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Materials Chemistry and Physics 78 (2002) 308312

Material science communication

Investigation of phase evolution during the formation of calcium

potassium sodium orthophosphate
Niu Jinlong a,b, , Zhang Zhenxi a , Jiang Dazong a
a

Institute of Biomedical Engineering, School of Life Science and Technology, Xian Jiaotong University, Xian 710049, China
b Northwest Institute for Nonferrous Metal Research, Xian 710016, China
Received 14 September 2001; received in revised form 7 March 2002; accepted 6 April 2002

Abstract
The formation of calcium potassium sodium orthophosphate (Ca2 KNa(PO4 )2 ) from sodium dihydrogen phosphate dihydrate (NaH2 PO4
2H2 O), potassium dihydrogen phosphate (KH2 PO4 ) and calcium carbonate (CaCO3 ) was investigated using differential thermal analysis
(DTA), thermal gravimetric analysis (TGA) and powder X-ray diffraction (XRD). DTA showed five distinct thermal events attributed
to dehydration of NaH2 PO4 2H2 O, dehydration of NaH2 PO4 and KH2 PO4 , the transition of amorphous calcium sodium phosphate to
-CaNaPO4 , the decomposition of CaCO3 to CaO, and the crystallization of Ca2 KNa(PO4 )2 . TGA showed 5.6% weight loss between
70 and 170 C due to the dehydration of NaH2 PO4 2H2 O to NaH2 PO4 ; the 7.3% weight loss between 170 and 280 C is due to the
dehydration of NaH2 PO4 and KH2 PO4 ; a continuous weight loss over 280760 C due to the reaction of melted alkali metal phosphates
with CaCO3 and an approximate 8% weight loss between 670 and 840 C due to the calcination of residual CaCO3 . XRD analysis, as a
function of temperature, supported the evolution of these events and phases, showed the formation of other intermediates: -CaKPO4 and
calcium potassium pyrophosphate (CaK2 P2 O7 ). The proposed mechanism of the reaction to Ca2 KNa(PO4 )2 involves the formation and
consumption of these intermediates: acid alkali metal pyrophosphate, metaphosphate, CaK2 P2 O7 and -CaNaPO4 .
2002 Elsevier Science B.V. All rights reserved.
Keywords: Resorbable bioceramic; Calcium alkali phosphate; Thermochemical synthesis

1. Introduction
Being the main inorganic constituent of hard tissue,
calcium phosphates have long been attractive in hard tissue repair [1]. Calcium hydroxyapatite (Ca10 (PO4 )6 (OH)2 ,
HA) and the more resorbable -tricalcium phosphate
(-Ca3 (PO4 )2 , -TCP), are currently recognized as ceramic materials that significantly simulate the mineralogical
structure of bone [2,3]. When calcium phosphates ceramics
implanted in vivo, these materials are non-toxic, antigenically inactive, noncarcinogenic and bond directly to bone
without any intervening connective tissue layer. They show
good biological compatibility, safety and osteoconductivity in living tissues; therefore, they are clinically used for
hard tissue replacement [4,5]. It is of great interest for
both phosphorous chemists and biomedical engineer, as
well as material scientists to understand the mechanism of
Corresponding author. Present address: Institute of Biomedical Engineering, School of Life Science and Technology, Xian Jiaotong University, Xian 710049, China. Tel.: +86-29-2668664.
E-mail address: niujinlong@sina.com (N. Jinlong).

the formation of calcium phosphate ceramics at high temperature. Because of different process, calcium phosphate
ceramic would have different physicochemical, mechanical
and biological properties.
HA and -TCP both are bioactive materials, but their
biodegrabilities are different. HA is much less degraded and
resorbed by living tissue than -TCP [6]. Though -TCP is
biodegradable and resorbable bioceramics, its biodegrability
and/or bioresorbability are worth improving for fast repair of
bone defect. To improve the degradability of calcium phosphate ceramic with no toxic additive, alkali metals phosphate was added to tricalcium phosphate, and a new kind
of crystal ceramic was formed with the chemical formula
Ca2 KNa(PO4 )2 [7,8]. Because K+ and Na+ are the basic
constituent of body fluid and whole blood, the relatively
high solubility of Ca2 KNa(PO4 )2 ceramic would make it a
promising material for fast healing of bone defect in living
body.
A solid state reaction was selected to synthesize crystal
Ca2 KNa(PO4 )2 , the phase evolution during the formation of
Ca2 KNa(PO4 )2 was investigated in this project to understand
the mechanism of the reaction path.

0254-0584/02/$ see front matter 2002 Elsevier Science B.V. All rights reserved.
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2. Experiments
Because of the difference between solubility of calcium
and alkali metal phosphates, crystal ceramic Ca2 KNa(PO4 )2
cannot coprecipitate from aqueous system, the only synthesis method may be solid state reaction [7,8]. Analytical purity chemical reagents of calcium carbonate (CaCO3 CC),
potassium dihydrogen phosphate (KH2 PO4 KHP), sodium
dihydrogen phosphate dihydrate (NaH2 PO4 2H2 ONHP)
were mixed stoichiometrically with formula Ca2 KNa(PO4 )2
in 2:1:1 molar ratio and milled for 2 h in alumina roller.
Each 10 g of the mixture was uniaxially compressed under 50 MPa and placed in alumina crucible, heated in SiC
furnace. Samples were removed from the furnace at 400,
600, 800, 900, 1000, 1100, 1200 and 1300 C after held at
the given temperature for half-hour. These samples were removed out from crucible and crushed, grounded immediately
in an alumina mortar to powder and kept in a dry container.
The sample powder was packed into a special aluminum
container used for powder X-ray diffraction (XRD) measurement. Powder XRD was performed at room temperature using a diffractometer (PW1710, Philips) with Cu K radiation
= 1.5406 , generator tension 40 kV and current 30 mA.
Monochrometer and Scintillation detector were used. Sample was scanned step by step over the 2 range of 2055 ,
using a step size of 0.02 and a scan rate of 0.02 s1 .
Thermal gravimetric analysis (TGA) (TGA 51 Thermogravimetric Analyzer, TA Instruments) and differential

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thermal analysis (DTA) (DSC 910S Differential Scanning

Calorimeter, TA Instruments) were performed on precursor powder over a temperature range of 251000 and
251300 C, respectively with a heating rate of 20 C min1 .

3. Results and discussion

DTA and TGA data during the reaction of CC (CaCO3 )
and KHP (KH2 PO4 ) with NHP (NaH2 PO4 2H2 O) to form
Ca2 KNa(PO4 )2 are shown as curves DTA and TGA in Fig. 1.
The bulk reaction may be shown as
2CaCO3 + KH2 PO4 + NaH2 PO4 2H2 O
Ca2 KNa(PO4 )2 + 4H2 O +2CO2

(1)

The theoretical total weight loss, due to the escape of all

gaseous species, calculated from the reaction (Eq. (1)) is
32.5%. The total weight loss, observed upon heating to
1000 C, was 30%.
Powder XRD was used as a method to detect phase evolution during the reaction. All the samples removed at different temperatures were measured and their XRD patterns
were shown in Fig. 2. All detected crystalline phases are
labeled (Fig. 2).
Powder XRD shows, after rolled in alumina roller for 2 h,
the main crystalline phases of the precursor powder were
CC (CaCO3 , JCPDS #5586) and KHP (KH2 PO4 , JCPDS

Fig. 1. Thermal analysis data (DTA and TGA) for the reaction of CaCO3 with KH2 PO4 and NaH2 PO4 2H2 O to form Ca2 KNa(PO4 )2 at a heating rate
of 20 C min1 .


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N. Jinlong et al. / Materials Chemistry and Physics 78 (2002) 308312

Fig. 2. XRD patterns of samples showing the phase evolution during the formation of Ca2 KNa(PO4 )2 . Temperatures at which samples were removed are
shown. Labels are as follows: CC (CaCO3 ); KHP (KH2 PO4 ); NHP (NaH2 PO4 2H2 O); CKP (CaK2 P2 O7 ); CNP (-CaNaPO4 ); CKNP (Ca2 KNa(PO4 )2 ).

#35807). The diffraction peaks of NHP (NaH2 PO4 2H2 O,

JCPDS #10198) were not clearly shown in the XRD pattern
of precursor, but there were two weak peaks of sodium dihydrogen phosphate monohydrate (NaH2 PO4 H2 O, JCPDS
#11651) of d = 3.37 (2 = 26.42 ) and d = 3.16
(2 = 28.18 ). There is a possibility that the first strong peak
(d = 3.70 ) of NaH2 PO4 2H2 O may be overlapped by the
strongest peak of KH2 PO4 (d = 3.72 , JCPDS #35807),
as shown in Fig. 2, the observed peak is d = 3.71 (2 =
23.93 ). This suggested that NaH2 PO4 2H2 O would lose a
little crystal water and NaH2 PO4 H2 O would form after long
time rolling, because of the frictional heat and long time
contact of NaH2 PO4 2H2 O with CaCO3 .
When the mixture was heated to 400 C, the XRD pattern
of the resulting material showed that the peaks of KH2 PO4
and NaH2 PO4 2H2 O disappeared, yet crystalline phase
of CaCO3 still remained, and a new phase was formed
which was determined as calcium potassium pyrophosphate (CaK2 P2 O7 , CKP, JCPDS #22805). DTA and TGA
showed, as comparison with XRD, that a substantial endothermic event and weight loss occurred between 70 and
170 C, peak value was about 83 C. This is suggested as
the dehydration process of NaH2 PO4 2H2 O to NaH2 PO4 .
The weight loss is about 5.6%, slightly lower than theoretical value (7.3%). The slightly small weight loss may be
due to the little water loss at the beginning of the mix stage.
NaH2 PO4 2H2 O would lose all its crystal water before
100 C [9]. The experiment showed that the fast dehydration
process began at about 70 C, the peak was about 83 C. It

is proposed consequently that NaH2 PO4 2H2 O has lost its

crystal water completely by 170 C. The reaction, occurred
within this stage, may be described as follows:
NaH2 PO4 2H2 O NaH2 PO4 + 2H2 O

(2)

At about 241 C (between 170 and 280 C), there was another significant endothermic event and a substantial weight
loss (6.7%), this is due to the melting process and the dehydration of KH2 PO4 and NaH2 PO4 . Since the melting
points are about 253 and 190 C, respectively, the mixture
of KH2 PO4 and NaH2 PO4 may have a melting point between theirs. It is known that KH2 PO4 and NaH2 PO4 will
decompose and dehydrate to acid pyrophosphate when the
temperature is higher than their melting points [9]. When the
temperature was increased to a much higher degree, the acid
pyrophosphate may become to metaphosphate. The melted
salt would solidify to glassy state when they were cooled.
The glassy phase gives very weak XRD intensity, so that
it cannot be detected by XRD. Meanwhile, the melted acid
pyrophosphate would react with CaCO3 inevitably, which
resulted in the release of carbon dioxide. The changes occurred at this stage may include the following reactions:
2NaH2 PO4 Na2 H2 P2 O7 + H2 O

(3)

2KH2 PO4 K2 H2 P2 O7 + H2 O

(4)

K2 H2 P2 O7 +CaCO3 CaK2 P2 O7 +H2 O +CO2

(5)

TGA showed a continuous weight losing (about 8.5%) between 280 and 670 C. This means that the melted acid

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N. Jinlong et al. / Materials Chemistry and Physics 78 (2002) 308312

pyrophosphate reacted with CC continuously, and carbon

dioxide and water vapor were released simultaneously. XRD
pattern of the sample produced at 400 C has shown the disappearance of dihydrogen phosphates and the formation of
CKP (CaK2 P2 O7 , JCPDS #22805).
XRD pattern of sample produced at 600 C showed
clearly the existence of CaK2 P2 O7 and CaCO3 phases.
Besides the two main phases, a new phase was detected
as -calcium sodium phosphate (-CaNaPO4 -CNP,
JCPDS #291193), because its three strong lines, d = 2.75,
2.70, 2.66 (2 = 32.58, 33.10, 33.71 , respectively) were
clearly found. The existence of -calcium potassium phosphate (-CaKPO4 , JCPDS #331002) may be possible,
because its three strong lines d = 2.98, 2.79, 2.06 may
be overlapped by the three lines of CaK2 P2 O7 (JCPDS
#22805) d = 3.00, 2.83, 2.06 , respectively. It can be
seen from the XRD pattern that the two peaks, d = 3.04
and 2.83 (2 = 29.40 and 31.60 ) are not symmetrical.
The right extension of the two peaks may conceal the two
lines of -CaKPO4 (d = 2.98 and 2.78 ). DTA showed
an endothermal peak at about 500 C without substantial
weight loss. This may be the phase transition of amorphous
calcium sodium and potassium phosphate to -CaNaPO4
and -CaKPO4 . NHP and KHP will melt and dehydrate
above 200 C; a glassy phase of pyrophosphate and/or
metaphosphate would be formed. The liquid glassy phosphates covered the reaction products of melt acid pyrophosphate with CaCO3 and an intermediate with molar ratio
Ca/P < 1 was formed. With the increase of reaction temperature, the Ca/P of intermediate would increase gradually.
CKP (CaK2 P2 O7 ) with Ca/P = 0.5 was first formed, then
at about 500 C, amorphous calcium potassium or -CNP
with Ca/P = 1 would produced in a little quantity. The intermediate phases were amorphous, diffraction peaks were
very weak, until the amorphous intermediate with Ca/P of
0.5 or 1 changed to crystalline phase. Besides the main
crystalline phases of CaCO3 and CaK2 P2 O7 , XRD pattern
of sample at 600 C showed the existence of -CaNaPO4 ,
supported the discussion above. So the reaction occurred
between 280 and 670 C may include Eq. (5) as well as the
following equations:
Na2 H2 P2 O7 + 2CaCO3
2CaNaPO4 (amorphous) + H2 O +2CO2
CaNaPO4 (amorphous) -CaNaPO4

(6)
(7)

DTA showed a significant endothermic event between 670

and 840 C that owed to the decomposition of CC. TGA
showed 8% weight loss over the same temperature range.
The reaction is shown below:
CaCO3 CaO + CO2

(8)

Although DTA showed that CaCO3 decomposed at about

780 C, TGA showed the calcination was not completed
until 840 C. XRD pattern of sample produced at 800 C

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showed significant amount of CaCO3 , which means CaCO3

would not decomposed completely at 800 C. -CaNaPO4
and CaK2 P2 O7 were also found as crystalline components
of the product. Besides CaCO3 , -CaNaPO4 and CaK2 P2 O7
crystals, there appeared some new peaks that were determined as diffraction lines of Ca2 KNa(PO4 )2 [8], because
these peaks appeared at the same position in the XRD pattern of sample produced at higher temperature. The reaction
may be as follows:
CaK2 P2 O7 + 2CaNaPO4 + CaO 2Ca2 KNa(PO4 )2

(9)

A slowly endothermic event was shown in DTA between

840 and 1300 C; it can be considered as the melting process of Ca2 KNa(PO4 )2 at high temperature, because the only
crystalline phase was Ca2 KNa(PO4 )2 in the samples produced at 900 C or higher temperature. The formation of
Ca2 KNa(PO4 )2 began at about 800 C with the decomposition of CaCO3 , but it was a solid state reaction of CaO with
CaK2 P2 O7 and -CaNaPO4 ; the lattice structure would not
be perfect at the initial stage of the reaction, it is necessary
to increase the reaction temperature. The appearance of the
sample tablet, produced at different temperatures, was of
benefit to the explanation of the reaction process. The white
block was formed at 900, 1000, 1100 and 1200 C, but the
tablet produced at 1300 C was semitransparent crystalline.
Hardness and strength of the sample increased with the reaction temperature. It is suggested that the melting degree
increased with the reaction temperature. Between 840 and
1000 C, there was a weight loss of 1.2%. The little weight
loss might attribute to the decomposition of CaCO3 that did
not calcine completely below 840 C.
The measured total weight loss of the precursor was about
30% between room temperature to 1000 C; it corresponded
to theoretical weight loss of 32.5%. The little difference
between the observed weight loss and calculated value may
be resulted from the dehydration of NaH2 PO4 2H2 O at the
initial mixing stage or the dehydration of the precursor stored
in the desiccator.

4. Conclusion
The formation of Ca2 KNa(PO4 )2 from the reaction of CC
(CaCO3 ), KHP (KH2 PO4 ) and NHP (NaH2 PO4 2H2 O) with
a molar ratio of 2:1:1 followed a complex chemical reaction
path. At the beginning stage of the reaction, NaH2 PO4 2H2 O
lost its total crystal water and formed NaH2 PO4 . Then, between 170 and 400 C the acid phosphate of sodium and
potassium melted and dehydrated to acid pyrophosphate, and
the melted salt reacted with CC to form CKP. The amorphous intermediate of calcium potassium and/or sodium
phosphate transformed to -CNP and -calcium potassium
phosphate by 600 C. The residual CC decomposed at about
800 C, and Ca2 KNa(PO4 )2 began to form. The perfect crystalline phase of Ca2 KNa(PO4 )2 was formed completely by
1300 C.


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N. Jinlong et al. / Materials Chemistry and Physics 78 (2002) 308312

Acknowledgements
The project was supported by the Doctorate Foundation
of Xian Jiaotong University (DFXJU2000-9) and Shaanxi
Provincial Science Foundation of China (2000C17).
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