (granulated blast furnace
slag, natural pozzolana, fly ash, silica fume) the effect of
these substances on ultimate strength must be also
considered. Different additives affect strength differently.
It appears questionable whether at present this rather
complex relationship can be described quantitatively in
the form of a single equation.
If hydration takes place at other than the standard
temperature, the effect of temperature on ultimate
strength has also to be considered, as the binding capacity
o f the hydrates formed may vary with hydration
temperature as well.
Unlike cement quality, the fineness of grinding may
have little effect on ultimate strength and probably does
not need to be taken into consideration, if only the
ultimate strength is estimated.

12.1 Effect of porosity

After the cement binding capacity - - which may be
expressed as the strength present at a given starting water/
cement ratio or at a given total porosity - - has been
established, the contribution of the existing porosity on
strength of the studied cement paste has to be determined.

154

6 8 - M M H : Mathematical modelling of cement hydration

Equations that express such a relationship (i.e. strength

versus porosity or strength versus w/c ratio) have been
proposed and may be employed. The difficulty in doing
so, however, is the fact that all equations of this kind
include constant terms (e.g. 'strength at zero porosity')
that have to be known and may depend on the quality of
the cement employed and/or testing procedure. In
systems hydrating at other than 'normal' temperatures,
the effect of temperature on the resultant 'bonding
capacity' and the course of the existing strength-porosity
plot also have to be considered. The effect of variations of
pore size distribution on strength may be reflected in
variations of the bonding capacity of the binder brought
about by differences in its phase composition, or by
variations of the conditions of hydration, especially
hydration temperature.
The development of a model for determination of
strength at any degree of hydration rather than for fully
hydrated cement paste may be even more difficult. The
difficulty lies in the fact that the progress of strength
development is affected, in addition to cement quality,
also by the fineness of the cement, by the hydration
temperature, by the starting water/cement ratio, by
chemical admixtures and by other factors. Thus, all these
factors have to be considered and their effect quantified in
deriving a model for predicting the strength development.
The development of an appropriate mathematical
expression for determining strength present at time t may
be simplified by linking the strength development to the
progress of cement hydration, and thus making use of
models expressing mathematically the progress of
hydration as a function of time. As there are indications of
an approximately linear relationship between the degree
of hydration and strength (at constant starting w/c ratio)
it appears possible in this way to estimate the strength at
any hydration time t, provided that one knows
(a) the strength at complete hydration (for a 'standard'
w/c ratio),
(b) the degree of hydration at zero strength (for a
'standard' w/c ratio),
(c) the progress of hydration as function of time, and
(d) the effect ofw/c variation or of variation in porosity
on strength at any degree of hydration.

Task Group 1
I. Odler, Chairman
B. Osbaeck
V. Johansen
P. Pratt
K. Scrivener
(3. Frohnsdorff
H. F. W. Taylor
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Concrete Hardening' (in Russian) (Stroiizdat, Moscow,

1964).
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temperature curing of concrete under atmospheric
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12. Kantro, D. and Weise, C. H., 'Hydration of various betadicalcium-silicate preparations', 3".Amer. Ceram. Soc. 62
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silicates stabilized with Na-AI, K-A1, Na- and K-Fe', in
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hydrated C3S', Cem. Concr. Res. 6 (1976) 583-590.
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