January 1972 Journal of The American Ceramic Society-Discussions and Notes 55

Identification of BaO*4TiO2=Al203in the System

BaO-Ti 02 -A12 03
J. P. GUHA and D. KOLAR

I N AN investigation of compatibility relations between BaTiO,

and ALO, d lines which could not be identified as those of
known phases in the system Ba0-TiOL-AI20,occurred in the
Table I. X-Kay Diffraction Data for
Ba0*4Ti02*A1,0,
X-ray diffraction patterns of several samples. Thus, a sys-
tematic attempt was made to detect an unknown phase in the 18 3.52 3.542 022
100 3.18 3.195 114
system, and a new ternary compound having the probable 12 2.81 2.835 115
composition Ba0.4Ti0z.A120, was identified in the Ti02-rich 30 2.46 2.464 032
portion of the system. 15 2.23 2.236 034
A mixture of stoichiometric amounts of reagent-grade 30 2.19 2.199 221
10 2.01 2.011 133
BaCO,, TiOt, and ALOa was fired at 120OOC in a P t envelope 6 1.96 1.966 036
with intermittent cooling, crushing, mixing, and pressing to 18 1.87 1.877 042
ensure homogeneity. The fired sample was cooled to room 5 1.77 1.771 044
temperature and subjected to X-ray analysis. Equilibrium 5 1.72 1.729 232
2 1.66 1.667 141
was considered to have been attained when the X-ray dif- 8 1.57 1.573 144
fraction patterns of successively heated samples showed no 7 1.47 1.470 146
further change. 7 1.43 1.435 333
X-ray powder patterns were obtained with a Geiger-counter 5 1.405 1.406 334
5 1.376 1.378 150
diffractometer" using Ni-filtered CuKa radiation at a scanning 7 1.320 1.320 154
rate of 1"2s/min. The 2s values were calibrated against the 7 1.311 1.311 246
known peaks of pure Au. Debye-Scherrer powder diffraction 5 1.266 1.266 062
patterns were obtained in a camera 114.6 mm in diameter 5 1.248 1.249 342
using CuKa radiation. Simultaneous TG and DTA measure-
ments were performed on previously prepared samples; re-
peated runs were conducted at temperatures up to 1530°C a t reversal corresponds to the melting of the compound. Ob-
a heating rate of 10"C/min. Temperature was measured with servations in the heating microscope indicated that the com-
Pt-PtlORh thermocouples, and the DTA apparatus was cali- pound melts readily at a temperature <1500°C and then
brated at the melting point of diopside, CaMgSizOo (mp slumps completely. Metallographic examination of the melted
1395.1"C). The melting behavior of the compound was also sample showed that the compound melts congruently. This
investigated in a heating microscope.t Melted samples were result was supported by X-ray analysis of the melted sample,
examined metallographically. which produced a pattern identical to that of the unmelted
The X-ray diffraction data for the compound, BaTiaAI2Ol2, compound.
are given in Table I. These powder data are distinctly dif- Work is in progress to determine the crystal structure of
ferent from those for the starting materials and for binary the compound and its compatibility relations with binary
compounds known to exist in the system Ba0-TiO2-AIz0,or phases in the system Ba0-TiOL-AIzOa.
mixtures thereof. This diffraction pattern was indexed on the
basis of a hexagonal unit cell with a=8.860 A, c-18.458 A,
and a/c=0.480. Received November 8, 1971.
The DTA and TG results revealed only an endothermic The writers are with Institut "J6zef Stefan," Ljubljana,
peak at 1470°C which was not accompanied by a weight Yugoslavia.
"Siemens Corp., Iselin, N. J.
change. This pronounced endothermic effect with a sharp TLeitz, Opto-Metric Tools, Inc., New York, N. Y.

Stability of Ettringite o n Heating

P. K. MEHTA

E TTRINGITE, 3CaO.Al2O3.3CaSOa-32H2O,is the principal hy-

dration product responsible for expansion in shrinkage-
compensating and chemically prestressing cement concretes.
Because many &O molecules are incorporated into its crystal
lattice, the behavior of ettringite exposed to heat is signifi-
cant in the thermal durability of concrete members which may
contain significant proportions of ettringite in the hydrated
cement paste.
Kuehl and Albert' reported that ettringite decomposes at
temperatures > 100°F; Lieber,' however, found that ettringite
definitely exists in aqueous solutions heated to 194°F. It a p
Received September 7, 1971; revised copy received October
18, lg71.
Supported by Stressed Structures, Inc., Denver, Colo.
The writer is with the Department of Civil Engineering,
University of California, Berkeley, Calif. 94720.
56 Journal of The American Ceramic Society-Discussions
(A)
r, u ROOM TEMP.
il
1
I1
11"'
d AUTOCLAVED AT
Fig. 1. X-ray diffraction patterns of ettringite exposed to ( A ) drying Conditions,
steam.
pears, therefore, that the thermal stability of ettringite is en-
hanced in an aqueous environment; this result is important in
relation to the thermal durability of concrete.
Published data on the properties of ettringite usually per-
tain to samples produced by chemical reaction in dilute solu-
tion. In actual concrete practice, however, the H,O-cement ra-
tios used are much lower than those of dilute solutions, and
the characteristics of ettringite samples produced from dilute
solutions may not be similar to those of ettringite formed in
pastes. Mehta' showed that the morphology of ettringite pre-
pared from pastes with low &O-cement ratios differed from
that reported by investigators4 who worked with dilute solu-
tions. In contrast to the long, slender needles which result
from dilute solutions, ettringite formed in such pastes occurred
as short prisms with hexagonal cross sections having a thick-
ness-length ratio of ~ 1 : 3 .
The ettringite samples of the present investigation were pro-
duced by hydration at the H20-cement ratios normally used in
commercial concrete practice. The materials and details of
the procedure were described by Mehta and Klein.'
Ettringite was exposed to heat under dry and moist condi-
tions. In dry exposures, samples were heated for 1 h in a dry-
ing oven at loo', 150°, and 200°F. In moist exposures, sam-
ples in contact with distilled water were heated for 1 h at loo",
150", 200°, 300°, and 450'F (the 300' and 450" exposures
were achieved in an autoclave).
X-ray diffraction patterns of the samples were obtained be-
fore and after heat treatment (Fig. 1 ) using a standard dif-
fractometera with a Cu target; the pattern of ettringite at
room temperature is included for reference. As a first approx-
imation, the heights of the principal ettringite peaks a t 9.1'20
and 15.8"20 indicate the relative proportions of ettringite pres-
ent.
Ettringite heated in a dry environment was stabIe a t 150°
but decomposed partially at 200'F (Fig. 1( A ) ) , in contrast to
reports' that it decomposed at temperatures >100"F. In moist
hot environments (Fig. 1(B) ) , the ettringite peak heights
were not reduced significantly after 1 h at ZOOOF, and there
was no evidence of decomposition of the ettringite to other
compounds. However, when it was exposed to saturated steam
and Notes Vol. 55, No. 1
L
il
,* n
(B) moist conditions, and (C) saturated
at 300°F for 1 h, ettringite decomposed to the monosulfate
hydrate. In the specimen autoclaved at 450"F, the presence
of a hydrogarnet phase, 3Ca0.A1203.6R0, was apparent from
the diffraction pattern; however, a considerable proportion of
the ettringite remained undecomposed after this exposure.
The thermal resistance of the ettringite observed in the pres-
ent study is superior to that reported previously under both
dry and moist conditions; this result is attributed to the im-
proved durability of a product formed in systems with low
RO-cement ratios. It is also concluded that the thermal dur-
ability of expansive cement concretes containing significant
proportions of ettringite may not be affected adversely by the
large amount of water of crystallization in ettringite. It is real-
ized that dehydration of a material is both time- and temper-
ature-dependent. No attempt was made to determine the effect
on the stability of ettringite of long exposures a t dehydration
temperatures; hence, the relevance of the data reported is
limited to the experimental conditions described. However, the
information may be useful for applications in which the tem-
peratures to which products containing ettringite are exposed
are not severe and in which the presence of many H,O mole-
cules in the ettringite may be a cause for concern.
Acknowledgment
The contribution of P. S. Sethee to the experimental work is
gratefully acknowledged.
QNorelco, North American Philips Co., Inc., New York, N. Y.
'H. KuehI and H. Albert, "Influence of Temperature on
Structure of Calcium Sulfoaluminates," Zement, 12, 279, 285
(1923).
a W. Lieber. ''Ettrinpite Formation at Elevated Temoera-
tures," Zem.-KaZk-Gips~lG[9] 364-65 (1963).
P. K. Mehta, "Morphology of Calcium Sulfoaluminate Hy-
drates." J. Amer. Ceram. Soc., 52 r91 521-22 (1969).
William Lerch, F. W. Ashton,-ahd R. H: B o b e , "Sulfoalu-
minates of Calcium," J. Res. Nat. Bur. Stand., 2 [4] 715-31
(1929).
P. K. Mehta and A. Klein, "Formation of Ettringite by Hy-
dration of a System Containing an Anhydrous Calcium Sulfoalu-
minate," J . Amer. Ceram. SOC.,48 [8] 435-36 (1965).