Constitution of Bone China: Ill, High-Temperature Phase

Equilibrium Studies in the System Tricakium Phosphate-

A n o rthite-Si Iica
by P. D. S. ST. PIERRE
Mines Branch, Department of Mines and Technical Surveys, Ottawa, Ontario, Canada

The primary-phase fields of the system trical- P

cium phosphate-anorthite-silica are delineated,
and the distribution of isotherms is related to the
firing of bone china. The system is a true ter-
nary with a eutectic at 11% tricalcium phosphate,
51% anorthite, 380/, silica that melts at 1290’ +
5°C.

1. Introduction
HE purpose of this series of papers on the constitution of

T bone china’ is t o make a preliminary survey of t h e sub-

ject in order t o determine t h e most profitable fields for fur-
ther research. Thus the conclusions drawn in Part I from
the study of t h e tricalcium phosphate-alumina-silica plane in
relation t o t h e quaternary system lime-alumina-phosphorus
pentoxide-silica indicated that a n idealized bone china* might
be described i n terms of a compatibility tetrahedron trical-
cium phosphate-anorthite-mullite-silica.On this basis, mul-
lite would be the least-abundant phase, if t h e bone china com-
pletely crystallized. T h e present investigation therefore was
commenced b y a study of the major components, namely, tri-
calcium phosphate, anorthite, and silica. The location in the
lime-alumina-phosphorus pentoxide-silica tetrahedron of this A
and other planes relevant t o the discussion is shown i n Fig. Fig. 1. The tetrahedron lime-alumina-phosphorus
1. pentoxide-silica showing internal planes relevant to
the study o f bone china. N o t e AS2 is not a corn-
The experimental methods used to delineate phase fields pound; the formula only indicates the theoretical
and t o determine liquidus temperatures were those described composition of dehydrated kaolin.
in P a r t I.

11. Previous Research I800 -1800

Two of the binaries bounding the ternary system CsP-CAS-
St have already been investigated. The binary C3P-S was
1700 -1700

Received June 13, 1955.

This paper, abstracted from Technical Paper No. 12, Depart-
ment of Mines and Technical Surveys, is the third in a series on I600 -1600
bone china. ,-.
At the time this work was done, the author was metallurgist, W

Mines Branch, Government of Canada. He is now research 4

Wu O)
I
associate, Research Laboratory, General Electric Company,
Schenectady, New york. 5 1500 500
( a ) P. D. S. St. Pierre, “Constitution of Bone China: I, m -u
w
High-Temperature Phase Equilibrium Studies in the System Tri-
calcium Phosphate-AluminaSilica,” J . Am. Ceram. Soc., 37 [S]
nw nE
I-0
w
243-58 (1954). W

( b ) P. D. S. St. Pierre, “Constitution of Bone China: 11,

- 1400

Reactions in Bone China Bodies,” ibid.,38 [GI 217-22 (1955).

* It must be emphasized that in these preliminary phase inves-
tigations only alkali-free systems are considered. If a practical
china were fully crystallized, soda and potash feldspars would 1300
also be found in notable quantities. At firing temperatures, how-
TRlDYMlTE 8 ANORTHITE
ever, the feldspars are decomposed (see Part I1 of this series)
and on cooling they do not crystallize out again (see Parts I
and 11). Thus their alumina and silica contents can be accounted
for in the idealized system, leaving only the 1 to 3% NazO + 1200
KzO, normally found in practical bodies, to be considered as being
extraneous. SI o2 COMPOSITION co elp20B
t Abbreviations used throughout this paper: C = CaO, A = IWT % 1
AL03, P = PzO~, S = SOP, C3P = tricalcium phosphate, CASz =
anorthite, A S 2 = mullite. Fig. 2 The system onorthite-silica.
1A7
 148 Journal of The American Ceramic Society-St. Pierre Vol. 39, No. 4
discussed briefly in Part I of this series. This system, by it-
self, is not of direct interest in bone china technology, but fur- LIQUID
ther discussion is warranted because the present writer has 2 LlOUIOS

learned of a previous publication by Tromel and co-workers.2

Although there is general agreement on the form of the dia-
gram, there are differences in the details. Since the earlier
work on this system carried out by the present writer was in- I!\ I C R I S T O B A L I T E + LlOUlD I
tended only as a preliminary survey to provide background
information for the bone china study, it was considered advis-
able to study the system C,P-S more closely during the present
investigation. The results of these new experiments are given TRICALCIUM PHOSPHATE
in the next section. 8
CRISTOBALITE
Andersen’s, work on the system CAS2-S has been widely
accepted for some years and it therefore was thought unneces-
sary to check his diagram. The system CASrS is shown in 1400 1400
I I I I I I I I I
Fig. 2.
111. The System Tricalcium Phosphate-Silica
Tromel places the eutectic in this system a t approximately
lOyoSiOpwitha melting point of 154OoC.,although a minimal
temperature of 1530°C. is recorded a t 8% SiOp in his table of
data. He indicates solid solution up to a maximum of 5%
SiOs a t the eutectic temperature. Below this point the maxi-
mum solid solution remains a t 50/, SOz. A range of liquid Table 1. Thermal Data for the Binary System C3P-S
immiscibility is indicated extending from 12.5% Si02 to ap- ( A ) Quenching Runs*
proximately 95% SiO,. Composition Dura-
The experiments made in this new investigation were par- (wt. 7%) tion
7--7 of run Temp.
ticularly intended to check the preceding observations. The CIP S (min.) (OC.) Microscooic examination
data given in Table I are the results of the new experiments. 97 3 30 1651 Strained glass
The eutectic and liquidus temperatures were determined by 30 1638 Strained glass blebs of +
the quenching method, and the range of liquid immiscibility C3P; higher index than
strained glass
was obtained by observation of cone fusions as described in
Part I. Figure 3 is a revised diagram of the system C,P-S re-
30 1562 Strained glass
c,p
blebs of +
sulting from the data yielded by these new experiments. 30 1554 C,f+ glass S +
As a result of the additional data the eutectic may be more 95 5 30 1550 + +
Strained glass C3P tr. S
accurately located in the new diagram. It is now placed be-
94 6
30
30
1546
1578
+
C3P much S
Strained glass +
very mi-
tween 6% and 8% Si02 a t a temperature of 1555O f 5OC. nute trace Cap; o n C3P
This represents an intermediate position between the two side of eutectic
previous diagrams. Bearing in mind the over-all degrees of 40 1557 Strained glass +
C3P blebs
accuracy in the two investigations, the new eutectic tempera- 40 1553 Strained glass CsP + +
S
92 8 30 1603 Strained glass only
ture is in fairly satisfactory agreement with Tromel’s figure.
More precise experiments with improved furnace equipment
1595 Strained glass +
S; on S
side of eutectic
confirm the range of liquid immiscibility indicated by Tromel, 40
40
1557
1553
Strained glass
C3P +
S
S +
and the diagram has been modified accordingly.
No attempt was made to study in detail the extent of solid ( B ) Cone Fusions
solution in the system. However, a few quenching runs were Composition
(wt. 7%)
made and these indicated the presence of 4y0 ( f 1%) silica in
solid solution in the phosphate a t the eutectic temperature. CaP s Remarks
Below this temperature the range of solid solution appeared to 86 14 Softened at 1575OC.; collapsed at 1600°C.;
diminish rapidly. completely molten at 1725OC.; chilled button
showed very small siliceous central core; must
IV. The System Tricalcium Phosphate-Anorthite be very close to beginning of two-liquid region
80 20 At 1560°C. trace of liquid on cone; prolonged
The data for this hitherto unknown system weie obtained run a t 1675°C. would not bring cone down;
by the Geophysical Laboratory quenching method. Quench- went down at 1725°C.; chilled button showed
ing runs were made on compositions from 20 to 70% trical- small central siliceous core; definitely in two-
liquid region
cium phosphate and to this point either homogeneous glasses
or readily distinguished devitrites were obtained on quenching. * Only limiting runs are recorded. The Geophysical tempera-
A t higher phosphatic contents the study was made more ture scale was used throughout with an estimated accuracy of
f 5°C. on each run.
difficult by the high liquidus temperatures and the mobility
of the fluid melts. No evidence of extensive solid solutions
was obtained by X-ray or optical methods during the investi-
gation of several mixtures in the system. For instance, X-ray
powder diagrams of a 5y0anorthite mixture quenched from presence of anorthite. As usual, only the 3.18 a.u. line of an-
temperatures close to the eutectic temperature showed the orthite appeared in the pattern (see Part I of this series),
and unfortunately this line is almost coincident with one line
of a weak couplet in the ot-tricalcium phosphate pattern.
However, by making direct comparisons with a reference a-
tricalcium phosphate diagram, i t was possible to detect the
2 G. Tromel, H.-J. Harkort, and W. Hotop, “Investigations in presence of anorthite by the slight broadening of the faint line
the System Ca0-P20s-Si02,” 2. anorg. chem., 256 [5-6] 253-72 in the phosphate pattern. Detecting with certainty lesser
(1948); Ceram. Ahstr., 1950, April, p. 85f.
3 Olaf Andersen, “The System Anorthite-Forsterite-Silica,”
amounts of anorthite would be even more difficult and was not
Am. J . Sci., [4th Series], 39,407-54 (19151. attempted in this investigation.
April 1956 Constilution of Bone China, 111 149
Table II. Quenching Runs in the System C3P-CAS2
lBoo 1 ~
_-_--_
Composition (wt. %)

_
CIP
_ _
CASz
Refractive
index of
glass
Liquidus
temp.
("C. f 20)*

( A ) Primary Field of Tricalcium Phosphate

70 30 1559
60 40 1520
50 50 1.596 1482
40 60 1,590 1454
37 63 1.591 1447
I TRICALCIUM ' \ 34 66 1.591 1433
( B ) Primary Field of Anorthite
30 70 1.585 1438
20 80 1.580 1470
* The over-all accuracy probably does not exceed +5"C., but
liquidus points were bracketed by runs 4°C. apart.

TRlCALClUM PHOSFHATE

roo
8

I3O0

1200
11 , , I
ANORTHITE

, I , , j 1200
Table 111.

C3P
~
Quenching Runs in the System C3P-CAS2-S
Composition (wt.
CASn
Yo)
S
Refractive
index of
glass
Liquidus
temp.
("C. f 20)*

0 10 20 30 40 50 60 70 80 90 I00 ( A ) Primary Field of Tricalcium Phosphate

co3[Po4)z COMPOSITION Co A$Si20e 20 55 25 1.553 1363
(WT.% I 20 50 30 1.546 1383
20 45 35 1 539 1412
Fig. 4. The system tricalcium phosphate-anorthite. 20 1.536 1425
25 1.550 1414
25 1.554 1448
30 1.564 1420
30 45 25 1.556 1443
30 40 30 1.550 1458
35 57 8 1.580 1434
35 47 18 1.568 1442
35 37 25 1 555 1465
40 50 10 1.580 1444
40 40 20 1 568 1458
40 35 25 1.562 1463
45 45 10 1 ,582 1463
50 40 10 1.533 1472
50 35 15 1.578 1464
50 30 20 1475
60 30 10 1488
70 20 10 1499
80 15 5 1544
90 6 4 1585
( B ) Primary- Field of Silica
8 42 50 1.524 1332
10 45 45 1.525 1448
15 45 40 1.532 1441
15 42 43 1.529 1520
20 35 45 1.530 1544
20 40 40 1.534 1463
20 30 50 1.525 1592
30 35 35 1.544 1483
30 30 40 1.536 1599
40 1554
50 1558
Fig. 5. The system tricalcium phosphate-anorthite-silica. 60 1499
80 1519
( C ) Primary Field of Anorthite
8 54 38 1.532 1332
Data on the compositions made are given in Table 11, and 15 70 15 1 ,560 1447
the phase diagram is shown in Fig. 4. It will be observed that 15 61 24 1.553 1380
20 60 20 1.559 1384
the system is a simple binary with a eutectic (32% C3P, 68% -
CAS2) that melts a t 143OOC. (A5'). Mixtures on or near Boundary Lines
Liquidus
Composition (wt. yo) Refractive temp.
V. The System Tricalcium Phosphate-Anorthite-Silica 7

C3P CAS2 S
- indexof
glass
("C. f
2O)* Boundary
No information has been published on this system and the
discussion which follows is based on the results of the present 8 52 40 1.529 1329 CASz/S
investigation. The system was studied by the quenching 9.3' 51.3' 39.3' 1.531 1299 CASz/S
11 52 37 1.533
1.534 1306
1308 CaP/CASz
CsP/S
method. Such a study is not without difficulties, since many 12 50 38
mixtures containing more than 30% CZP do not readily form 15 55 30 1 544 1315 CJ'jCASr
true glasses, whereas many with less than 10% CSP form very 15 47.5 37 5 1.536 1372 CaP/S
stable glasses. Neither type of product is readily studied by 30 60 10 1.575 1413 CoP/CASz
the quenching method. With experience, however, i t is pos- * The over-all accuracy probably does not exceed iz5"C.. but
sible to work with such compositions. liquidus points were bracketed by runs 4°C. apart.
150 JournaI of T h e American Ceramic Society-St. Pierre Vol. 39, No. 4
I

1700

1650

1600

1550

1500

1450

1400

1350

1300

1250 -J
0 10
I

20 30 40 50 60 70 80 90
c
100
EUTECTIC COMPOSITION C q p q&
IWT.%)

Fig. 7. A section through the system C3P-CAS2-S between CSP and the
eutectic ( 1 1 C3P, 51 CASz, 38 S).
/
CaAl,SlzO,
v v v v v Y v dSlOZ

Fig. 6. lsofract diagram for the system tricalcium phosphate-anorthite-
silica.
Data on the quenching runs are given in Table 111.
Figure 5 is a phase diagram showing that the system is a
simple ternary with a eutectic a t 11 C3P, 51 CASZ,38 S that
melts at 1290° + 5OC. The region of liquid immiscibility ob-
served in the system CBP-S probably extends to some extent
into the ternary system, but its limits were not accurately de-
termined in this investigation. Similarly the very minor
amount of solid solution of silica in tricalcium phosphate was
not determined precisely, since its existence is of little im.
portance in the present study. The three phases which
crystallize out were described in Part I and call for no further
comment at this time.
Figure 6 is an isofract diagram for glasses in the system.
this system. If practical bone china compositions were modi-
fied to fall within the system C3P-CAS2-S, it would be pos-
sible to make this correlation without further phase equilib-
rium studies. The small quantities of alkalis present in prac-
tical bodies probably enter the liquid formed first during fir-
ing, and thus their effect, other than that of modifyingliquidus
temperatures, can be dismissed in preliminary calculations.
It is interesting to observe that the ratio of solid to liquid
may alter rapidly with temperature change in the region of the
diagram closest to practical bone china compositions. Figure
7 is a section through the diagram from the C3P corner to the
eutectic. All compositions lying in this section begin to melt
a t the eutectic temperature and complete their liquefaction
a t the liquidus line shown in the figure. Consider, for in-
stance, the behavior of a mixture composed of equal parts of
C3P and eutectic. Table I V shows the percentage of liquid
present in such a mixture a t various temperatures.

VI. General Discussion

As a result of the earlier investigation of the plane C3P-A-S Table IV. Percentage of Liquid in a 1 : 1 ::CZP: Eutectic
in the system C-A-P-S i t was possible to obtain some idea Mixture at Various Temperatures
of the phase systems relevant to bone china compositions. -
Temp. ( " C . ) Liquid (I%)
The system C3P-CM-S is one such combination but is only
a first approximation since practical compositions have a 1290 50
higher aluminosilicate content than can be described by these 1450 61
1475 81
three components. Thus, even if the alkalis are neglected, the 1490 100
china compositions still fall in a quaternary subsystem. Mul- - -~

lite has been suggested as the fourth member of a compati-

bility tetrahedron, and if this is valid many china compositions
would fall on or close to a 10% mullite plane above a C3P-
CASP-Sbase. It is not unreasonable to assume that the steep
liquidus surface observed in the silica field of the C3P-CAS2-S
base would also find expression in the 10% mullite plane and
therefore in the intervening space. It will be appreciated,
then, that indiscriminate additions of silica to the body may
bring the composition into.the steep liquidus region of the
silica field. Although the resulting increase in refractoriness
does not necessarily mean that the ratio of solid to liquid a t
firing temperatures will be radically changed, the tendency for
silica to dissolve will be definitely diminished. Any coarse
free silica left undissolved might, for instance, change the tex-
ture and the translucency of the fired ware.
Since the system CIP-CASZ-S is a true ternary, it is pos-
sible to calculate the ratio of solid to liquid for all its com-
positions at any given temperature. Thus solid/liquid ratios
could be correlated with deformation data for mixtures within
Thus i t is seen that in the early stages of melting the de-
velopment of liquid is much slower than in the later stages.
It is reasonable to expect a similar condition in the C3P field
in the 10% mullite plane above this point. Practical bone
china should react similarly, although it must be remembered
that in the early stages of firing its behavior should be inter-
preted in terms of the properties and interactions of the raw
materials. However, after approximately 1000°C. is reached
in the normal firing, one may reasonably begin to discuss the
properties of the china in terms of the final products, viz.,
p-C3P, CASz, and siliceous glass (see Part 11).
Acknowledgment
The author wishes to acknowledge the work of A. L. Wilkins
and J. F. Tippins, technicians, who, at various times, have as-
sisted in this project. The continued encouragement of A. T.
Prince, head, Physical and Crystal Chemistry Section, is also
gratefully recorded.