The phosphorous fertilizers are a product of natural sedimentary phosphorite ores. Using this raw material to produce phosphoric acid and classic phosphorous fertilizers has generated well-known ecological problems. A new and perspective way to use the same materials is creating a new type of time-delayed fertilizers applying high-energy milling (HEM) activation method. The impact of the mechanical forces over the solids is mostly revealed through the changes of the quantities being related to the energetic stability and reactivity of the solid phase. The aim of this work is to report the results from the investigation on the chemical and thermal reactions in composites of natural apatite , which are HEM activated for different times and thermally treated, (from Tunisia) and ammonium sulphate. The Tunisian phosphorite belongs to the ‘basic’ apatites having a Ca/P ratio of 1.70–1.77 and is characterized by a complex mineral composition with major component carbonate-fluorapatite. The used ammonium sulphate—(NH4)2SO4 is obtained as a by-product from cleaning industrial waste gases, using e-beam technology. The composites of Tunisian phosphorite ores and ammonium sulphate, mixed in a mass ratio 1:1, were HEM activated during 10 min to 50 h with 20 mm Fe-milling bodies and temperature treated up to 1,100 °C. As a result, the chemical properties of the treated composites changed. Proofs were found for (i) formation of new phases during HEM activation such as NH4Ca(PO3)3 (NH4)2CaH4(P2O7)2, (NH4)2Ca3(P2O7)2.6H2O, CaH2P2O7 and α-Ca2P2O7; and (ii) decreasing of temperature intervals of phase changes in comparison to untreated composite.
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Natural carbonate fluorapatite Ca5F(PO4)3
Non-activated mixture Ca5F(PO4)3 + (NH4)2SO4 – mass ratio 1:1
Mixture Ca5F(PO4)3 + (NH4)2SO4 – mass ratio 1:1, HEM activated 5 min
Mixture Ca5F(PO4)3 + (NH4)2SO4 – mass ratio 1:1, HEM activated 10 min
Mixture Ca5F(PO4)3 + (NH4)2SO4 – mass ratio 1:1, HEM activated 30 min
Mixture Ca5F(PO4)3 + (NH4)2SO4 – mass ratio 1:1, HEM activated 60 min
Mixture Ca5F(PO4)3 + (NH4)2SO4 – mass ratio 1:1, HEM activated 5 h
Mixture Ca5F(PO4)3 + (NH4)2SO4 – mass ratio 1:1, HEM activated 10 h
Mixture Ca5F(PO4)3 + (NH4)2SO4 – mass ratio 1:1, HEM activated 15 h
Mixture Ca5F(PO4)3 + (NH4)2SO4 – mass ratio 1:1, HEM activated 30 h
Mixture Ca5F(PO4)3 + (NH4)2SO4 – mass ratio 1:1, HEM activated 40 h
Mixture Ca5F(PO4)3 + (NH4)2SO4 – mass ratio 1:1, HEM activated 50 h
Powder X-ray diffraction
Furies transform infrared
- TG/DTG/DTA TA:
- P2O sol5 :
- P2O tot5 :
Pelovski Y, Petkova V, Dombalov I. Thermotribochemical treatment of low grade natural phosphates. J Therm Anal Cal. 2007;88:207–12.
Chaikina MV. Mechanochemistry of natural and synthetic apatites. In: Avvakumov EG, editors. Novosibirsk, Publishing house of SB RAS, Branch “GEO”, 2002, p. 11–15; 105–107; 114–115; 139.
Wieczorek-Ciurowa Kr, Gamrat K. Mechanochemical syntheses as an example of green processes. J Therm Anal Calorim. 2007;88:213–7.
Petkova V, Pelovski Y, Dombalov I, Tonsuaadu K. Thermochemical investigations of natural phosphate with ammonium sulphate additive. J Therm Anal Cal. 2005;80:701–8.
Yaneva V, Petrov O, Petkova V. Structural and spectroscopic studies of the Nanosize Appatite (Syrian). Mat Res Bull. 2009;44:693–9.
Ivanova V, Petkova V, Pelovski Y. Thermal analysis of new soil sorption regulators. J Therm Anal Cal. 2003;74:387–94.
Petkova V, Serafimova E, Petrova N, Pelovski Y. Thermochemistry of triboactivated natural and NH4-exchanged Clinoptilolite mixed with Tunisian Apatite. J Therm Anal Cal. 2011;105(2):535–44.
Petrova N, Petkova V. Structural changes in the system natural apatite - NH(4) clinoptilolite during triboactivation. Bulg Chem Commun. 2011;43(2):301–7.
Arasheva M, Dombalov Jv. Investigation on thermal stability and phase transformations in the system Marocco phosphorite - (NH4)3H(SO4)2 - NH4HSO4. J Therm Anal. 1995;43:359–68.
Koleva V, Petkova V. IR spectroscopic study of high energy activated Tunisian phosphorite. Vib Spectrosc. 2012;58:125–32.
Petkova V. Investigation of Investigation of the thermal decomposition of triboactivated samples of ammonium sulphate. Int J Bal Trib Assoc. 2004;10(3):344–54.
Petkova V, Pelovski Y, Hristova V. Thermal analysis for identification of E-beam nanosize Ammonium Sulfate. J Therm Anal Cal. 2005;82:813–7.
Pelovski Y, Petkova V, Dombalov I. Thermal analysis of mechanoactivated mixtures of tunisia phosphorite and ammonium sulfate. J Therm Anal Cal. 2003;72:967–80.
Petkova V, Yaneva V. The effect of mechano-chemical activation on the chemical activity, structural and thermal properties of carbonate substituted apatite from Syria. Part I. Chemical, structural, and spectroscopic investigations. J Environ Prot Ecol. 2012;13(2A):979–94.
Tõnsuaadu K, Kaljuvee T, Petkova V, Traksmaa R, Bender V, Kirsimäe K. Impact of mechanical activation on physical and chemical properties of phosphorite concentrates. Int J Min Pro. 2011;100(100):104–9.
Petkova V, Pelovski Y, Dombalov I, Kostadinova P. Influence of triboactivation conditions on the synthesis in natural phosphate. Ammonium sulphate system. J Therm Anal Cal. 2005;80:709–14.
Šulcová P. Thermal stability and colour properties of new pigments based on BiREO3. J Therm Anal Calorim. 2012;109:639–42.
Šulcová P, Večeřa J, Strnadlová L. Study of doped CeO2 prepared by different synthesis. J Therm Anal Calorim. 2012;108(2):519–23.
Tõnsuaadu K, Gross KA, Plūduma L, Veiderma M. A review on the thermal stability of calcium apatites. J Therm Anal Calorim. 2012;110(2):647–59.
Jebri S, Boughzala H, Bechrifa A, Jemal M. Structural analysis and thermochemistry of “A” type phosphostrontium carbonate hydroxyapatites. J Therm Anal Calorim. 2012;107(3):963–72.
Kostova B, Petrova N, Petkova V. The high energy milling effect on position of CO3-ions in the structure of sedimentary apatite. Bul Chem Commun. 2013;45(4):601–6.
Gorodylova N, Dohnalová Z, Šulcová P. Effect of the synthesis conditions on the formation of MgSrP2O7 and its characterisation for pigmentary application. J Therm Anal. 2013;113(1):147–55.
Larson PR, Madden AS, Tas A. Cuneyt, non-stirred synthesis of Na- and Mg-doped, carbonated apatitic calcium phosphate. Ceram Int. 2013;39:1485–93.
Boldyrev BB. Mechanochemistry of inorganic solids. Proc Indian Natl Sci Acad. 1986;52A:400–17.
Balaz P. Mechanochemistry in nanoscience and minerals engineering. Springer-Verlag Berlin Heidelberg, ISBN: 978-3-540-74854-0 e-ISBN: 978-3-540-74855-7, 2008.
Baláž P, Achimovičová M, Baláž M, Billik P, Cherkezova-Zheleva Z, Criado JM, Francesco D, Dutková E, Gaffet E, Gotor FJ, Kumar R, Mitov I, Rojac T, Senna M, Streletskii A, Wieczorek-Ciurowa K, Hallmarks of mechanochemistry: from nanoparticles to technology. Chem Soc Rev. 2013;42:7571–637.
Authors gratefully acknowledge the financial support of this work by the Central Fund of Strategic Development of New Bulgarian University. The Slovak agency ‘Grant’ and the Ministry of Education and Sciences of Bulgaria are gratefully acknowledged also for the financial support granted under contracts Nos. VEGA 2/0009/11 and DNTS/Slovakia/01/3.
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Kostova, B., Petkova, V. Effect of high-energy milling and thermal treatment on the solid-phase reactions in apatite–ammonium sulphate system. J Therm Anal Calorim 116, 737–746 (2014). https://doi.org/10.1007/s10973-014-3747-x
- Waste ammonium suphate
- High-energy milling
- Thermal decomposition