CEMENT and CONCRETE RESEARCH. Vol. 22, pp. 689-694, 1992. Printed in the USA.

0008-8846/92. $5.00+00. Copyright © 1992 Pergamon Press Ltd.

A NEW PERSPECTIVE ON THE HYDRATION CHARACTERISTICS

OF CEMENT PHASES

J.J. Beaudoin and V.S. Ramachandran

Institute for Research in Construction
National Research Council Canada
Ottawa, Ontario K1A 0R6
(Communicated by F. Massazza)
(Received Sept. 4; in final form Nov. 21, 1991)
ABSTRACT

The cement phases, C3S, C2S, C3A and C4AF of same particle size distribution
characteristics were hydrated at a water : solid ratio of 0.45 and their hydration, strength
and porosity characteristics were followed from a few days up to 1 year. Significant
differences from Bogue-Lerch data were observed for relative strengths. The strength
values at 10 days were in the order C4AF>C3S>C2S>C3A, whereas those of Bogue-
Lerch were in the order C3S>C2S>C4AF>C3A. At 1 year the values were
C3S>C2S>C4AF>C3A but those of Lerch-Bogue were C3S= C2S > C3A>C4AF. On a
semi-log plot of strength vs porosity, the data points for the phases C3S, C2S and C4AF
showed linearity and fell on the same line. The points for the C3A phase showed
linearity but had a different slope from other phases. The 'intrinsic strength', defined as
the strength extrapolated to zero porosity, was the same for all the pastes, the value
being 500MPa.

Introduction

Portland cement, the most extensively used of all cements, contains four
principal mineral components* : Tricalcium Silicate (C3S), Dicalcium Silicate (C2S),
Tricalcium Aluminate (C3A) and Calcium Aluminoferrite, of average composition C4AF.
Hydration and other chemical aspects of these compounds have been studied
extensively (1,2). However, strength and other engineering properties of these
materials have been investigated to a much lesser extent, because a pioneering
contribution in 1934 by Bogue and Lerch has to-date been viewed worldwide as 'prima
facie' evidence of the relative rates of strength development of cement minerals (3).
Re-evaluation of this valuable contribution reveals several facets of the conclusions
relevant to strength development that are inconsistent with their stated objectives. For
a reasonable comparison of the hydration properties of the components of cement, the
physical nature of the material and the experimental parameters should be maintained
constant. In the earlier work (3) inconsistencies such as inadequate control of the
particle size distribution of the minerals, variable amounts of water (ie. water/soild ratio
from 0.30 to 0.60 ), inappropriate specimen geometry (cylinder with length/diameter <

* C e m e n t C h e m i s t r y N o m e n c l a t u r e C = CaO; A = A 1 2 0 3 ; Si = SiO2; F = F e 2 0 3

689
690 J.J. Beaudoin and V.S. Ramachandran Vol. 22, No. 4

2) and inaccurate methods of estimating the degree of hydration have led to

questionable conclusions. In addition the strength differences were attributed mainly to
changes in structure and nature of hydrated material and amount of so-called fixed
water was used to explain strength differences. The role of porosity and pore structure
was not considered. Many of the shortcomings mentioned above were circumvented or
minimized by the following procedure so that a better understanding of the role of
cement components in cements could be developed.

Experimental

Experiments were conducted with well characterized starting materials and

pastes were prepared by uniform procedure. The particle size distribution based on
the percentage number of particles rather than on weight percentage was the same for
all samples so that variation in the reaction kinetics due to this factor could be avoided
(Fig. 1). The mixes were prepared at the same water/solid ratio of 0.45 as engineering
behaviour is dependent on this parameter. Strength measurements were carried out
on 1.27 cm diameter x 2.54 cm cylinders of the pastes to realize a length to diameter
ratio of 2, thus minimizing the end effects occurring due to shear in the compression
test. Microhardness values were also determined by Vicker's microhardness Indentor
as they reflect the nature of the interparticle bonds at a microlevel (4). The degree of
hydration was obtained by XRD and calculated on the basis of the residual amount of
anhydrous phase, a more realistic indicator of the degree of hydration. Porosity and
pore size distribution values obtained by mercury porosimetry provided a means to
measure the intrinsic characteristics of the paste samples.
100

8O

6O

E
0 40

2O

0 . , , , ,

100
• • • • , , , ,

10
, , ,
J\
, ,

Particle Size (urn)

Figure 1 Particlesize distributionof C3S,C2S,C3A and C4AF

cement components.

Results and Discussion

Results of compressive strength versus time and compressive strength or

microhardness versus degree of hydration or porosity are plotted in figures 2 to 4.
Significant differences from the Bogue-Lerch data on the relative values of
compressive strength of the mineral phases occur as a function of time at early ages (1-
10 days), [Figs. 2 (a) and 2 (b)]. Compressive strength values at 10 days of the pastes
in this work are ranked in the following order: C4AF > C3S > C2S > C3A. At 14 days
strengths are in the order C3S > C4AF > C2S > C3A. The
Vol. 22, No. 4 INTRINSIC STRENGrH, CEMENT PHASES,HYDRATION 691

80
tt

6O
~' -.- css
(/)
e) 40
._>
/ I -'-

100 Present Study (b)

"0 15 /I/~u
(/} ///

o
"o - - ~ - - ~ - ~ - -
° . . . . . . . . .

100 200 300 4OO

Time (days)

Figure 2 (a) Compressivestrengthof hydratedC3S,C2S,C3A and

C4AF pasteversustime afterBogue-Lerch,ref. 3
(b) Compressivestrengthof hydratedC3S, C2S,C3A and
C4AF pasteversustime, presentstudy.

Bogue-Lerch strength values both at 10 and 14 days are ranked C3S > C2S > C3A >
C4AF. The present study shows values having the following order at 1 year: C3S >
C2S > C4AF > C3A. Bogue-Lerch estimates at 1 year are ranked C3S = C2S >C3A >
C4AF. Our studies demonstrate that up to at least one year
the strength of C2S pastes lags that of the C3S pastes. The relative rankings at 1 year
however, are broadly similar to the extent that the silicates have significantly greater
strengths than the aluminates. The iron bearing aluminate phase, however, is
considerably stronger than the tdcalcium aluminate phase, as evidenced in this work,
whereas in the Bogue-Lerch's study, C3A paste is marginally stronger than that of
C4AF paste. A direct comparison of the strength data of Bogue and Lerch and those of
the present work is meaningless because as already stated Bogue and Leroh did not
control the physical characteristics of the starting materials.

Microhardness measurements were carried out to investigate the surface

characteristics of the hydrated materials at a microlevel. Microhardness has been
shown to correlate with compressive strength for portland cement systems (4).
Microhardness versus time curves are not presented as they are similar in nature to
corresponding curves for compressive strength.
Strength or microhardness versus degree of hydration curves, figure 3 (a) and 3
(b), are separately shown for each system. Strength and microhardness generally
increase with degree of hydration. The strength data indicate that C2S > C3S for
692 J.J. Beaudoin and V.S. Rarnachandran Vol. 22° No. 4

degree of hydration in the range 30 to 60%. Strength of C3S > C4AF > C3A for degree
of hydration 70 to 100%. C2S was hydrated only about 60% at 1 year. Microhardness
data indicate that C3S and C2S values overlap up to about 60% hydration. The
hardness values are in the following order from 60 to 100% hydration: C3S > C2S >
C4AF > C3A. This is a similar ranking to the strength data at 1 year.

,3

O-

Degree of Hydration (%)

Figure 3 (a) Compressivestrengthof hydratedC3S, C2S,C3A and C4AF

pastes versus degreeof hydration
(b) Microhardnessof hydratedC3S,C2S,C3A and C4AFpaste
versus degreeof hydration.
Comparison of strengths as a function of time, or degree of hydration at best, can
yield only relative values, providing the starting material, experimental procedures and
other parameters are maintained constant. In the work of Bogue and Lerch these were
not followed and hence comparisons of the relative rates of hydration and strength
development are in error.

One realistic approach to compare the inherent strength properties of pastes is

to determine their 'intrinsic' strengths. The strength of the material at zero porosity
determines its real intrinsic strength. Another method is to determine the strengths at
the same porosity (Sp) or at the same degree of hydration (SR) called "relative intrinsic
strengths". During hydration, the porosity and the degree of hydration change,
depending on the amount of hydration. The strengths, Sp and SR, depend amongst
others on the number of bonds and bonding area, type of bonding, microcracks, etc.

Compressive strength or microhardness versus porosity curves, figure 4 (a) and

4 (b), provide a new perspective on the intrinsic characteristics of
Vol. 22, No. 4 INTRINSIC STRENGTH, CEMENT PHASES, HYDRATION 693

(a)

>+ 1 ~
r °
..
"'..
E]
C]

0
~..1
o •

.01 * ' ''

1000
(b)
n

100 "or"
o
c )

"Q [3
o
._o 1o

[3

1 I = t I =
0 20 40 60

Porosity (%)

Figure 4 (a) Compressivestrengthof hydratedC3S, C2S, C3A and C4AF

paste versus porosity
(b) Microhardnessof hydratedC3S, C2S, C3A and C4AFpaste
versus porosity.
hydrating cement minerals. Strength data points for C3S, C2S, C4AF fall
approximately on the linear plot over the porosity range 12 to 56% and have a zero
porosity (intrinsic) value of about 500 MPa. Validation for meaningful zero porosity
values of strength by extrapolating strength - porosity curves to zero porosity was
obtained by independent methods (5). Impregnation of pore space and application of
composite theory provided comparable results for intrinsic properties. This behavior
has been observed for other systems eg. gypsum and autoclaved calcium silicate
systems (4,6). Strength data for C3A fall on a separate curve below that for the other
systems at porosity values of 20-30% (Fig. 4a). The zero porosity (intrinsic) strength for
C3A is, however, approximately the same value as for all other systems.
Microcracking in C3A paste due to flaws could give lower strength at an equivalent
porosity but not affect its intrinsic strength.
Microhardness-porosity data can be considered to describe a single curve for all
the samples. Microhardness is apparently not as sensitive to microcracking as
compressive strength.

The zero porosity (intrinsic) value of microhardness is about 3000 MPa for all the
mineral systems. Coincidence of the strength, microhardness-porosity curves suggests
that the inherent or intrinsic 'cementing' characteristics of the pastes of four principal
cement minerals are similar. The strength values however, are particularly lower for
C3A paste with respect to others, in porous pastes. The results of this work reveal that
pore size distribution plays a less significant role (with the exception of C3A) in
694 J.J. Beaudoin and V.S. Ramachandran Vol. 22, No. 4

strength development as the data lie on a single curve (Fig. 4). Porosity is apparently a
more suitable descriptor of strength than time or degree of hydration. Important
parameters influencing strength development include mineral particle size and water-
solid ratio insofar as they influence the resultant porosity of the hydrating system.
Intrinsic strength or hardness appears to be independent of mineral type. Although
normally only very low strengths are obtained with C4AF and C3A at normal
temperatures and w/s ratios, very high strengths may be obtained when the pastes are
prepared at very low w/s ratios and high temperatures (7,8). The compressive strength-
time curves presented by Bogue-Leroh cannot be considered as universal descriptors
of strength development of C3S, C2S, C3A and C4AF and should be interpreted with
caution. Our work based on a more rational approach has presented results on the
rate of hydration and intrinsic strength characteristics of hydrated products of cement
components at normal hydrating conditions. It is apparent that there is no unique
strength-time relation for hydrated cement systems. The results also have revealed that
by manipulating the right conditions same strengths can be obtained with all the
cement compounds.
Conclusions

(1) The pioneering data of Bogue/Lerch on compressive strength development with

time for the four cement phases has to be revised.

(2) In the first ten days of hydration strength of C4AF pastes exceeds that of C3S.

(3) Comparison of strength as a function of the degree of hydration reveals that at

hydration degree of 70-100% the strength is in the decreasing order C3S>
C4AF>C3 A.

(4) Compressive strength vs porosity curves on a semi-log plot show a linear

relationship for all pastes. The lines seem to merge to the same value of
strength (about 500 MPa) for all pastes at zero porosity. This would
indicate all the phases have the same inherent strength.

(5) No unique value can be assigned to the strength of the pastes as a function of
time of hydration. The relative values depend on the particle size distribution,
w/s ratio, method of mixing, temperature, time, and other parameters.

References
1. H.F.W.Taylor, Cement Chemistry, p 475, Academic Press, New York Press, New
York (1990).4. J.J. Beaudoin and R.F. Feldman, Cem. Concr. Res., 5, 103 (1975).
2. V.S. Ramachandran R.F. Feldman and J.J. Beaudoin,Concrete Science, p 328,
Heydon & Sons, London (1981)
3. R.H. Bogue and W. Lerch, W., Ind. and Eng. Chem., 26, 837 (1934).
4. J.J.Beaudoin and R.F.Feldman, Cem. Concr. Res., 5. 103 (1975).
5. R.F. Feldman and J.J. Beaudoin, Cem. Concr. Res., ]_, 143 (1977).
6. I.Soroka and P.J. Sereda, Proc. Vth Int. Syrup. Chem. of Cement, Tokyo, Vol. III,
p67 (1968).
7. V.S. Ramachandran, and R.F. Feldman, Appl. Chem. Biotechnol., 23, 625 (1973).
8. V.S. Ramachandran and J.J. Beaudoin, J. Matls. Sci., ~ 1893 (1976).