Kinetic Studies on the Thermal Synthesis of Fluorapatite: Model Free and Model-Fitting Methods

Abstract:

The kinetic study for the synthesis of Fluorapatite has been done using the thermogravimetric technique under non-isothermal conditions and at four heating rates of 5, 10, 15 and 20 °C. Both model free and model-fitting methods were used to investigate kinetic parameters. Calcium oxide, phosphorus pentoxide and calcium fluoride were used as the precursor materials. The activation energy values were calculated through model-fitting and isoconversional methods and were used to predict the reaction model and pre-exponential factor. In this case several techniques were considered such as master plots and compensation effects. The results indicated that the reaction mechanism was chemically controlled with second and third order reaction models in the whole range of conversion which the activation energy varied from 25 to 43 kJ/mol.

• Periodical: Advanced Engineering Forum (Volume 28)
• Pages: 75-89
• DOI: https://doi.org/10.4028/www.scientific.net/AEF.28.75
• Online since: June 2018
• Authors: Javadinejad Hamidreza*, Hosseini Sayed Ahmad, Saboktakin Rizi Mohsen, Aghababaei Eiman, Hossein Naseri
• Keywords: Activation Energy, Fluorapatite, Isoconversional Method, Non-Isothermal Kinetics, Solid-State Synthesis

References

[1] Aleksandra Szcześ, Lucyna Hołysz and Emil Chibowski, Synthesis of hydroxyapatite for biomedical applications, Advances in Colloid and Interface Science, 99 (2217) 235–239.

DOI: 10.1016/j.cis.2017.04.007

[2] V Bhadang, K.A. et al., 2010. Biological responses of human osteoblasts and osteoclasts to flame-sprayed coatings of hydroxyapatite and fluorapatite blends. Acta Biomaterialia, 6(4), p.1575.

DOI: 10.1016/j.actbio.2009.10.029

[3] F. Ghomi, S. Jalilifiroozinezhad, and M. Azami, New precipitation method for synthesis of nano-fluorapatite,, Materials Research Innovations, vol. 17, no. 4, p.257–262, Jun. (2013).

DOI: 10.1179/1433075x12y.0000000071

[4] C.J. Tredwin, A.M. Young, G.Georgiou, S.-H. Shin, H.W. Kim, and J. C. Knowles, Hydroxyapatite, fluor-hydroxyapatite and fluorapatite produced via the sol–gel method. Optimisation, characterisation and rheology,, Dental Materials, vol. 29, no. 2, p.166–173, Feb. (2013).

DOI: 10.1016/j.dental.2012.11.008

[5] J. Shen, B. Jin, Q. Jiang, Y. Hu, and X. Wang, Morphology-controlled synthesis of fluorapatite nano/microstructures via surfactant-assisted hydrothermal process,, Materials & Design, vol. 97, p.204–212, May (2016).

DOI: 10.1016/j.matdes.2016.02.091

[6] Z. Fereshteh, M. Fathi, and R. Mozaffarinia, Synthesis and Characterization of Fluorapatite Nanoparticles via a Mechanochemical Method,, Journal of Cluster Science, vol. 26, no. 4, p.1041–1053, Nov. (2014).

DOI: 10.1007/s10876-014-0793-2

[7] Brown, M. E., Maciejewski, M. and Vyazovkin, S., Computational aspects of kinetic analysis Part A: the ICTAC kinetics project-data, methods and results. Thermochimica Acta, 2000‏, 355, 125–143.

[8] R.Ebrahimi-Kahrizsangi, B. Nasiri-Tabrizi, and A. Chami, Characterization of single-crystal fluorapatite nanoparticles synthesized via mechanochemical method,, Particuology, vol. 9, no. 5, p.537–544, Oct. (2011).

DOI: 10.1016/j.partic.2011.07.001

[9] S. Vyazovkin, Computational aspects of kinetic analysis: Part C. The ICTAC Kinetics Project — the light at the end of the tunnel?, Thermochimica Acta, vol. 355, no. 1–2, p.155–163, Jul. (2000).

DOI: 10.1016/s0040-6031(00)00445-7

[10] A.Khawam, Application of solid-state kinetics to desolvation reactions, Theses and Dissertations University of Iowa, (2007).

[11] Sergey Vyazovkin (auth.)-Isoconversional Kinetics of Thermally Stimulated Processes-Springer International Publishing (2015).

[12] S. Vyazovkin, A. K. Burnham, J. M. Criado, L. A. Pérez-Maqueda, C. Popescu, and N. Sbirrazzuoli, ICTAC Kinetics Committee recommendations for performing kinetic computations on thermal analysis data,, Thermochimica Acta, vol. 520, no. 1–2, p.1–19, Jun. (2011).

DOI: 10.1016/j.tca.2011.03.034

[13] H. V. Maulding and M. A. Zoglio, Flexible Nonisothermal Stability Studies,, Journal of Pharmaceutical Sciences, vol. 59, no. 3, p.333–337, Mar. (1970).

DOI: 10.1002/jps.2600590312

[14] S. Vyazovkin, K. Chrissafis, M. L. Di Lorenzo, N. Koga, M. Pijolat, B. Roduit, N. Sbirrazzuoli, and J. J. Suñol, ICTAC Kinetics Committee recommendations for collecting experimental thermal analysis data for kinetic computations,, Thermochimica Acta, vol. 590, p.1–23, Aug. (2014).

DOI: 10.1016/j.tca.2014.05.036

[15] S.Vyazovkin, C.A. Wight, Isothermal and non-isothermal kinetics of thermally stimulated reactions of solids, International Reviews in Physical Chemistry, 17 (1999) 407- 433.

DOI: 10.1080/014423598230108

[16] G.I. Senum, R.T. Yang, Rational approximations of the integral of the Arrhenius function, Journal of thermal analysis and calorimetry, 11 (1977) 445-447.

DOI: 10.1007/bf01903696

[17] A.W. Coats, J.P. Redfern, Kinetic parameters from thermogeravimeteric data, Nature, 201 (1964) 68-69.

DOI: 10.1038/201068a0

[18] A.W. Coats, J.P. Redfern, Kinetic parameters from thermogeravimeteric data II, Journal of Polymer Science Part B: Polymer Letters, 3 (1965) 917-920.

DOI: 10.1002/pol.1965.110031106

[19] P.W.M. Jacobs, F.C. Tompkins, Chemistry of the Solid State, in: W.E. Garner (Eds.) ,London: Butterworth,1955, p.187.

[20] J. Pysiak, in: Heterogeneous Chemical Reactions, Nauka i Tekhnika, Minsk, 1970, p.71 (in Russian).

[21] S. Vyazovkin, W. Linert, Reliability of conversion-time dependencies as predicted from thermal analysis data, Analytica Chimica Acta, 295 (1994) 101-107.

DOI: 10.1016/0003-2670(94)80339-0

[22] C.D. Doyle, Kinetic analysis of thermogravimetric data, Journal of Applied Polymer Science, 5 (1961) 285.

[23] S. Vyazovkin, Computational aspects of kinetic analysis. Part A. The ICTAC kinetics project-data, methods and results,, Thermochimica Acta, 355 (2000) 125-143.

[24] A.K. Burnham, R.L. Braun, Global kinetic analysis of compelex materials, Energy Fuels, 13 (1999) 1-22.

[25] A. A. Jain, A. Mehra, and V. V. Ranade, Processing of TGA data: Analysis of isoconversional and model fitting methods,, Fuel, vol. 165, p.490–498, Feb. (2016).

DOI: 10.1016/j.fuel.2015.10.042

[26] Friedman .H.L, New methods for evaluating kinetic parameters from thermal analysis data ,, J. Polym. Sci., Part C: Polym. Lett.Vol. 6, pp.183-195, (1964).

[27] N. Sbirrazzuoli, Is the Friedman Method Applicable to Transformations with Temperature Dependent Reaction Heat?, Macromolecular Chemistry and Physics, vol. 208, no. 14, p.1592–1597, Jul. (2007).

DOI: 10.1002/macp.200700100

[28] Ozawa T, A New Method of Analyzing Thermogravimetric Data ,, Bull. Chem‏. Soc. Jpn.Vol. 38, pp.1881-1886, 1965‏.

[29] Flynn. J.H and Wall. L.A, A quick, direct method for the determination of activation energy from thermogravimetric data,, J. Polym. Sci., Part B: Polym. Lett.Vol‏. 4, pp.323-328, (1966).

DOI: 10.1002/pol.1966.110040504

[30] Kissinger.H.E, Variation of Peak Temperature with Heating Rate in Differential Thermal Analysis, J. Res. Nat. Bur. Stand.Vol. 57, pp.217-221, 1956‏.

DOI: 10.6028/jres.057.026

[31] Kissinger.H.E, Reaction Kinetics in Differential Thermal Analysis ,Anal‏. Chem.Vol. 29,pp.1702-1706, (1957).

DOI: 10.1021/ac60131a045

[32] A. Ortega, A simple and precise linear integral method for isoconversional data,, Thermochimica Acta, vol. 474, no. 1–2, p.81–86, Aug. (2008).

DOI: 10.1016/j.tca.2008.05.003

[33] Y.Han, T.Li, and K.Saito, A modified Ortega method to evaluate the activation energies of solid state reactions,, Journal of Thermal Analysis and Calorimetry, vol. 112, no. 2, p.683–687, Aug. (2012).

DOI: 10.1007/s10973-012-2591-0

[34] S. Vyazovkin, D. Dollimore, Linear and nonlinear procedures in isoconversional computations of the activation energy of nonisothermal reactions in solids, Journal of Chemical Information and Computer Sciences, 36 (1996) 42-45.

DOI: 10.1021/ci950062m

[35] S. Vyazovkin, Evaluation of activation energy of thermally stimulated solid-state reactions under arbitrary variation of temperature, Journal of Computational Chemistry. 18 (1997) 393-402.

DOI: 10.1002/(sici)1096-987x(199702)18:3<393::aid-jcc9>3.0.co;2-p

[36] S.Vyazovkin, Modification of the integral isoconversional method to account for variation in the activation energy, Journal of Computational Chemistry, 22 (2001) 178-183.

DOI: 10.1002/1096-987x(20010130)22:2<178::aid-jcc5>3.0.co;2-#

[37] P.Budrugeac, E. Segal, Some methodological problems concerning nonisothermal kinetic analysis of heterogeneous solid-gas reactions, international journal of chemical kinetics, 33 (2001) 564-573.

DOI: 10.1002/kin.1052

[38] S. Vyazovkin, Model-free kinetics Staying free of multiplying entities without necessity, Journal of Thermal Analysis and Calorimetry, 83 (2006) 45–51.

DOI: 10.1007/s10973-005-7044-6

[39] S.Vyazovkin, Some Methodological Problems Concerning Nonisothermal Kinetic Analysis of Heterogeneous Solid–Gas Reactions, international journal of chemical kinetics. 34 (2002) 418-420.

DOI: 10.1002/kin.10068

[40] S. Vyazovkin, A.I. Lesnikovich, Estimation of the pre-exponential factor in the isoconvertional calculation of effective kinetic parameters, Thermochimica Acta. 128 (1988) 297-300.

DOI: 10.1016/0040-6031(88)85372-3

[41] S. Vyazovkin, W. Linert, False isokinetic relationships found in the nonisothermal decomposition of solids, Chemical Physics. 193 (1995) 109-118.

DOI: 10.1016/0301-0104(94)00402-v

[42] S.Vyazovkin, Handbook of thermal analysis, Chapter 13, Vol.5, New York, 2008, pp.503-538.

[43] B. Janković, B. Adnađević, and J. Jovanović, Application of model-fitting and model-free kinetics to the study of non-isothermal dehydration of equilibrium swollen poly (acrylic acid) hydrogel: Thermogravimetric analysis,, Thermochimica Acta, vol. 452, no. 2, p.106–115, Jan. (2007).

DOI: 10.1016/j.tca.2006.07.022

[44] JiříMálek, The kinetic analysis of non-isothermal data, Thermochimica Acta, Volume 200, 8 July 1992, Pages 257-269.

DOI: 10.1016/0040-6031(92)85118-f

[45] E. H. Kim, J. J. Park, J. H. Park, I. S. Chang, and C. S. Choi, A new master plot using the differential method in kinetic analysis of non-isothermal TG data,, Thermochimica Acta, vol. 196, no. 2, p.495–502, Feb. (1992).

DOI: 10.1016/0040-6031(92)80111-9

[46] S. O. Kamphorst and J. K. L. da Silva, The Kinetics of Fragmentation Processes with Mass Loss,, Europhysics Letters (EPL), vol. 21, no. 3, p.261–266, Jan. (1993).

DOI: 10.1209/0295-5075/21/3/002

[47] G. Deng, Y. Zhang, C. Ye, Z. Qiang, G. E. Stein, K. A. Cavicchi, and B. D. Vogt, Bicontinuous mesoporous carbon thin films via an order–order transition,, Chem. Commun., vol. 50, no. 84, p.12684–12687, (2014).

DOI: 10.1039/c4cc02471k

[48] Y. Zhang, Z. Qiang, and B. D. Vogt, Relationship between crosslinking and ordering kinetics for the fabrication of soft templated (FDU-16) mesoporous carbon thin films,, RSC Adv., vol. 4, no. 85, p.44858–44867, Sep. (2014).

DOI: 10.1039/c4ra08316d

[49] G. Deng, Z. Qiang, W. Lecorchick, K. A. Cavicchi, and B. D. Vogt, Nanoporous Nonwoven Fibril-Like Morphology by Cooperative Self-Assembly of Poly(ethylene oxide)-block-Poly(ethyl acrylate)-block-Polystyrene and Phenolic Resin,, Langmuir, vol. 30, no. 9, p.2530–2540, Feb. (2014).

DOI: 10.1021/la404964c

[50] B.Nasiri-Tabrizi and A.Fahami, Reaction mechanisms of synthesis and decomposition of fluorapatite–zirconia composite nanopowders,, Ceramics International, vol. 39, no. 5, p.5125–5136, Jul. (2013).

DOI: 10.1016/j.ceramint.2012.12.008

[51] G.Mishra, J. Kumar, and T. Bhaskar, Kinetic studies on the pyrolysis of pinewood,, Bioresource Technology, vol. 182, p.282–288, Apr. (2015).

DOI: 10.1016/j.biortech.2015.01.087

[52] M. Khachani, A. El Hamidi, M. Halim, S. Arsalane, Non-isothermal kinetic and thermodynamic studies of the dehydroxylation process of synthetic calcium hydroxide Ca(OH)2, J. Mater. Environ. Sci. 5 (2) (2014) 615-624.

[53] Pradyot Patnaik, Handbook of Inorganic Chemicals, McGraw-Hill, (2003).

[54] I.-H. Jung and P. Hudon, Thermodynamic Assessment of P2O5,, Journal of the American Ceramic Society, vol. 95, no. 11, p.3665–3672, Aug. (2012).

[55] J. A. Rard and T. J. Wolery, The Standard Chemical-Thermodynamic Properties of Phosphorus and Some of its Key Compounds and Aqueous Species: An Evaluation of Differences between the Previous Recommendations of NBS/NIST and CODATA,, Journal of Solution Chemistry, vol. 36, no. 11–12, p.1585–1599, Oct. (2007).

DOI: 10.1007/s10953-007-9205-7

[56] Y.-Y. Qi.Y.Cheng, M.Liu, X.-R.Chen, and L.-C. Cai, Phase transition and thermodynamic properties of CaF2 via first principles,, Physica B: Condensed Matter, vol. 426, p.13–19, Oct. (2013).

DOI: 10.1016/j.physb.2013.05.033

[57] G. González, A. Sagarzazu, and R. Villalba, Mechanochemical transformation of mixtures of Ca (OH) 2 and (NH4)2HPO4 or P2O5,, Materials Research Bulletin, vol. 41, no. 10, p.1902–1916, Oct. (2006).

DOI: 10.1016/j.materresbull.2006.03.004

[58] W.Kim, Q.Zhang, F.Saito, Mechanochemical synthesis of hydroxyapatite from Ca (OH) 2-P2O5 and CaO-Ca (OH) 2-P2O5 mixtures,, JOURNAL OF MATERIALS SCIENCE 35 (2000) 5401 – 5405.

DOI: 10.3390/nano10112232

[59] S. Kannan, A. Rebelo, A. F. Lemos, A. Barba, and J. M. F. Ferreira, Synthesis and mechanical behaviour of chlorapatite and chlorapatite/β-TCP composites,, Journal of the European Ceramic Society, vol. 27, no. 5, p.2287–2294, Jan. (2007).

DOI: 10.1016/j.jeurceramsoc.2006.07.004

[60] K. Tõnsuaadu, K. A. Gross, L. Plūduma, and M. Veiderma, A review on the thermal stability of calcium apatites,, Journal of Thermal Analysis and Calorimetry, vol. 110, no. 2, p.647–659, Sep. (2011).

DOI: 10.1007/s10973-011-1877-y

[61] R. Ebrahimi-Kahrizsangi, M.H. Abbasi, Evaluation of reliability of Coats-Redfern method for kinetic analysis of non-isothermal TGA, Transactions of Nonferrous Metals Society of China, 18 (2008) 217-221.

DOI: 10.1016/s1003-6326(08)60039-4

[62] A. K. Burnham and R. L. Braun, Global Kinetic Analysis of Complex Materials,, Energy & Fuels, vol. 13, no. 1, p.1–22, Jan. (1999).

[63] S. V. Vyazovkin and A. I. Lesnikovich, An approach to the solution of the inverse kinetic problem in the case of complex processes,, Thermochimica Acta, vol. 165, no. 2, p.273–280, Aug. (1990).

DOI: 10.1016/0040-6031(90)80227-p

[64] J.A. Caballero, J.A. Conesa. Mathematical considerations for nonisothermal kinetics in thermal decomposition, J Anal Appl Pyrolysis, (2005), 73: p.85−100.

DOI: 10.1016/j.jaap.2004.12.003

[65] A. Khawam and D. R. Flanagan, Solid-State Kinetic Models: Basics and Mathematical Fundamentals,, The Journal of Physical Chemistry B, vol. 110, no. 35, p.17315–17328, Sep. (2006).

DOI: 10.1021/jp062746a

[66] S.Vyazovkin, on the phenomenon of variable activation energy for condensed phase reactions, New Journal of Chemistry, 24 (2000) 913-917.

DOI: 10.1039/b004279j

[67] A.K. Galwey, What is meant by the term variable activation energy' when applied in the kinetic analyses of solid state decompositions (crystolysis reactions), Thermochimica Acta, 397 (2003)249-268.

DOI: 10.1016/s0040-6031(02)00271-x

[68] S. V. Vyazovkin, V. I. Goryachko, and A. I. Lesnikovich, An approach to the solution of the inverse kinetic problem in the case of complex processes. Part III. Parallel independent reactions,, Thermochimica Acta, vol. 197, no. 1, p.41–51, Mar. (1992).

DOI: 10.1016/0040-6031(92)87037-b

[69] S. Vyazovkin, Conversion dependence of activation energy for model DSC curves of consecutive reactions,, Thermochimica Acta, vol. 236, p.1–13, May (1994).

DOI: 10.1016/0040-6031(94)80249-1

[70] D.W. Readey, Kinetics in materials science and engineering, CRC Press, (2017).

[71] T. Wang, A. Dorner-Reisel, and E. Müller, Thermogravimetric and thermokinetic investigation of the dehydroxylation of a hydroxyapatite powder,, Journal of the European Ceramic Society, vol. 24, no. 4, p.693–698, Apr. (2004).

DOI: 10.1016/s0955-2219(03)00248-6