RESEARCH ARTICLE | JUNE 24 2021

Novel fast firing method to synthesize tetracalcium

phosphate 
Muhammad S. Nizar  ; Naili Sofiyaningsih; Ria J. Manullang; Rizky B. Wijayanti; Irna Rosmayanti;
Dadan Sumardan

AIP Conf. Proc. 2349, 020001 (2021)

https://doi.org/10.1063/5.0051750

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 Novel Fast Firing Method to Synthesize Tetracalcium Phosphate
Muhammad S. Nizara), Naili Sofiyaningsih, Ria J. Manullang,
Rizky B. Wijayanti, Irna Rosmayanti, and Dadan Sumardan
Center for Ceramics, Ministry of Industry Republic of Indonesia
a)
Corresponding author: nizar@kemenperin.go.id

Abstract. Tetracalcium phosphate knows as a derivative of apatite based materials that are used in medical and pharmacy
applications such as for bone and dental cement and also for drugs. The synthesis of tetracalcium phosphate requires several hours
of calcining on a high-temperature furnace. In this paper, the novel fast-firing method was introduced to the synthesis process of
tetracalcium phosphate to modify the solid-state reaction by the Sargin, Agris, and Moseke process to reduce energy and time for
producing tetracalcium materials. One base precursor for tetracalcium phosphate was prepared by reacting calcium hydroxide and
phosphoric acid with molar ratio Ca/P 2:1. The base precursors are treated with different calcination temperatures, time variation,
and different quenching methods to verify which treatment will have high yield tetracalcium phosphate material. The calcination
temperature range is 1200oC to 1600oC, while the calcination time varied from 3 hours to under 1 hour, also quenched by air and
water. The samples were characterized by XRD to show different mineralogy yield and semi quantity measurement of tetracalcium
content. Synthesized tetracalcium phosphate characterized with XRD content several apatite minerals: montetite, brushite,

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tricalcium, and hilgenstokite with different ratio percentages content. The semi-quantity method form XRD analysis is used to
calculate the ratio. Tetracalcium phosphate yield range from 7,62% to 56,7%. The best result that yields 56,7% was treated with
calcination temperature 1400oC under 1 hour and quenched with air. The results show that the fast-firing method can optimize the
current solid-state reaction synthesis process, and it looks promising to develop this method to the production process.

BACKGROUND
Tetracalcium phosphate or hilgenstockite is a derivative of apatite-based materials used in medical and pharmacy
applications such as bone and dental cement and drugs1. Other apatite calcium-based materials such as tricalcium phosphate,
dicalcium phosphate and hydroxyapatite are used in combination with tetracalcium phosphate to compose biomaterials2 as
dental and bone cement, bone scaffold, artificial bone and dental, drug carrier, and also pharmacy fine chemical materials.
Tetracalcium phosphate has such a broad application in the medical industry and pharmacy industry because of its particular
material characteristic, which has good biocompatibility, bioresorbable, biomimetic, and good osteoconductivity3,4.
The synthesis of tetracalcium phosphate requires several hours of calcining on a high-temperature furnace. The synthesis
could be ranging from 24 hours of calcining on 1600oC5 and the addition of a slow increase in temperature firing rate could
add more time to the calcining process. Because the tetracalcium powder is not solid ceramics body that needs to be sintered
at slow speed firing rate and because of the calcium nature that could withstand high-temperature firing6, it should be
possible to synthesize tetracalcium phosphate at higher firing rate, thus leads to investigate rapid change on precursor phase
converted to tetracalcium mineral phase7. The amount of energy and time to synthesize tetracalcium phosphate needs to be
reduced to decrease cost production. In this paper, the novel fast-firing method was introduced to the synthesis process of
tetracalcium phosphate to modify the solid-state reaction combination by Sargin, Agris, and Moseke process8-10 to reduce
energy and time for producing tetracalcium materials.

4th International Seminar on Chemistry

AIP Conf. Proc. 2349, 020001-1–020001-6; https://doi.org/10.1063/5.0051750
Published by AIP Publishing. 978-0-7354-4100-2/$30.00

020001-1
 METHODS
Raw materials for synthesizing tetracalcium phosphate are taken from natural calcite minerals, and technical grade 85%wt
phosphoric acid was used for phosphate source. The calcite mineral was converted into slaked lime or calcium hydroxide,
and the water content was measured to calculate the molar ratio for the reaction. One base precursor for tetracalcium
phosphate was prepared by reacting calcium hydroxide and phosphoric acid with molar ratio Ca/P 2:111. Phosphoric acid
diluted four times of volume and reacted with calcium hydroxide with titration wet precipitation process on temperature
range 60oC to 80oC at pH 3 to 4 and 10 to 111211with stirring approximately 6 hours. After the titration reaction, the product
was settled for 12 hours and then decanted. The base precursors are treated with different calcination temperatures, time
variation, and different quenching methods to verify which treatment will have high yield tetracalcium phosphate material.
The calcination temperature range is 1200oC to 1600oC9,10, while the calcination time varied from 8 hours to under 1 hour,
and the last treatment methods are quenching medium, which is air quenched and water quenched13. The final powder
product milled and sieved 200 mesh. The samples were characterized by XRD to show different mineralogy yield and semi
quantity Rietveld refinement measurement of tetracalcium content. Figure 1 show the flow process diagram of tetracalcium
phosphate synthesis in this research.

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FIGURE 1. Tetracalcium synthesis process flow diagram.

The sample code for each treatment combination condition is shown in Table 1. The synthesis treatment iteration was
determined by each step treatment, which will give the best result. The better result treatment continues to be used on the
next sample treatment on each iteration.

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 TABLE 1. Sample code synthesis treatment combination
Sample Calcination Calcination
Quenching
Code Temperature Time
Medium
No. (oC) (hour)
6 1200 3 water
7 1200 1 water
8 1400 1 water
9 1400 1 air
10 1400 3 water
11 1400 3 air
12 1300 1 air
13 1500 3 air
14 1300 3 air
15 1500 3 air
16 1500 3 air

RESULTS
Samples number 1 to 4 figure 2 is the initial test batch to prepare the tetracalcium precursor, sample no 5. Sample no. 5
were prepared by reacting calcium hydroxide and phosphoric acid as described in the previous method with molar ratio Ca/P
= 2 resulted in tetracalcium precursor with pH 7 exothermic reaction with temperature range 40 to 80oC with the gradual

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increase in viscosity. In contrast, the reaction occurs and decreases after its peak viscosity becomes more viscous because the
reaction materials inside have hygroscopic properties.

FIGURE 2. Tetracalcium phosphate synthesized products.

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 TABLE 2. Semi quantity XRD analysis result of tetracalcium phosphate samples.

Phase Quantity (%wt)

Sample Tetracalcium Monetite Brushite Portlandite Calcite
No. Phosphate Tricalcium-Į Tricalcium-ȕ
(DCPA) (DCPD) (CaOH2) (CaCO3)
(TTCP)
5 - 71,40 4,12 16,77 7,7 - -
6 - 98,00 0,30 1,59 - - -
7 32,16 21,35 0,14 7,03 12,20 3,16 20,81
8 56,70 20,50 9,20 2,90 0,42 - 10,30
9 56,30 19,10 10,20 2,78 1,62 - 10,10
10 12,98 3,37 - - - 4,93 78,70
11 11,06 3,48 - 0,63 - 4,29 80,57
12 8,65 1,78 - 0,37 - 33,80 55,40
13 7,62 0,85 - - - 27,03 62,55
14 8,73 3,30 0,09 - - 20,18 76,67
15 8,02 2,72 - - - 26,21 63,11
16 8,11 3,17 - - - 21,39 67,3

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FIGURE 3. X-Ray Diffractogram sample No. 7 T=1200oC, No. 12 T=1300oC. No. 8 T=1400oC, No 13 T=1500oC

Figure 3 shows that different diffractogram samples with different calcination temperatures are compared. Sample no. 8
peaks are coinciding clearly with tetracalcium phosphate peaks on JCPDS compared to the other sample. Synthesized
tetracalcium phosphate product characterized with XRD content several apatite minerals: montetite, brushite, tricalcium, and
hilgenstockite with different ratio percentage content. For tetracalcium phosphate, the peaks are identified base on JCPDS
pattern number 25-113714. The semi-quantity method form XRD analysis is used to calculate the ratio15.

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 13 October 2023 03:31:06
FIGURE 4. X-Ray Diffractogram of sample No 8 with calcination time 1 hour
and sample No 10 with calcination time 3 hours.

Sample no. 8 peak at 30.5o 2ș and that indistinct with sample no. 10 with different temperature calcination process 1 and
3 hour on overall peaks of tetracalcium phosphate, thus show higher yield on semi-quantity calculation on sample no. 8 than
sample no. 10.
Tetracalcium phosphate yield range from 7,62% to 56,7%. The best result yield of 56,7% was treated with calcination
temperature 1400oC under 1 hour and quenched with air, sample no. 8. The tetracalcium phase tends to form an amorph
structure 16caused by the quenching process, halting the phase transformation17,18, These phases were metastable because of
excessive Ca atoms19. The best calcination temperature ranges from 1300 to 1350oC according to phase change characteristic
of tetracalcium phosphate. The quenching medium with water is better than the air because water can decrease temperature
rapidly than the air, so the tetracalcium phase was locked and did not have the chance to transform into tricalcium phosphate
slowly. The results show that the fast-firing method can optimize the current solid-state reaction synthesis process, and it
looks promising to develop this method for the production process.

CONCLUSIONS
A new novel, fast-firing tetracaclium phosphate synthesis process with precursor materials from calcium hydroxide and
phosphoric acid was treated with calcination temperature 1400oC under 1 hour and quenched with air shows the promising
result to synthesize tetracalcium phosphate with high yield. The fast-firing method reduces energy consumption and time
process that affect the production cost.

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 ACKNOWLEDGEMENTS
This research was conducted in the Center for Ceramics Research Facilities and fully funded by the Industrial Research
and Development Agency Republic of Indonesia Ministry of Industry.

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