Materials Chemistry and Physics 48 (1997) 230–233

Phase equilibria in the P2O5-rich part of the system La2O3–CaO–P2O5

Wanda Jungowska, Teresa Znamierowska
Department of Inorganic Chemistry, Faculty of Engineering and Economics, Academy of Economics, 118/120 Komandorska, 53345 Wrocław, Poland

Received 20 December 1995; accepted 6 August 1996

Abstract

The system La(PO3)3–Ca(PO3)2–P2O5 was investigated using the methods of thermal analysis and X-ray powder diffraction, and its phase
diagram was obtained. The occurrence of a ternary compound CaLa(PO3)5, which was peritectically formed at a temperature of 9008C and,
with respect to its stoichiometry, was situated in the system La(PO3)3–Ca(PO3)2, was found. The phosphate CaLa(PO3)5 with lanthanum
ultraphosphate gives the pseudobinary system CaLa(PO3)5–LaP5O14. The related phase diagram, as well as a one for the sidesystemLa(PO3)3–
Ca(PO3)2, was obtained.
Keywords: Phase equilibria; Thermal analysis; X-ray powder diffraction; Pseudobinary systems

1. Introduction Additionally, to define phase equilibria, the quenching

The investigation of the La(PO3)3–Ca(PO3)2–P2O5 sys-
tem represents part of the work on calcium–lanthanum phos-
phates. The phase equilibria for the system was not known,
so far.
Phase diagrams for two side systems only, of La(PO3)3–
P2O5 [1] and Ca(PO3)2–P2O5 [2] were known.
technique was also used; the samples were packed into plat-
inum capsules, equilibrated in an electric furnace and then
quenched in water or ice.
The initial compounds and the phases formed in the system
La(PO3)3–Ca(PO3)2–P2O5 were identified by powder X-ray
diffraction on a HZG-4 diffractometer (Guinier camera, Cu
Ka radiation, Ni filter).

2. Experimental 3. Results and discussion

Samples for investigations of the system La(PO3)3–
Ca(PO3)2–P2O5 were prepared from the following original
compounds: 99.99% La2O3, 85% H3PO4, Ca(H2PO4)2H2O
p.a., CaHPO4 p.a. and CaCO3 p.a.
La(PO3)3 [3], LaP5O14 [3], Ca(PO3)2 [4] and Ca2P2O7
[5] were prepared in our laboratory. The investigations were
performed by means of differential thermal analysis (DTA)
during heating and X-ray. Test samples were presynthesized
by reactions in the solid phase. The DTA was performed in
a derivatograph type 3427 (MOM, Hungary) over the tem-
perature range 20–13508C. Samples from 250 to 450 mg were
used: air atmosphere; platinum crucibles; standard substance
Al2O3 p.a. The temperature was measured with a Pt/PtRh 10
thermocouple which was standardized by using the melting
points of NaCl (8018C), K2SO4 (10738C), Ca2P2O7
(13538C) and the polymorphic transition temperature of
K2SO4 (5838C).
0254-0584/97/$17.00 q 1997 Elsevier Science S.A. All rights reserved
PII S0254-0584(96)01891-3
A series of experiments was carried out, the aim of which
was to determine the phase equilibria in the P2O5-rich part of
the ternary system La2O3–CaO–P2O5. The composition range
covered in the investigation was La(PO3)3–Ca(PO3)2–P2O5.
During the course of the initial work certain difficulties
appeared. First, P2O5-rich samples decompose at higher tem-
peratures. This decomposition is accompanied by P2O5 evap-
oration and the corresponding mass decrement. During the
course of heating at a rate of 58 miny1 the decomposition
begins at a temperature of approximately 10008C and is
observed mainly in the LaP5O14-rich part of the system. In
addition, the samples crystallize with difficulty and readily
form glasses. The obstacles mentioned did not permit
employing some investigation techniques such as thermal
analysis of cooling. Hence, it was not possible to determine
the exact phase equilibria in the entire composition range
La(PO3)3–Ca(PO3)2–P2O5. In consequence, the examina-

Journal: MAC (Materials Chemistry and Physics) Article: 1890

 W. Jungowska, T. Znamierowska / Materials Chemistry and Physics 48 (1997) 230–233
tion was confined to the region of La(PO3)3–Ca(PO3)2–
LaP5O14.
It was initially assumed that the phosphates LaP5O14 and
Ca(PO3)2 yield a pseudobinary section. In order to verify the
assumption, the initial phosphates were mixed for various
molar ratios and then underwent different thermal treatments.
The samples were sintered over the temperature range 600 to
9008C for several hours and then slowly cooled to room
temperature. Also quenching from the sintering temperatures
was applied. The phase composition of the mixtures after
thermal treatment was successively monitored by X-ray pow-
der diffraction.
It has been found that the initial composition of the
samples changed depending on (i) the molar ratio of
LaP5O14:Ca(PO3)2 of the initial sample, and (ii) the thermal
treatment employed. The following phases were found:
LaP5O14, Ca(PO3)2, La(PO3)3 and another new, unknown
phase. For example, the X-ray investigation showed that:
(i) samples that were sintered at 6008C comprised a mix-
ture of LaP5O14 and Ca(PO3)2;
(ii) samples sintered for a short period at 700–7508C com-
prised a mixture of LaP5O14 and Ca(PO3)2;
(iii) samples sintered for a long time (several hours) at
700–7508C comprised a mixture of LaP5O14, Ca(PO3)2 and
La(PO3)3;
(iv) the qualitative and quantitative composition of the
samples sintered at 8008C was particularly sensitive to the
time of heating at this temperature as well as to the initial
composition range, for instance, in the composition range
70–90 wt.% of LaP5O14 (Fig. 1) predominant is La(PO3)3;
in the range 40–70 wt.% of Ca(PO3)2 (Fig. 1) the samples
comprise La(PO3)3, LaP5O14, Ca(PO3)2 and a new,
unknown phase (the reflections produced by the new phase
were clearly visible in the X-ray diffraction patterns).
It should be stressed here that for the samples specified
above, the La(PO3)3 was formed as a result of decomposition
of LaP5O14.
Fig. 1. DTA heating data for precalcined samples containing heteromolar
mixtures of LaP5O14 and Ca(PO3)2.
231
Fig. 2. T, DTA and TG curves of LaP5O14, ms440 mg in air atmosphere.
The ultraphosphate LaP5O14 melts congruently at 10958C.
Nota bene, the compound is known to be thermal-unstable
[1]. Decomposition proceeds according to the reaction net-
work: LaP5O14™La(PO3)3qP2O5 (g). During the course
of differential thermal analysis of heating at a rate of 58 miny1
a slow decomposition of the lanthanum ultraphosphatebegins
at a temperature between 930–9508C (cf. Fig. 2). However,
in the case of prolonged heating, decomposition of the com-
pound initiates at temperatures as low as 700–7508C.
Using X-ray powder diffraction and thermal investiga-
tions, it has been found that the system LaP5O14–Ca(PO3)2
is not, in fact, a two-component system within the whole
composition range, up to 10008C. Fig. 1 shows the DTA data
for the compositions containing 10–90 wt.% Ca(PO3)2 (90–
10 wt.% LaP5O14) which were presynthesized by the reaction
in the solid state at 6008C for 24 h (for a different initial
thermal treatment employed, the location of the effects would
be different). The high temperature thermal effects of Fig. 1
are connected with (i) the melting of the samples in the
Ca(PO3)2-rich region; (ii) decomposition of LaP5O14 in the
LaP5O14-rich region. Interpretation of the effects occurring
in the whole range of composition at 8008C as well as the
high temperature effects in the composition range 40–60
wt.% of Ca(PO3)2 was difficult. It should be noted that during
the thermal analysis of heating no mass decrement was
observed in the TG-curves up to 10008C.
Accordingly, the system La(PO3)3–Ca(PO3)2 was chosen
for investigation. The phase diagram of the system is not
known. Inspection of literature indicates that the studies of
binary systems of the type Ln(PO3)3–MIPO3 (where MI
denotes alkali metal, Ln is lanthanide) have yielded the iden-
tification of two types of binary metaphosphates with the
formulae MILn(PO3)4 and MI2Ln(PO3)5 [6–13]. Nota bene,
when only one binary metaphosphate is formed in the system,
it has the formula MILn(PO3)4. Binary metaphosphates are
known to melt incongruently. Literature lacks data about
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232 W. Jungowska, T. Znamierowska / Materials Chemistry and Physics 48 (1997) 230–233

binary systems of the type Ln(PO3)3–MII(PO3)2 (where MII wt.% Ca(PO3)2 (75–50 wt.% La(PO3)3 (see Fig. 3). It was
denotes alkaline earth metal). The phase diagram of the sys- found that the phosphate CaLa(PO3)5 is stable down to room
tems Y(PO3)3–Ca(PO3)2 and Y(PO3)3–Mg(PO3)2 has temperature and does not reveal polymorphic transitions. In
been provided in our laboratory [4,14]. The binary meta- the system La(PO3)3–Ca(PO3)2 an eutectic occurs for the
phosphates CaY(PO3)5, Ca2Y(PO3)7 and MgY(PO3)5 have content of 80 wt.% Ca(PO3)2, at 8558C. The lanthanum met-
been observed in these systems; the compounds melt aphosphate La(PO3)3 melts incongruently forming LaPO4
incongruently. and a liquid. This fact is reflected in the system under consid-
In order to elaborate the phase diagram of the system eration by a peritectic reaction which is involved in the com-
La(PO3)–Ca(PO3)2, the samples comprising heteromolar position range from 0 to 18 wt.% Ca(PO3)2.
mixtures of the initial phosphates were presynthesized by In the area La(PO3)3–Ca(PO3)2–LaP5O14, the CaLa-
annealing at a temperature between 750–8008C for 20 h. The (PO3)5–LaP5O14 system was examined. Samples for the
sintered samples were treated through DTA of heating. Inter- investigation of the system were prepared from the phos-
pretation of the thermal effects manifested in DTA-curves phates La(PO3)3, Ca(PO3)2 and LaP5O14, which was owing
was backed by X-ray examination. X-ray diffractograms of to difficulties in winning a phase-pure compound of
presintered samples with composition ranging between 25 CaLa(PO3)5. The above compounds, mixed in definite ratios
and 45 wt.% Ca(PO3)2 (75 and 55 wt.% La(PO3)3) showed by weight, were preheated at 7008C for 20 h. On the basis of
mainly reflections originating from the initial phosphates. DTA of heating of the samples as well as of X-ray analysis,
Moreover, the reflections characteristic of a new phase, that the phase equilibria were determined and the phase diagram
were observed during the course of investigations of the sys- of the CaLa(PO3)5–LaP5O14 system was plotted. Equilib-
tem LaP5O14–Ca(PO3)2, occurred in this case. This phase rium diagram of this system is presented in Fig. 4. The system
was assumed to be an unknown binary calcium–lanthanum does not reveal all the features of the pseudobinary system.
metaphosphate. In its upper, high-temperature part it has a multiphase char-
Consequently, an attempt was made to win the phosphate acter. Above 8108C four phases appear, viz. liquid C and the
in the form of phase-pure. The following preparations were
employed as the initial material: (i) La(PO3)3 and Ca(PO3)2
mixed in the molar ratio of 1:1 and 1:2, (ii) LaP5O14 and
Ca(PO3)2 mixed in the ratio 1:1 and 1:2, (iii) CaCO3 and
LaP5O14 mixed in the ratio 1:1 and 2:1, (iv) La2O3 and
CaCO3 and NH4H2PO4 mixed in the molar ratio 1:2:10 and
1:4:14. The mixtures mentioned were pressed into pellets,
then treated through the following thermal action: (i) they
were sintered at different temperatures and then quenched
from these temperatures (with ice) or cooled slowly to room
temperature, (ii) they were heated to a temperature at which
the preparations became partly fused or completely melted,
and then slowly cooled (employing grafting to initiate crys-
tallization) to room temperature.
The phase composition of the products was determined
each time by powder X-ray analysis. The result appeared to
be unsatisfactory. Specimens obtained were at least diphase Fig. 3. Phase diagram of the system La(PO3)3–Ca(PO3)2.
preparations containing a considerable amount of La(PO3)3
besides the calcium–lanthanum binary metaphosphate. Also,
calcium metaphosphate was present in some preparations.
The most effective result was obtained upon sintering of an
equimolar mixture of Ca(PO3)2 and LaP5O14 at a temperature
of 8008C for 10 h. The presence of calcium–lanthanumbinary
metaphosphate was manifested by high intensity reflections
in the X-ray diffractogram of the sample.
The phase diagram of the La(PO3)3–Ca(PO3)2 system,
which is presented in Fig. 3, was determined on the basis of
this investigation. The run of the liquidus and solidus curves
was identified from DTA of heating. A formula of
CaLa(PO3)5 has been ascribed to the binary metaphosphate
present in the system. The compound melts incongruently at
9008C. This is confirmed by the thermal effects apparent on
the DTA-curves at 9008C, in the composition range 25–50 Fig. 4. Phase diagram of the system CaLa(PO3)5–LaP5O14.

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 W. Jungowska, T. Znamierowska / Materials Chemistry and Physics 48 (1997) 230–233
Fig. 5. Phase diagram of the system La(PO3)3–Ca(PO3)2–P2O5.
phosphates La(PO3)3, LaP5O14 and CaLa(PO3)5. As a result
of the peritectic reaction, liquid C and lanthanum metaphos-
phate La(PO3)3 are used up to form the metaphosphate
CaLa(PO3)5. Under equilibrium conditions, in the subsoli-
dus area, the system described is therefore a binary system,
i.e. below the temperature 8108C only the two phases
CaLa(PO3)5 and LaP5O14 should occur. Under our experi-
mental conditions, the ternary-phase samples obtained were
a mixture of CaLa(PO3)5, LaP5O14 and La(PO3)3. The pres-
ence of La(PO3)3 resulted from the fact that it was not pos-
sible for us to obtain a phase-purity CaLa(PO3)5. It could be
mentioned that a small mass decrement, apparentlyconnected
with decomposition of LaP5O14 and evaporation of P2O5, was
noted in the DTA-curves of heating (at a rate of 7.5–108
miny1). For LaP5O14-rich samples, the mass decrement
started with a temperature of 850–9008C, for samples with a
lower content of LaP5O14, the evaporation of P2O5 was noted
at a temperature of approximately 9508C, like the case of pure
LaP5O14.
Fig. 5 presents a phase diagram of the system La(PO3)3–
Ca(PO3)2–P2O5 in the P2O5-rich part. In view of the exper-
imental difficulties noted at the beginning of the paper, these
phase equilibria are only tentatively proposed. The effects
seen from Figs. 1 and 4 at approximately 8008C indicate that
a ternary peritectic, P1, is present in the area of interest.
Composition of the peritectic remains unknown. However,
the direction of run of the line of the binary eutectic e2P1 and
binary peritectic p1P1 has been identified. In the region
233
La(PO3)3–CaLa(PO3)5–P1–LaP5O14, at a temperature of
8108C, a ternary peritectic reaction proceeds according to the
network: CP qLa(PO3)3 ™CaLa(PO3)5qLaP5O14 (where
1
CP denotes a liquid composed of the ternary peritectic P1).
1
The peritectic curve p2p3 is associated with the reaction
Cp p qLaPO4™La(PO3)3 (where Cp p denotes a liquid
2 3 2 3
with a composition corresponding to the points in the line
p2p3). The reaction does not affect the phase equilibria of the
system in question at lower temperatures.
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