August 1965 Journal of The American Ceramic Society-Discussions
bulk and boundary diffusion are nearly equal. This leads t o the
uniform skin development schematically shown in Fig. 2. If
the defect concentration is reduced by lowering the La content,
then Darainhoundary > D b u l k for oxygen and only a thin reoxidized
skin is formed on the surface of each grain. This model may
explain “oxidation” of the La-doped BaTiO3 ceramics reported
by MacChesney et U Z . ~ and the “blocking layer” for the P T C
anomaly proposed by Heywang.G
Acknowledgments
The authors are greatly indebted to S. Mori for the X-ray
analyscs and t o M. Fujimura for technical assistance.
W. D. Kingery, Introduction to Ceramics; p. 241. John
Wiley & Sons, Inc., New York, 1960
6 J. B. MacChesney and J. F. Potter, “Factors and Mechanisms
hffccting the Positive Temperature Coefficient of Resistivity of
Uariurn Titanate,” .7 Am. Cermn. SOG.,48 121 81-58 (1965).
Formation of Ettringite by Hydration of a System Containing
an Anhydrous Calcium Sulfoaluminate
by P. K . MEHTA and A. KLEIN
A CCORDING t o Dana’ the natural mineral ettringite has the
probable composition 6Ca0. AlzO3. 3SOa. 33H20 and occurs
as colorless, acicular crystals. A hydrate of identical chemical
composition and resembling the mineral ettringite in crystal
characteristics is important in the chemistry of hydraulic ccmenti-
tious inatcrials. I t s formation during the carly stages of hydra-
tion of normal portland cements is generally believed to be
responsiblc for the prevention of quick-set which, in the absence
of CaS04 in cement, could occur because of the precipitation of
calcium aluminate hydrates. In supersulfated cements, the
ceincnting action is attributed to the formation of ettringite.
Furtlierinore, cttringite is generally believed to be the cause of
destructive expansion which occurs when some portland cement
coneretcs comc in contact with aggressive sulfate watcrs. The
latter conccpt has been used in thc production of expanding
cements where the expansion incidental to the formation of
cttringitr is hariicssed for shrinkage compcnsation and for chem-
ically prestressing concretc.2
Starting with Candlot3 in 1890, several investigators4 have re-
ported the synthetic preparation of ettringite by precipitation
from solutions such as Al,(SO)a, Ca(OH)g, CaS04, and
3Ca0. A1203. The product thus obtained consists of long, slender,
needle-shaped hexagonal crystals.
In the prcsent investigation, however, ettringitc was prepared
by direct hydration of an anhydrous molar composition, 6Ca0 *
A1203.3S03, which was made by calcining stoichiometric pro-
portions of high-purity CaC03, Al( OH)3, and CaS04.2HzO a t
1300°C in a Globar furnace. Since 4Ca0.3AIz03.SOa is the
only stable ternary phasc known presently,6 the composition of
the anhydrous compound 6Ca0. AlzOl.3S03, as determined by
quantitative X-ray diffraction analysis, was 30y0 4Ca0.3A1203-
SOs, 53.5y0 CaSOd, and 16.5% CaO. The material was ground
to about 4000 cm2/g* and was subsequently hydrated with a
stoichiometric amount of distilled water t o yield 6Ca0. AlzOs.
3S08.33H20. The paste was cast in cylindrical plastic molds 1
in. in diameter. The hardened paste was removed from the
molds, wrapped in cotton pads soaked with distilled water, and
transferred to an airtight container for further hydration. The
progress of hydration was followed by X-ray diffraction analysis;
in 7 days the material was completely hydrated to ettringite.
and Notes 435
CERAMIC SURFACE
GRAIN
Fig. 2. Development of skin by
diffusion-controlled reoxidation i n
the defect structure B ~ o . & ~ ~ . o ~ ~ ~ o . o ~ ~
TiO3. (Dgrain boundary z5 D b u l k . )
W. Heywang, “Resistivity Anomaly in Doped Barium Ti-
tanate,” ibid., 47 [lo]454-90 (1964).
X-ray diffraction analysis of the completely hydrated sample did
not show carbonation products, hydrated compounds other than
ettringite, or nnhydratcd constituents.
This procedure for preparing ettringite by hydration is not
only less tedious than the conventional techniques involving inter-
action of solutions with specific ionic concentrations and elaborate
filtering and drying procedures in Con-free atmospheres, but it
also yields a product of fine particle size, which is more representa-
tive of the ettringite phase actually formed in portland cements
hydrated with limited amounts of water. In fact the crystals
Received March 1, 1965; revised copy received June 1, 1965.
This work was sponsored by National Science Foundation
Grant No. 616.
The writers are, respectively, assistant professor, and research
engineer and lecturer, Department of Civil Engineering, Uni-
versity of California, Berkeley, California.
E. S. Dana, Textbook of Mineralogy, 4th ed.; p. 770. Re-
vised by W. E. Ford. John Wiley & Sons, Inc., New York, 1932.
( a ) A. Klein and G. E. Troxell, “Studies of Calcium Sulfo-
aluminate Admixtures for Expansive Cements,” Am. Soc. Testing
Muter. Proc., 58, 986-1008 (1958).
(.b) Alexander Klein, Tsevi Karby, and Milos Polivka, “Prop-
erties of an Expansive Cement for Chemical Prestressing,” J . Am.
Concrete Inst., 58 [I]59-82 (1961).
( c ) T. Y. Lin and Alexander Klein, “Chemical Prestressing of
Concrete Elements Using Expanding Cements,” ibid., 60 [9]
1187-1218(1963).
3 E. Candlot, Bull. Soc. Encour. Ind. Nut., 102, 682 (1890).
( a ) A. A. Klein and A. J. Phillips, “Hydration of Portland
Cement,” Natl. Bur. Std. Tech. Paper, No. 43 (1914).
( b ) H. Kuhl and H. Albert, Zement, 12, 279 (1923).
(c) William Lerch, F. W. Ashton, and R. H. Bogue, “Sulpho-
aluminates of Calcium,” J . Res. Nutl. Bur. Std., 2 [4] 715-31
(1929) R P 54.
( d ) G. L. Kalousek, “Sulfoaluminates of Calcium as Stable
and Metastable Phases,” Dissertation, University of Maryland,
1941.
6 P. E. Halstead and A. E. Moore, “Composition and Crystal-
lography of an Anhydrous Calcium Aluminosulfate Occurring in
Expanding Cement,” J . Appl. Chem. (London), 12 [9] 413-17
(1962).
* ASTM Specification C 204-55, Fineness of Portland Cement
by Air Permeability Apparatus.
OH. E. Swanson, N. T . Gilfrich, M . I. Cook, R. Stinchfield,
and P. C. Parks, “Standard X-Ray Diffraction Powder Patterns,
Vol. 8 ” . pp. 3-4 in Nutl. Bur. Std. ( U . S.) Circ., No. 539, 76 pp.
(April i959).
436 Journal of The 1merican Ceramic Society-Discussions and Notes Vol. 48, No. 8
Table I. X-Ray Powder Diffraction Pattern of 6Ca0.A120s.3SOa.33H20

h kl
,~_-___
d
_ -,
~-
Pi-esent study
I
- _ ~
Natl. Bur. vf Stds.
d
1

I hkl
______A
Present study
d I
,
Natl. Bur. of Stds.
d
__^--,
I
002 10 71 5 323 2 130 4 2.130 2
100 9 71 100 9 73 100 410 2 124 6 2.124 5
101 8 87 12 8 86 12 412 2 079 3 2.081 4
I02 7 23 5 324 2 059 6 2 062 5
t 03 5 76 11 413 2 033 1 2 033 1
110 5 61 80 5 61 81 317 2 027 1 2 027 1
112 4 98 25 4 98 24 325 2 004 2 1.979 2
200 4 86 7 4 86 6 414 1 971 3 1.975 3
104 4 70 45 4 69 36 500 1 943 9 1.946 10
4 41 3 407 1 904 2 1.905 1
203 4 02 10 4 02 10 503 1 875 1 1.875
-. ~ 2
114 3 88 70 3 88 51 2-1-10 1 854 c
1.853 6
210 3 67 6 3 67 7 332 1 843 5 1.845 8
204 3 60 16 3 60 14 42 1 1 828 3 1.829 4
212 3 48 32 3 48 31 422 1 806 3 1.812 4
213 3 26 10 3 27 4 1 789 2 1.786 2
300 ?J 24 21 3 24 19 1 763 5 1.768 4
116 3 02 9 3 02 6 1 748 1
220 2 81 6 2 81 6 1 723
304 2 77 45 2 77 38 1 705 4
222 2 712 5 2 714 6 1 679 4
310 2 688 9 2 6971 12 1 663 10
008 2 680j 7 1 620 A
3 12 2 616 19 2 616 21 1 598 2
216 2 S66 55 2 564 45 1 574 6
313 2 5’27 6 2 5’24 4 1,515 J
224 2 490 4 2 487 3 1.510 2
400 2 430 2 2 434 2 1,462 2
118 2 422 4 2 422 2 1.392 1
306 2 408 12 2 401 10
208 2 352 5 2 347 4
320 2 231 7 2 230 20
226 2 210 50 2 209 43
32% 2 184 6 2 185 8
316‘ 2 152 26 2 154 23

wcrc so s i i ~ ~that
l l it was impossible t o confirm the acicular habit
by petrographic microscopy. Since the iiitciisities of X-ray
tliffractioii pcaks arc affcctcd by tlic particle size of thc crystals,
it is obvious that the ettriiigite produced by hytlration is better
suited for application in quantitative X-ray diffraction analyses.
The X-ray diffraction pattern of the ettriiigitc prepared by the
authors is shown in Tablc I. I t includes some data, in addition
to the data earlier reported by the National Bureau of
on a syntlictic specimen of ettringite prepared by precipitation
froti1 appropriate solutions.

Thermal Expansion of Polycrystalline Hf0,-ZrO, Solid S o h tions

b y 0. M. S T A N S F I E L D

solid solutioii in tlie I-ifOl- ZrOn binary system lias

C OMPIXIE
been reportctl. N o Iiigh-teiiiperature therinal expaiisioii
(1:tt:i exist, however, for coiiipositions contaiiiing appreciable
:iiiiouiits of both coiiipoIieiits. This iiotc reports the thernial
c~sp:msion of polycrystalline IHf02-Zr02 bodies betwceii 900’
; i t i t l 2600°C as deteriiiined by tlilatometry.
Hafiiia w:is o1)t:iiiictl iii two purities: 99,9 \vt% IHOl coii-
t:iiiiitig 180 ppin Zr and 96 w t % HfOz containing 2.2 w t % %r,
Received April 22, 1965; rcviscd copy received June 14, 1965.
Tliis work was sponsored by the (Jnitetl States Air Force, Air
Force Materials and Processes I,aboratory, undcr Contract AI’
:13(657)-11269.
The writcr is a rcsearch cngineer a t Solar, a 1)ivisioii of Intcr-
n:itiorial Harvester Cornpany, San Dicgo, California.
i C. E. Curtis, L. M. 1)oiiey. and J. I<. Jolitisoii, “Sortie Proyer-

0.2 wtO/, Ti, iiiid 0.2 w t % I’e. The %rOS w:is 98 wt% pure
witli less than 50 ppiii Nf. Only the liigli-purity HfO, was used
to iil;ikc pure HfOn speciiiieiis. The lcss pure HfO, was used in
tiiakiiig HTOz-%rO2bodies since it was deterniiiietl that tlie iiii-
purities tiid riot affect the tlierinal expansion.
‘l‘lic t1il:rtonieter :rnd tlic procedure used to fabi-ic;rte the speci-
tiiciis Iiavc heen described elscwhcre.” The :iccuracy of tlic
ties o f Hafiiiuni Oxide, Hafniuiii Silicate, Calcium Hafnate, a n d
I-Iafniuin Carbide,” J . A m . Cwm?.Soc., 37 [lo] 458-65 (1854).
I<. 1’. Domagala, “Study of the Zircotiia-Hafnia System,”
Illiiiois Institute of Technology I<csearch Institute, Summ:iry
Report No. IITKI-13194-23, 17 pp., April 1964; Contract )\IT
33(616- 7074).
Basil Olinysty atid P. I<. liosc, lieriiiat Expansion Meas-
urements on Thoria and Hafnia t o 4500°F,” .I. An?.. Cevui?~.Sot,
47 181 398-400 (1964).