C-86 Communications of the American Ceramic Society May 1983

ing to complete hydration. The value of n

Orthosilicate Analyses: A Measure
of Hydration in Pastes of Alite and
Portland Cement
Wu,* Joe HRILJAC,CHAO-LUNG
ZIIAO-01 HWANG,AND J. FRANCIS
YOUNG*
Lkpartmcnts of Civil Engineering and Ceramic Engineering, University of Illinois, Urbana,
Illinois 61801
The proportion of monomeric silicate in a hydrated paste can be used to estimate
the degree of hydration of alite or portland cement. The monomer was estimated
bv gel permeation chromatography of the trimethylsilylated pastes.
RECENT
studies'.2 have shown that poly-
merization of the orthosilicate ions
(monomeric silicate) occurs during the hy-
dration of tricalcium silicate (alite). The
degree of hydration ( a )appears to corrclate
with the decrease in the proportion of or-
thosilicate derivative in the trimethylsily-
lated (TMS) paste. This communication
confirms this relation and applies it to port-
land cement systems and to a variety of
cxpcrimental conditions.
Studies were conducted on pastes pre-
pared from several cementitious systems,
as shown in Table I . Unless otherwise indi-
catcd, thc water:solid ( w / s ) ratio was 0.4
and the curing temperature 25°C. The hy-
drated pastes were reacted according to the
method used in Ref. 3 to form the TMS
derivatives, which were then separated
Received December 2, 1982; revised copy re-
ceivcd February I , 1983; approved February 2, 1983.
Supporfed in pan by the Nalional Science Foun-
dation under Grant No. ENG 78-22068 and by the
People's Republic (if China.
*Member, the American Ceramic Society.
*Permanent affiliation: Research Institute for
Dullding M;irerials, Beijing. China.
by gel permeation chromatography';
the amount of orthosilicate derivative
(monomer) was determined quantitatively.
Details of the method will b e given
elsewhere .4
Quantitative X-ray diffraction analy-
ses (QXDA) were conducted using the in-
ternal standard method with the 2.19 nm
peak of alite and the 2.38 nm peak of TiOz
(anatase) and 3 different packings. Ignition
loss data were determined by oven drying
the samples at 105°C for 24 h and then
heating them in a muffle furnace, first at
580°C for 4 h to measure combined water,
and then at 1000°C for 4 h to measure com-
bined carbon dioxide. The degree of hy-
dation is calculated using the equation':
(W,,,,- W s d + 0.4 1 (Wsxo- W,,I,,)
a/,=
n.w ,000
x 100% (1)
where W,,,, etc. represent the sample
weights at each temperature and n is the
nonevaporable water content correspond-
'HPLC Series 6000A with a 50 nm p-styragel
column and an R-401 refractive index detector, Waters
Associates, Inc., Milford, MA.
was taken as 0.21 g/g for alite pastes6
and 0.23 g/g for pastes of cements and
clinkers.'
The results for pastes made with alites
A-1 and A-2 are given in Fig. 1, where the
percent of monomer consumed (aTMS)is
plotted against the degree of hydration de-
termined by QXDA (aXRI)). Least-squares
regression analysis gives a good linear fit
indicating that the measurements are not
affected by the most common hydration
variables: the w/s ratio, curing tempera-
ture, or the presence of admixtures. The
best-fit line does not quite match the line
of correspondence and indicates that 3%
monomer is consumed at zero hydration.
The anhydrous alites yielded only -95%
of monomer and 5% of dimer. This re-
sult could be due to side reactions during
derivatization and to surface hydration dur-
ing storage.
Figure 2 shows data obtained from the
pastes made with alite (A-2), cements and
clinkers, in which aTMbis plotted against
the degree of hydration determined by ig-
nition loss (aIGN). Again, least-squares
analysis gives a good linear fit although
there is considerable variation in the
amount of calcium sulfoaluminate hydrates
formed. Most of the pastes were well-
hydrated, and complete reaction of the alu-
minate phases probably occurred. The three
data points near zero represent the un-
hydrated solids. The regression line devi-
ates more from the line of correspondence
than was the case with the QXDA compari-
son because TMS analysis only measures
the silicate fraction of the systems; there are
also errors inherent in the assumptions used
to calculate a I G N .
Gel permeation chromatography is ad-
vantageous because it permits simultaneous
analysis of the polymerized silicates; other

Temp: A 65", o 25", o 4",

+SP, vW/S=O.3, oW/S=0.4

~ T M =S 3.00 + 0.91 aXRD

R = 0.981

"0 20 40 60 80 100
DEGREE OF HYDRATION BY QXDA (UXRD) 7' DEGREE OF HYDRATION BY IGNITION LOSS (alGN)Yo

Fig. I . Comparison of degree of hydration by QXDA and TMS methods Fig. 2. Comparison of degree of hydration by ignition loss and TMS
for alite pastes. Filled points represent series A-1 , open points series A-2. methods for cements and clinkers.
May 1983 Communications of the American Ceramic Society
methods, however, can be used to deter-
mine the residual monomer: gas chro-
matography of the TMS derivativesx,’ and
spectrophotometry of molybdate com-
plexcs,“’ for cxample. The accuracy of a.rMS
is considcred to be comparable to aXRD.
REFERENCES
IL. S . Dent Gla\ser, E. E. Lachowski, K . Mohan,
and H. F. W. Taylor, “A Multi-Method Study of C,S
Hydration.” Cem. Concr. Re.,., 8 [6] 733-40 (1978).
*L. J. Parrott. “Examination of the Silicate Struc-
ture nf Tricalcium Silicate Hydrated at Elevated Tem-
perature,” Cem. Concr. Res., 11 131 415-20 (1981).
IF. D. Tamas, A. K . Sarkar, and D. M. Roy,
“Effects of Variables on the Silylation Products of
Hvdrated Cements”: DO. 55-72 in Hvdraulic Cement
Pastes, Their Structirk and Properties: Proceedings.
Scholium Int., Flushing, NY, 1976.
4J. Hriliac. Z.-0. Wu, and 3. F. Young: submitted
fnr publicatik in CEment and Concrete Research.
’R. L . Berger, J . F. Young, and K . Leung,
“Acceleration of Hydration of Calcium Silicates by Car-
bon Dioxide Treatment,” Nuture (London), Phys. Sci.,
240 1971 16-18 (1972).
“F. W. Locher, “Stoichiometry of Tricalcium Sili-
cate Hydration,” Spec. Rep. Nut. Res. Counc. Highw.
Res. Bourd, No. 90, 300-308 (1966).
’T. C. Powers, “Physical Properties of Cement
PdSte”, pp. 577-608 in Proceedings of the Fourth Inter-
national Symposium on Chemistry of Cement, Vol. 11.
Application of Electrical Analog in
Composite Plates
ANILV. VIRKAR*
Department of Materials Science & Engineering, University of Utah, Salt Lake City, Utah
A simple experimental method is proposed for determining stress intensity factors
for composite plates in antiplane loading. The method relies on the fact that, in
antiplane loading, a single harmonic potential function describes the state of stress
und strain in an isotropic body in much the same way as a single potential function
describes local flux densities in an electric conductor.
ERAMICS often are comprised of more
Cthan one phase, e.g. transformation-
toughened ceramics, dispersion-toughened
glasses and ceramics, TiC-A120, com-
posites, Si3N, ceramics containing glass
globules, directionally solidified eutectics,
and glass-ceramics. Since in general the
elastic properties of the phases that form a
ceramic body will differ, the variation in
the stress intensity factor as the crack tip
enters one phase from another must be de-
termincd to accurately describe the fracture
behavior. Most analyses of the fracture be-
havior of ceramic-ceramic composites have
relied on the superposition principle to de-
termine the stress intensity factor, K . In
these analyses, stresses acting across a
hypothetical crack plane in an uncracked
body are used to evaluate K . However, as
Erdogan and co-w~rkers’--~ have shown, to
evaluate K in composite plates, the appro-
priate mixed-boundary value problem must
be solved. Unfortunately, this procedure is
EDITOR-R. 1. STOKES
CONTRIBUTING
Received December 8, 1982; approved January 27,
1983.
Supported by the National Science Foundation
unde; Grant No. DMR 79-12668
Member, the American Ceramic Society.
Table I. Systems Used For Hydration Studies
Series Compssition
A-l Monoclinic alite Admixtures
A-2 Monoclinic alite Tcmperature
w/s ratio
Admixtures
SYN Synthetic clinker Gypsum
(C,S, 87%; C3A, 13%)
WC White clinker Gypsum
(CS, 67%; CzS, 13%;
C?A, 14%)
OPC Portland cement, type I w/s ratio
Null. Bur. Stund. ( U . S.)Monogr., No. 43. 1962.
‘S. K . Sharma, L. S . Dent Glatser, and C R.
Masson, “Trimethylsilyl Derivatives for the Study of
Silicate Structures. Ill,” J. Chem. SOC. Dulton Truns.,
1973, No. 12, 3324-28.
’E. E. Lachowski, “Trimethylsilylation as a Tool in
84112
generally quite complicated, even for sim-
ple crack and specimen geometries, and a
solution in closed form cannot be obtained;
for complicated geometries numerical
methods are necessary. Erdogan and Cook4
have extended the analysis to determine K
in antiplane strain loading (lIIrd mode). In
this case, the solution is not in closed form,
and, again, mathematical procedures are
complicated even for simple geometries.
Erdogan and co-workers, however, have
shown that the variation in K near inter-
faces (crack orthogonal to the interface) is
similar for plane and antiplane strain. For
example, for a crack contained in a higher-
modulus body with the crack tip approach-
ing an interface separating a lower-modulus
body, the normalized K increases and be-
comes singular when the crack tip arrives at
the interface for both plane strain and anti-
plane strain. Similarly, if the crack is con-
tained in a lower-modulus material and is
approaching a higher-modulus material,
the normalized K decreases for both plane
strain and antiplane strain. Although K in
the plane strain problem cannot be easily
deduced, KIIr(antiplane) can be determined
quite easily by an experimental technique
which will be described in the present com-
munication. In view of the similarity be-
tween K I (plane strain) and KrIIfor many
c-87
Conditions of hvdration
Variable Range of values
CaCI2, CaS0,*2Hz0,
NaXO?. NaF (2 wt%
cacl, or equivalent)
6 5 T , 2 5 T , 5°C
0.4, 0.7, 20
Superplasticizer (SP),
silica fume, CIA,
gYPsum
0%, 7.5%, 11.3%
0%, 7.5%, 15%
0.23, 0.35, 0.40, 0.47,
0.59, 0.71
the Study of Cement Pastes: 11,” Cem. Concr. Res.,
9 [3] 337-42 (1979).
“’L. J. Parrott and M. G. Taylor. “Development of
the Molybdate Complcxing Method for the Analysis of
Silicate Mixtures,” Cem. Concr. Res.. 9 [4] 483-88
(1979). 0
geometries, K,,, may be used for studying
fracture behavior if KI is not known.
It has been demonstrated'.' that Kill
can be determined from electrical potential
measurements on cracked metallic foils.
For antiplane problems, stress and strain
fields are completely defined by a single
harmonic potential function, just as a single
harmonic potential function fully describes
local flux densities in the corrcsponding
electrical case. Displacement in antiplane
deformation is analogous to electric poten-
tial in the electrical problem; similarly,
shear modulus is analogous to electrical
conductivity. The objective of this commu-
nication is to extend the electrical analog to
composite plates.
THEORY
Figure 1 shows a composite plate of
materials 1 and 2 (with ends clamped) sub-
jected to a force, F, in the Z direction. The
shear moduli of materials 1 and 2 are p1
and p,, respectively. The free body dia-
gram shows that
F = ( T ~ W+TZWz)f
~ (1)
where t is thickness and ( ~ , / p , ) = ( ~ ~ / p ~
since shear strains are identical in both
plates.
A similar electrical problem is shown
in Fig. 2, where two plates (electrical con-
ductivities aI and a2,respectively) are
joined edgewise and a current, I , flows
through the composite plate. Then
I=(iiWi +i2W2)t’ (2)
where t’ is thickness and ii and i2 are cur-
rent densities. Furthermore, (il/al) =(iz/az)
or i,pl =izp2, where pi and pz are electrical
resistivities.
The displacement w in plates 1 and 2
(Fig. 1) satisfies
v2w=0 (3)