CEMENT and CONCRETE RESEARCH. Vol. 13, pp. 89-96, 1983. Printed in the USA.

0008-8846/83/010089-08503.00/0 Copyright (c) 1983 Pergamon Press, Ltd.

THE HYDRAULIC BEHAVIOUR OF RHOMBOHEDRAL ALITE

R.T.H. Aldous
Research Division, Blue Circle Technical, London Road,
Greenhithe, Kent, DA9 9JQ, England*.

(Communicated by H.F.W. Taylor)

(Received April 23, 1982)

ABSTRACT
A number of rhombohedral alltes have been prepared using impurities
of the type likely to be found in the alltes of commercial
cements. These alltes when ground to 330 m2/kg developed between
25 and 90% more compressive strength at 28 days than monocllnlc
or trlcllnic alltes. X-ray diffraction of alite pastes, in which
hydration was arrested, indicates that rhombohedral alltes yield
higher strengths not only because they react more vigorously with
water but, for the same degree of hydration the hydrates
from rhombohedral alltes contribute significantly more to
strength. A mixture of rhombohedral alite with C3A and CaSO4.~H20
developed much higher strengths at a given age than a similar mix-
ture with trlcllnic allte.

Introduction

Tricalclum silicate (C3S) can exist as three major different poly-

morphs. In the pure system the polymorphlsm is temperature dependent as
follows:-
higher than I050°C : rhombohedral
I050-980°C : monocllnlc
below 980°C : tricllnic
Chemical impurities in C3S can, however, stabilize either the monoclinlc or
rhombohedral form at room temperature. In most production cements the
impurities present stabilize the monoclinlc form. Nevertheless, rhom-
bohedral allte may occasionally occur and there is evidence of a correla-
tion between the presence of rhombohedral alite in commercial cements and
higher strengths(l).

Ono et al(2) reported on the element combinations necessary to stabi-

lize rhombohedral allte, but did not hydrate the alltes. Harada et al(3)
hydrated a rhomhohedral allte, but this was stabilized after Nurse et al(4)
with 2.9% MnO and 0.7% F. It is unlikely that any commercial clinker

* Present address: Exploration Department, Broken Hill Proprietrary

Limited, Wolfstep Building, 695 Burke Road, Camberwell, Victoria 3124,
Australia.
89
90 Vol. 13, No. 1
R.T.H. Aldous

would contain alites with anywhere near this level of Mn0. Typically the
Mn203 content is less than 0.1% in most UK clinkers. The strengths
reported for this alite by Nurse(4) were low compared to other alites.

A number of workers have shown that alite reactivity and strength

development could be influenced by the type of impurity present; e.g.
Mascolo and Ramachandran(5). On this basis rhombohedral elites were pre-
pared using element combinations of the the type and quantity more likely
to occur in some commercial clinkers.

Methods

Using the survey by Ono et al(2) of element combinations required to

stabilize rhombohedral alite, those combinations which were most likely to
occur in a commercial clinker were employed in the present work. Those of
interest were the systems containing combinations of C3S , A1203, Ti02 and
Fe203. The high levels used by Ono were not used since excess quantities
of AI203 and Fe203 would produce some C3A and C4AF thus reducing the purity
of the alite preparation. Equally, high levels of F are known to have an
adverse effect on alite hydraulicity(4). To avoid these adverse effects a
set of alites for each system was initially prepared by varying the level
of the impurity elements to establish the stability requirements of the
rhombohedral polymorph after three 1 hour burns at 1400°C.

The alites were prepared using CaC03 and Si02, proportioned to give
C3S , to which the weighed quantity of impurities were added; the source of
fluorine was calcium fluoride. The mix was blended, pressed into pellets,
fired at 1400°C for 1 hour and crushed to pass a 150~m sieve. This process
/
was repeated three times.

The polymorph stability fields for four systems are shown in Figure i.

Having established the minimum level of these impurities, larger

batches were then made with compositions both within and outside the stabi-
lity fields. These preparations were given a sufficient number of i hour
burns to bring the free lime down to 0.5% or less.
For comparative purposes a batch of pure C3S was prepared and also a
batch of monoclinic alite, with additions of Mg0, AI203 and Fe203 (at 1.9,
1.0 and 2.0% respectively). The alites were ground to 330 m2/kg (~15m2/kg)
analysed and strengths determined using 25mm micro-concrete cubes, made
with graded fine sand and a coarse grit (2.3 - 4.75mm) for aggregate. Two
cubes were tested at each age.

Results

Details of all the compositions and the polymorphism are shown in Table I.
The sample code is a guide to the composition. After grinding, the product
was dried and analysed.
The strength results for the AI203 + F samples are shown in Figure 2.
Two were tricllnic and two were rhombohedral. The latter have much greater
strength growth between i and 7 days than the tricllnic samples, and the
superior strength is maintained at 28 days. An ordinary portland cement
tested using the same method is shown for reference.

A similar trend is apparent in all the other alltes prepared - see

Figures 3 and 4. In Figure 3 the Fe203 system, it is clear that the rhom-
Vol. 13, No. 1 91
RHOMBOHEDRAL ALITE, IMPURITIES, HYDRATION

C35" AI203 • F C35. F¢203" F

1"51 T M_ R:.. R : : R : 1.51 T T '~/:R:.:.":R::-'I.R;

o~ "O 1T T T T T ~-mI0 T T T'~%::R :R

FIG. 1 +:1 ++'c T T T T T

:1 +++
T T T T T
Stability Fields of Rhombohed- 6 .i .~ .~ .,i 6 .i .} .~' .,i
ral Alite. °/o F °/o F
C35.A1203. F¢203. F ~ C3 S. A1203" Fe203"TiO2
T ~ . R: : T ~ R: R
~:
cT T T M R. 'R

,~OT + T M~'-~'rT ~0+53TTRICLIN;

C ~ T

o T T T T T o 0 T T T T
o 6 .i .~ .~ ,~ o 6 0:s ,:0 i'.s
%e °/o Ti02

M=MIXTURE OF POLYMORPHS

bohedral sample with Fe203 and F shows enhanced strength growth, but this
is not as impressive as the AI203 bearing systems in Figure 2. However, a
mixture of Fe203 and AI203 with F is also shown in Figure 3 and the pre-
sence of AI203 markedly improves the strength growth.

TABLE 1

Compositions and Polymorphism of Synthetic Alites

SAMPLE CODE ANALYSIS POLYMORPH

SiO 2 AI203 Fe203 Ca0 F Free llme

0.4F/I.6A 25.4 1.6 0.I 72.1 0.4 0.3 Rhomb.

0.7F/I.4A 25.4 1.4 0.i 71.6 0.7 0.3 Rhomb.
0.3F/I.IA 25.9 i.i 0.04 71.9 0.3 0.5 Tricl.
O.0F/I.5A 25.6 1.5 0.I0 71.5 0.03 0.4 Tricl.

0.7F/I.OFe 25.5 0.07 1.0 72.0 0.7 0.2 Tricl.

0.6F/I.hFe 24.6 0.I 1.5 72.4 0.6 0.i Rhomb.

0.5F/O.hFe/O.6A 25.4 0.6 0.5 72.7 0.5 0.I Rhomh.

0.9T/I.OFe/O.7A 24.2 0.7 1.0 72.7 0.03 Ti02=0.9 1.5 Rhomb.

I.IF/2.4Mn/I.IA 23.0 i.i 0.I 71.5 i.i Mn203=2.4 0.5 Rhomb.

Pure C3S 25.7 73.8 0.3 Tricl.

2.0Fe/I.OA/I.TMg 24.8 1.0 2.0 70.6 0.02 Mg0=l.7 0.4 Mono.

Note: F=Fluorine, A=AI203, Fe=Fe203, Mn=Mn203, T=TiO 2

Mg=MgO.
 92 Vol. 13, No. i
R.T.H. Aldous

~
60 RHOMBOHEDRAL
ALITE5

50.

REFERENCE
40- // O~V~. ---CEMENT
// I ~ ~ -- /~TRICLINIC FIG. 2

30-
<1/
< / ...- Strength Growth for
Alites in the
C3S-F-A1203 S y s t e m .
20-

I0

AGE-DAYS ( ,/- SCALE)

60 ¸

50.
(.,~~ ~>RHOMBOHEDRAL
J _. 1ALITES

40 ¸ /
/ ~ !
/ O ? C , ~ -- ~ --/'LTRICLINIC
REFCEMENT
/ /. ~ i\.5~ /ALITE FIG. 3
I /i- ~.1~u-~-
Strength Growth for
Alites in the Systems
C3S-F-Fe203 and
20-
C3S-F-Fe203-AI203 •

I0-

. - " i / / /
i g ~ 2g
AGE-DAYS (./-SCALE)

60

50- L ~ I ~>RH°M~°H~DRAL

40-
/ ~ ,,.l~s .ONOCUN,C FIG. 4
T ,CL, N,C

30- Strength Growth for

z
Other Synthetic Alite
Preparations.
20-

I0-

O,
i ~ ~ 78
AGE-DAYS ( ./--SCALE)
Vol. 13, No. 1 93
RHOMBOHEDRAL ALITE, IMPURITIES, HYDRATION

Figure 4 compares some other compositions which produced rhombohedral

alite with pure C3S and a monoclinic alite. Again the rhombohedral alites
exhibit better strength growth with superior strengths at 28 days. For
some samples 3 month data were generated showing that the superior strength
of the rhombohedral samples was maintained.

Comparison of Alites Hydrated with C3A and CaSO4.~H20

To investigate the behaviour of these rhombohedral alites when C3A and

CaS04.~H20 are also present in the hydrating system the following two
cements were prepared.

A) Rhombohedral alite + C3A + hemihydrate

B) Triclinic alite + C3A + hemihydrate.

The alites used were 0.4F/I.6A (rhombohedral) and 0.0F/I.SA

(triclinic). After burning and initial crushing C3A was added to each ~lite
to give two mixtures, each with 90% C3S and 10% C3A. Hemihydrate was then
added to give an SO 3 of 2.5%. The cements were ground in a Pascall Mill to
350 m2/kg and strength tested using 25mm cubes.
Figure 5 shows that the compressive strength of the cement A with the
rhombohedral alite was markedly better than B with triclinic alite; both
cements gave better strengths than the alites ground without C3A and
CaS04.~H20.

The Enhanced Reactivity of Rhombohedral Alite

Measurement of the heat evolved from the hydration reaction of alite,

using conduction calorimetry, indicates that the rhombohedral samples
tend to have longer dormant periods than the other polymorphs. The rhom-
bohedral alites also show a broader alite peak where the rate of heat out-
put does not diminish so quickly as it does with the monoclinic and
triclinic varieties (see Figure 6).
This continued higher rate of heat output in the rhombohedral alites
reflects a higher rate of reaction. This difference in shape of the con-

70
A)RHOMBOHEDRAL.C3A.HEMIHYDRATE
60

50
FIG. 5 %
E 40
Comparison of Alites
in the Presence of
C3A and Hemihydrate. ~ ]0~

20-

I0

O, ~ ~ 2'8 9b
AGE-OAYS ( ~-SCALE )
94 Vol. 13, No. i
R.T.H. Aldous

o) PURE C3S - TRICLINIC

5g AT 0'.40 W/S RATIO
6-

4" 400
-q

TOTAL HEAT . . . . . . .

2- 200 ~
/

FIG. 6
. HEAT RATE
Conduction Calorimetry of
I0 20 3b 40 50 6'0 76 B'O 9b I00 I1'0 120
HOURS Rhombohedral and Triclinic
Alite Samples.
b) 0"4 FI I' 6 A - RHOMBOHEDRAL
5g AT 0'40 W/S RATIO
4-
~-400
-t

200

2
rE
0,
io 2b 3b 4o sb ~ 7b 8b 9b oo lio l}o
HOURS

duction calorimetric profile was the same for all the rhombohedral alites
studied, though the length of the dormant period was increased with
increasing F level.

The rate of reaction of the two alites in Figure 6 was also assessed
by X-ray diffraction. The hydration of alite pastes was arrested with ace-
tone at various ages and the product analysed to determine the amount of
C3S used up. The water bound as hydrates was assessed by thermogravimetric
analysis. This was used to calculate the loss free quantity of material
for XRD analysis, when determining the % C3S reacted at a given time. The
% alite hydrated is plotted against time in Figure 7. The rhombohedral
alite reacted much faster than the tricllnlc allte after the initial 24
hours. By 3 days the rhombohedral alite has hydrated 40% more than the
triclinic one, although by 28 days the difference is less marked. This
spurt of activity in the middle ages (I-i0 days) must contribute signifi-
cantly to the enhanced strength growth.
This greater reactivity seems to he an intrinsic property of the rhom-
bohedral alite, they all show faster rates of heat evolution, after what is
sometimes an extended dormant period. The greater reactivity would appear
not to be a product of the impurities themselves, since AI203 and F in
quantities just below those necessary to stabilize rhombohedral alite cause
triclinic alite to stabilize. This behaves in the same way as other
triclinic alites, i.e. there is no gradation of reactivity as the impurity
elements are increased.
Vol. 13, No. 1 95
RHOMBOHEDRAL ALITE, IMPURITIES, HYDRATION

90~

80 ~ 5
M
°/°ORE~ALAL
T
I~E
70

FIG. 7
60
c~

Comparison of the Rate of so

Reaction of Rhombohedral
and Triclinic Alites at
40
0.5 w/c.

30

20
-II%
ALTM
IEO
RR
E
AE
O
C
TF
E
DR
HO
MB
OH
ED
RA
L

I0

3 7 218
DAYS
OFH
YD
RA
O
TIN(J-SCALE)
Compressive Strength Yield from Calcium Silicate Hydrates

The greater reactivity of the rhombohedral alites does not fully

account for the greater strength properties, especially at 28 days. To
demonstrate this it is useful to compare the strength after the same amount
of alite has reacted in each type of alite pastes. As Figure 8 shows, for
a given quantity of hydration (say 50% for example) the strength developed
by the rhombohedral alite is more than twice that of the triclinic alite.
To show that the hydrates of the rhombohedral alite do not contain
more bound water, and hence occupy a larger volume than the monoclinic
alite, the ratio of the weight of water bound up as hydrates to the weight
of alite reacted to form those hydrates has been deduced from thermogravi-
metry and X-ray diffraction. A plot of this ratio against the degree of

60-

0"4F/I.6A
50 R
HO
MB
OH
ED
RA IE/
L ALT

FIG. 8
Strength as a Function of ~. 30
Percent Alite Hydrated.
20

I0

o I'o 2b 3b 4~o ~o o'o 7b go 9b

°/o ALITEHYDRATED
96 Vol. 13, No. 1
R.T.H. Aldous

0.7 ~

x PURE C35 (TRICLINIC)

0"6- • 0 . 4 F I 1.6A (RHOMBOHEDRAL)

FIG. 9
Water Content of Hydrates
with Degree of Hydration.
0.3

0'2
0 ,; z'o 3'o 4; 50 6; 7; 80 ~0
% AUTE HYDRATED

hydration (% of alite hydrated) indicates that the quantity of water in the

hydrates decreases as hydration proceeds, as Figure 9 shows. Also, there is
little difference in the water content of the two alite types at any degree
of hydration. It follows that at a certain degree of hydration (% of alite
hydrated) both types of alite must produce the same quantity of hydrates.
However, the strengths developed by the rhombohedral alites are notably
better than those of the triclinic alites, as shown in Figure 8. It must
therefore be concluded that the hydrates from the rhombohedral alites
contribute more to strength than those from the triclinic alites.
Harada et al(3) showed that their rhombohedral alite yielded hydrates
with a different morphology from those derived from monoclinic alite which
in turn differed from those of the triclinic alite. The hydrated rhom-
bohedral alites also displayed a different pore size distribution.
However, Harada did not determine strengths on these samples. It is
possible that such differences in morphology could account for the improved
strengths shown by the rhombohedral alites in this study.
Conclusions
It is clear that after what may be an extended dormant period, rhom-
bohedral alites react faster in the first 28 days of hydration than
monoclinic or triclinic alites. This contributes to the increased
strengths of rhombohedral alite pastes; however the hydrates formed from
rhombohedral alite also develop more strength in the paste than similar
quantities of hydrates from triclinic alites.
The superior strength derived from rhombohedral alite is still
apparent when the alite is hydrated in the presence of C3A and hemihydrate.
These experiments suggest that rhombohedral alite would make a noticeable
difference to the strength growth of a cement, providing an explanation
for the statistical findings of Gourdin et al(1) that the presence of rhom-
bohedral alites in commercial cements is associated with higher compressive
strenghs. Acknowledgements
The author wishes to thank Blue Circle Industries for their permission to
publish this work.
References
i. P. Gourdin, E. Demoulian, F. Hawthorn and C. Vernte. VII Intern. Cong. Chem.
Cement. II.I-223-228 (1980).
2. Y. Ono, T. Uno and Y. Kanai. Rev. 19th Gen. Meeting Cement Assoc. Japan 36-41
(1965).
3. T. Harada, M. Ohta and S. Takagi. J. Ceram. Soc. Jap. 86, 195-202 (1978).
4. R.W. Nurse, H.G. Midgley, W. Gutt and K.E. Fletcher. Highway Research Board,
Special Report 90, 258, Washington (1966).
5. G. Mascolo and V.S. Ramachandran. Mater. Constr. 8, 373-376 (1975).