Fluid Phase Equilibria 456 (2018) 46e56

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Fluid Phase Equilibria

jour n al ho m e p a g e : ww w .e l s ev i er . c om / lo c at e/ fl u id

Thermodynamic equilibrium in the system H 2OþP2O5þCaCO 3 at 25

and 70   C: Application for synthesis of calcium phosphate products
based on calcium carbonate decomposition
Z. Bakher *, M. Kaddami
Laboratory “Physical Chemistry of Processes and Materials” Faculty of Science and Technology, University Hassan 1, Settat, Morocco

ar t i c l e i n f o ab s t r a c t

Article history: The solid-liquid equilibrium of the ternary system of water-phosphorus pentoxide-calcium carbonate
Received 12 July 2017 was studied using a synthesis method based on the measurement of the solution conductivity under
Received in revised form atmospheric air pressure. Two isotherms were established at 25   C and 70   C with control of calcium
3 October 2017
carbonate decomposition in contact with aqueous sol utions of P 2O 5. A phase sequences study was car-
Accepted 5 October 2017
ried out at 25   C in the isoplethic section of CaCO 3-H 2O-P 2O5 system. The solid phases observed at these
Available online 7 October 2017
temperatures are: dehydrated calcium hydrogen phosphate CaHPO 4$2H 2O, Hydroxyapatite
Ca 10(PO 4)6(OH) 2, anhydrous calcium hydrogen phosphate CaHPO 4 and calcium dihydrogen phosphate
Keywords:
Phase diagram
monohydr ate Ca(H 2PO 4)2$H2O. All stable solids are characterized by X-ray diffraction and the Schrei-
Calcium phosphate products nemaker method.
Schreinemaker's method © 2017 Elsevier B.V. All rights reserved.
Isotherm 25 and 70   C
Conductimetric method

1. Introduction
Calcium phosphates compounds of high purity are produced for
different uses including pharmaceutical and nutritional applica-
tions. There are five distinct groups of cal cium phosphates:
Ca(H 2PO4)2 anhydrous monocalcium phosphate (MCPa), Ca(H 2-
PO 4)2$H2O monocalcium phosphate monohydrate (MCPM), CaH-
PO 4$2H 2O dicalciums dehydrate DCPD, CaHPO4 anhydrous salt
(DCPa) and Ca 5(OH)(PO 4)3 hydroxyapatite (HAP). In connection
with the experimental preparation of calcium phosphates com-
pounds, many methods have been reported for their synthesis. For
example, HAP including solid-state reaction, solegel, precipitation
methods and electrophoretic deposition methods [1,2]. In addition
to that, hydroxyapatite can be used in different areas, according to
Yapıncak Go €ncü et al. [3] HAP is widely used in orthopedic implants
for the repair and reconstruction of bone tissue defects due to their
chemical composition and crystal structure compared to those
inorganic parts of the bones and teeth. For R. F. Bonan et al. [4] one
way to improve these properties is to combine HAP with other
materials such as zirconia, alumina, bioglasses or titanium in order
to combine the desirable properties of the two chemical elements
(HAP and the added element). Therefore, the determination of the
stability zone of HAP based on calcium carbonate is very important
and can be very useful industrially.
Different s ources of calcium can be used to produce calcium
phosphate compounds. Calcium oxide and calcium hydroxide have
been widely studied. The exploitation of calcium carbonates to
produce HA P and phosphate products is more economical given
their abundance and pr ice. Hence the interest of the study of the
ternary system CaCO 3-H 2O-P 2O5.
To achieve this objective and to determine the stability zone of
pure HAP and the other phases already mentioned , knowledge
about the phase equilibr ia in the ternary system calcium carbonate-
phosphorus pentoxide-water was investigated by the solubility
determination of hydroxyapatite, anhydrous monocalcium phos-
phate, monocalcium phosphate monohydrate, dicalcium dehydrate
and dicalcium anhydrous salt at 25   C. Since the reaction between
carbonate and phosphoric acid is exothermic and can reach tem-
peratures around 70, the isotherm at 70  C has also been studied.
Since the reaction between the calcium carbonate and phosphoric
acid produces CO 2, the CaCO 3-P2O5-H 2O system is included in
quaternary system CO 2-CaO-P 2O5-H2O.

* Corresponding author.
E-mail address: z.bakher@uhp.ac.ma (Z. Bakher).

https://doi.org/10.1016/j.fluid.2017.10.005
0378-3812/© 2017 Elsevier B.V. All rights reserved.
 Z. Bakher, M. Kaddami / Fluid Phase Equilibria 456 (2018) 46e56 47

2. Literature review

Several studies have been carried out to determine the stability

domains of phosphate products with different sources of calcium,
the most recent is the work of Labgairi et al. [5] that studied the
ternary diagram H 3PO4-Ca(OH) 2-H 2O at 15 and 45   C. Roger I
Martin [6] published a diagram of the same system at the tem-
perature 25   C. Other temperature was investigated by VanWazer
[7]. On the other hand, Elmore et al. [8] have published several
articles, the most important of these is the study of equilibrium in
the system calcium oxide-phosphorus pentoxide-water at
25,40,50.7, 80 and 100   C. According to the results of Elmore [8], the
solubility of each salt varied regularly with temperature, in the
presence of stable phases: CaHPO 4$2H 2O, CaHPO 4, Ca(H 2PO 4)2$H2O
and Ca(H 2PO 4)2, but the stability domain of hydroxyapatite is not
investigated by the author.

3. Experimental methods

a. Isotherm determination at 25 and 70   C

In the present study, the branches of solubility isotherms at 25 Fig. 2. Experimental setup: (1) magnetic bar, (2) aqueous solution, (3) thermostatic
jacket, (4) Capillary water-inlet, (5) conductivity meter, (6) opening for gas outlet with
and 70   C explored in this work were determined under atmo- closure cap, (7) thermometer, (8) Closure cap, (9) refrigerator.
spheric pressure by the use of a synthetic method based on
conductimetric measurements [9e11]. This method was success-
fully and effectively used to define the branches of solubility of Table 1
several complex systems. It is based on the variation of the elec- Information of the chemicals compounds.
trical conductivity of solutions according to their dilution. Reference Chemical formula Provider Purity (Weight percentage)
This method determines accurately and completely the phase
214701 P 2O5 Sigma-Aldrich 99%
equilibria diagrams and the different stability zones in the system. 12010 CaCO 3 Sigma-Aldrich > 98%
Fig. 2 shows the experimental setup of the conductimetric method, 27285 EDTA Riedel-de Haen > 99%
it consisting in gradually adding small amounts of water, generally 30620 NaOH Sigma-Aldri ch 98%
0.5 ml at each addition, by capillary water-inlet (Fig. 2) in a solid-
liquid mixture M with a total mass of 30 g. The mixture is already
prepared and placed in the thermostatic jacket, at constant pres- constant conductivity value is observed while an invariant equi-
sure and at constant temperature. The temperature control was librium is ana lyzed, Fig. 1. The analysis of seri es of mixtures allowed
carried out by the thermostat VWR Model 1197P (USA). After each to define the liquidus curves of each element in the ternary system.
addition of water, the mixture is stirred using magnetic bar then the In this study, the starting materials are: Calcium carbonate
conductivity of the solution is measured, the equilibrium is reached CaCO 3, Phosphorus pentoxide P 2O5 and water that was distilled
when the conductivity value stabilizes. The gas formed in ther- twice using bi-distiller combined to resin column with conductivity
mostatic jacket is released using the opening for gas outlet (Fig. 2). in the order of 6 ms at 291.15 K. Complexometric calcium determi-
The operation is repeated until the complete dissolution of the nation with high purity of EDTA. The concentration P 2O5 aqueous
precipitated salt. The curves (conductivity ¼ f (water volume or solution was determined using titration by sodium hydroxide. The
well chosen solution)) obtain breaks at each phase change and a following table presents all informations of the chemical

Fig. 1. Conductivity study variation of the isothermal dilution of mixture M in the ternary system H 2O-A-B.
48 Z. Bakher, M. Kaddami / Fluid Phase Equilibria 456 (2018) 46e56

Fig. 3. X-ray diffraction analysis of CaCO3 (ech1).

Fig. 4. The evolution of the phosphate monocalcium reaction as a function of time: 2 min(Z1), 15 min(Z2) and 3 h(Z3).( -): the characteristic rays of the MCPM, ( :) the char-
acteristic rays of the CaCO 3.
 Z. Bakher, M. Kaddami / Fluid Phase Equilibria 456 (2018) 46e56 49

Table 2 Table 3
Experimental composition of the saturated solution for the ternary system CaO- Experimental composition of the saturated solution for the ternary system CaO-
P2O5-H 2O at 25   C and P ¼ 0,1 MP. P2O5-H 2O at 70   C and P ¼ 0,1 MP.

system CaO-P 2O5- Solid phases in equilibrium with saturated solution system CaO-P 2O5- Solid phases in equilibrium with saturated solution
H2O H2O

Liquidus Liquidus
composition composition
(Weight percentage) (Weight percentage)

w CaO w P2O5 w CaO w P 2O5

0.84 2.12 CaHPO 4$2H 2O 0.27 1.97 CaHPO 4$2H 2O

1.49 4.36 CaHPO 4$2H 2O 0.94 5.34 CaHPO 4$2H 2O
2.00 6.13 CaHPO 4$2H 2O þ CaHPO 4 1.88 10.27 CaHPO 4$2H 2O þ CaHPO 4
3.94 15.78 CaHPO 4 2.30 12.79 CaHPO 4
4.22 16.88 CaHPO 4 2.80 15.31 CaHPO 4
5.00 20.58 CaHPO 4 3.02 16.82 CaHPO 4
5.34 23.17 CaHPO 4 3.60 18.26 CaHPO 4
5.88 25.16 CaHPO 4 þCa(H 2PO 4)2$H2O 3.89 20.35 CaHPO 4
5.35 26.39 Ca(H 2PO 4)2$H2O 4.05 22.16 CaHPO 4
5.09 27.87 Ca(H 2PO 4)2$H2O 4.41 24.24 CaHPO 4
4.71 29.58 Ca(H 2PO 4)2$H2O 4.48 25.39 CaHPO 4
4.23 31.73 Ca(H 2PO 4)2$H2O 4.92 27.99 CaHPO 4
3.59 34.35 Ca(H 2PO 4)2$H2O 5.11 29.96 CaHPO 4
2.80 38.10 Ca(H 2PO 4)2$H2O 5.33 31.62 CaHPO 4
1.69 43.41 Ca(H 2PO 4)2$H2O 5.58 33.54 CaHPO 4þCa(H 2PO4)2$H2O
1.22 45.93 Ca(H 2PO 4)2$H2O 5.41 34.67 Ca(H 2PO4)2$H2O
0.70 50.14 Ca(H 2PO 4)2$H2O 5.21 35.63 Ca(H 2PO4)2$H2O
4.68 37.17 Ca(H 2PO4)2$H2O
Estimated standard uncertainties u are: u(T) ¼ 0.1   K,u(w) ¼ 0,05 and u(P) ¼ 5Kpa.
4.00 39.94 Ca(H 2PO4)2$H2O
3.51 41.90 Ca(H 2PO4)2$H2O
3.25 43.28 Ca(H 2PO4)2$H2O
compounds (see Table 1): 3.02 44.71 Ca(H 2PO4)2$H2O
The purity of the phosphate products depends directly on the 2.69 45.97 Ca(H 2PO4)2$H2O
origin of calcium. To verify the purity of cal cium carbonate, the 2.37 47.83 Ca(H 2PO4)2$H2O
1.99 49.58 Ca(H 2PO4)2$H2O
product is analyzed by DRX, then its spectrum is compared with
1.75 50.97 Ca(H 2PO4)2$H2O
that published by Sitepu H [12] in Fig. 3. The spectrum does not 1.49 52.98 Ca(H 2PO4)2$H2O
present aberrant rays, therefore, we can conclude that our product 1.26 54.25 Ca(H 2PO4)2$H2O
is pure. 0.74 57.92 Ca(H 2PO4)2$H2O

Estimated standard uncertainties u are: u(T) ¼ 0.1   K,u(w) ¼ 0.05 and u(P) ¼ 5Kpa.
b. Cha racterization:

All the solids were analyzed by x-ray diffraction allowed to define
the nature of the solid phases in equilibrium in different saturated
solutions, using BRUKER type: D2 Phaser (Cu-Ka 1,541874 A) with a
LYNXEYE detector, each stable solid was analyzed for a period of
20 min between 10 and 80   .
4. Experimental results
4.1. Conductimetric analysis
During the first tests of the conductimetric analysis, it was
observed that the decomposition of calcium carbonate by the
attack of phosphorus pentoxide solution is not complete and is
carried out in a progressive way. It has been decided to check the
kinetics of the reaction and determine the time of total decompo-
sition of calcium carbonate.
4.1.1. The kinetics of decomposition of calcium carbonate
As previously mentioned, the reaction between calcium car-
bonate and phosphor pentoxide solution is exothermic with release
of carbon dioxide. To make sure that the reaction of phosphate
monocalcium does not cross by intermediary phases and to
determine the time of total decomposition of calcium carbonate, a
kinetics study of the reaction was established by the follow-up of
the progress of the reaction in 2 min (Z1), 15 min (Z2) and 3 h (Z3),
Fig. 4, For the sample M1 in Fig. 6. Fig. 4 presents the evolution of
the phosphate monocalcium reaction as a function of time:
Fig. 4 shows the evolution analysis of the DRX spectra before
15 min (Z1) and at 15 min (Z2), the MCPM product is present with
calcium carbonate. After 15 min (Z3), the decomposition of the
calcium carbonate is complete, so the samples are prepared six
hours before beginning the conductimetric analysis.
4.1.2. Isotherms 25 and 70   C
The ternary system CaCO 3-P 2O5-H2O was established at two
temperatures 25 and 70   C. Since the decomposition of calcium
carbonate is complete with the release of CO 2, the liquidus of
different products solubility are presented in the system CaO-H2O-
P2O5. Tables 2 and 3 present the solubility values at 25 and 70   C
respectively. The obtained results are presented graphically in
Figs. 5 and 6 to visualize the relationship between the carbonate
system and the oxide system.
Both isotherms in 25 and 70   C present three branches of sol-
ubility (LI , I I 00 , I 00 W) and two invariant points (I , I 00 ).
The first branch LI presents the liquidus of Ca(H 2PO 4)2$H2O
which who is represented by MCPM in Figs. 5 and 6.
Both branches I I 00 and I 00 W present successively the liquidus of
CaHPO4 which is represented by DCPa and the liquidus of CaH-
PO 4$2H 2O which is presented by DCPD in Figs. 5 and 6.
In the two isotherms the three phases domain
DCPD þ DCPa þ liq represented by the triangle (I”, DCPa, DCPD) is
50 Z. Bakher, M. Kaddami / Fluid Phase Equilibria 456 (2018) 46e56

Fig. 5. Presentation of isotherm at 70   C in the ternary system CO 2-CaO-P 2O5-H 2O, (Dotted lines is the starting system CaCO 3-H 2O-P 2O5).

very small and appears in the two Figs. 5 and 6 similar to a single
line tri angle (I”,DCPa).
The HAP solubility in the water is very low that's why the sol-
ubility branch of solubility WZ is almost coincident with the binary
H2O-CaCO 3 (Figs. 5 and 6). On the other hand, we determined the
limits of the region of HAP stability by the conductimetric method.
Production reactions of MCPM, DCPa, DCPD and HAP are pre-
sented respectively:
MCPM: P2 O5 þ CaCO 3 þ H2 O/CaðH2 PO 4 Þ2 :H2 O þ CO 2
DCPa : P2 O5 þ 2CaCO 3 þ H2 O/2CaHPO 4 þ 2CO 2
DCPD : P2 O5 þ 2CaCO 3 þ 3H2 O/2CaHPO 4 :2H2 O þ 2CO 2
HAP : 3P2 O5 þ 10CaCO 3 þ H2 O/Ca 10 ðPO 4 Þ6 ðOHÞ2 þ 10CO 2
To compare the branches of solubility obtained in this study
with other works already realized by other authors in calcium oxide
system, Fig. 7 shows the isotherm at 25   C in this study presented in
the system CaO-H2O-P 2O5 with isotherm presented by Elmore et al.
[8] in 25   C for system CaO. The solubility branches of the MCPM
overlap perfectly.
4.2. Characterization by Schreinemaker's method and DRX analysis
In order to define the stability zones of each solid, the Schrei-
nemaker's method [13e15] consists in preparing different mixtures
in each domain (E1, E2, E3, E4, E5, E6 and E7), and are allowed to
stabilize in a five days. The solids (S1, S2, S3, S4, S5, S6 and S7) and
 Z. Bakher, M. Kaddami / Fluid Phase Equilibria 456 (2018) 46e56 51

Fig. 6. Presentation of isotherm at 25   C in the ternary system CO2-CaO-P 2O5-H 2O, (Dotted lines is the starting system CaCO 3-H 2O-P2O5).

solutions (R1, R2, R3, R4, R5, R6 and R7) are separated (Fig. 8). The
calcium is determined by EDTA and phosphoric acid in the solu-
tions by titration using sodium hydroxide.
Table 4 presents the composition of the starting mixtures and
the percentage of CaO and P 2O5 in the liquid and solid phases.
The calcium percentage compositions found for all of the resi-
dues R1, R2, R3,R4,R4, R6 and R7 remain somewhat lower than the
theoretical one, and this can be explained by the fact that the drying
is not complete and the crystals still contain traces of solution.
The following spectra show the DRX analysis of the residues R2,
R5, R6 and R7 presented in Fig. 8.
The comparison between the experimental DRX spectra (blue)
and the bibliographic data (red) confirms that the stable phases in
CaCO3-P2O5-H2O systems are Ca(HPO 4)$2H 2O, CaHPO 4, Ca(HPO 4)2
H2O and Ca 10 (PO 4)6(OH) 2. The spectrum of the residue R6 in Fig. 12
shows that the stable phase in the branch WI 00 is DCPD and not HAP
as mentioned by Brown P$W [16].
The following Table 5 shows the references of each DRX
spectrum:
4.3. Study of phase sequences at 25   C in the isoplethic section
y ¼ 1.63389x þ 100 of the CaCO 3-H 2O-P 2O5 system
The mixture of the calcium carbonate with aqueous solutions of
phosphorus pentoxide (61.2%) leads to different phosphate prod-
ucts. In order to evaluate the calcium carbonate effect on the nature
of the phosphate products obtained, six samples were prepared by
reaction between calcium carbonate and phosphorus pentoxide
solution (61.2%) according to isoplethic y ¼ 1.63389x þ 100,
where [y] is the percentage by weight of CaCO 3 and [x] is the
percentage by weight of phosphorus pentoxide. After five days, the
stable solids were separated and analyzed by DRX. The Fig. 13
52 Z. Bakher, M. Kaddami / Fluid Phase Equilibria 456 (2018) 46e56
Fig. 7. Comparison between the results of this study at 25   C and the bibliographic data of the Ternary system CaO-P 2O5-H 2O at 25   C.
shows the analysis results of each stable phase.
After the analysis of the DRX spectra: M1, M2 and M3 showed
that the stable phase is MCPM, we note for M4 and M5 the addition
of the characteristic rays of DCPa which proves the zone of stability
between MCPM and DCPa. M6 presents the stable phase of DCPa.
According to the results of analyses DRX, we can see the total
disappearance of calcium carbonate, in other term the release tota l
of carbon dioxide, and consequently the convergence of the plan
CaCO 3-H 2O-P 2O5 towards the plan CaO-H 2O-P 2O5.
The following Table 6 shows the composition of each sample
and the Fig. 13 presents the different spectra obtained.
5. Conclusion
The present work had for objective the study of the preparation
of MCPM, DCPD, DCPa and HAP products from the calcium car-
bonate because of their abundance and their lower cost. The tests
on the decomposition of CaCO 3 in the presence of aqueous phos-
phorus pentoxide solution show that their decomposition is
complete after 15 min at laboratory scale. In this work, we defined
the stability domain of these products at two temperatures 25 and
70  C. The characterization of the obtained solid phases was made
by Schreinemaker method and the DRX analysis.
This study confirms that liquidus and domains of stability of the
MCPM, DCPD, DCPa and HAP stay the same whatever is the calcium
raw material's source (Ca(OH) 2, CaO or CaCO 3), carbonate of cal-
cium remains the most economic choice.
Both isotherms in 25 and 70   C present three branches of sol-
ubility and two invariant points with a domain of stability of Hy-
droxyapatite with basic solution, this domain can be very useful
industrially to produce HAP with a very high purity and with less
energy because the reaction is feasible in 25   C. According to the
isotherm 70   C. We note that the solubility of MCPM increases, but
the solubility of DCPa and DCPD decreases according to the
temperature.
This study clarifies on the one hand the preparation of MCPM,
DCPD, DCPa and HAP from various resources bringing the calcium
element into these products. On the other hand, in addition to
 Z. Bakher, M. Kaddami / Fluid Phase Equilibria 456 (2018) 46e56 53

Fig. 8. Presentation of the results of the Schreinemaker's method in the system CaO-H 2 O-P 2O5 at 25   C.

Fig. 9. X-ray diffraction analysis of Ca(H 2PO4)2$H2O (R2).

54 Z. Bakher, M. Kaddami / Fluid Phase Equilibria 456 (2018) 46e56

Table 4
The results of the Schreinemaker's method at 25   C.

Mixture Compositions of starting mixtures solu tions (S) composition Solides (R) composition

composition by mass CaCO 3 composition by mass CaO

% CaCO 3 % P 2O5 % CaO % P 2O5 % CaO % P2O5 % CaO % P 2O5

E1 10.09 52.05 5.92 54.47 1.08 53.84 19.57 66.30

E2 15.01 44.24 9.00 47.36 1.90 42.19 20.83 66.67
E3 15.09 34.59 9.05 37.05 4.41 29.41 21.05 66.32
E4 20.36 19.76 12.52 21.70 5.26 21.05 40.20 72.06
E5 24.49 26.52 15.37 29.72 2.86 11.43 40.40 71.72
E6 12.48 4.29 7.40 4.54 1.16 4.21 35.71 63.39
E7 11.65 10.68 6.88 11.26 1.53 0.10 54.55 69.09

Estimated standard uncertainties u By repetition of dosage are: u(%[CaO]) ¼ 0,12 ,U(%(P 2O5)) ¼ 0,1.

Fig. 10. X-ray diffraction analysis of Ca 10(PO 4)6(OH) 2 (R7).

Fig. 11. X-ray diffraction analysis of CaHPO 4 (R5).

 Z. Bakher, M. Kaddami / Fluid Phase Equilibria 456 (2018) 46e56 55

Fig. 12. X-ray diffraction analysis of CaHPO 4$2H 2O (R6).

Table 5 Table 6
The bibliographic references of each X-ray diffraction. Composition of each sample and their stable phase.

Samples Stable phase Figure references Entry Sample ID Compositions of Stable phases obtained
mixtures (Weight
R6 Ca(HPO 4)$2H 2O Fig. 12 [17] 96-153-3076 percentage)
R2 Ca(HPO 4)2$H2O Fig. 9 [18] 96-231-0631
R5 CaHPO 4 Fig. 11 [19] 96-210-6085 w CaCO 3 w P 2O5
R7 Ca 10 (PO 4)6(OH) 2 Fig. 10 [20] 96-900-1234
M1 5.60 57.77 Ca(H 2PO 4)2$H2O
M2 12.92 53.29 Ca(H 2PO 4)2$H2O
M3 29.35 43.24 Ca(H 2PO 4)2$H2O
establishing the new isotherm at 70   C, it brings new values of M4 33.53 40.68 Ca(H 2PO 4)2$H2O þ CaHPO 4
solubility in 25   C of the global system calcium oxide-water- M5 37.24 38.41 Ca(H 2PO 4)2$H2O þ CaHPO 4
phosphorus pentoxide, what is going to strengthen the modelling M6 33.17 34.17 CaHPO 4

Fig. 13. X-ray diffraction analysis of isopleth: ( :) the characteristic rays of the MCPM, (C) the characteristic rays of the DCPa.
56 Z. Bakher, M. Kaddami / Fluid Phase Equilibria 456 (2018) 46e56
thermodynamics of this system.
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