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Insights into the kinetics of thermally induced crystallization of amorphous calcium phosphate

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2018
PCCP-2018.pdf (2.356Mb)
Authors
Uskoković, Vuk
Marković, Smilja
Veselinović, Ljiljana
Škapin, Srečo Davor
Ignjatović, Nenad
Uskoković, Dragan
Article (Accepted Version)
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Abstract
Transformations between amorphous and crystalline apatite mechanistically govern some of the most essential processes in bone metabolism, including biomineralization and bone remodeling. Fundamental understanding of this phase transition can help us gain control over the formation and dissolution of boney tissues in vivo and utilize that knowledge for various therapeutic ends. Crystallization of hydroxyapatite (HAp) and two tricalcium phosphate (TCP) polymorphs from the metastable precursor, amorphous calcium phosphate (ACP) was here studied kinetically and mechanistically using thermal analyses, X-ray diffraction and Fourier-transform infrared spectroscopy. Crystallization was detected in the differential thermal analysis as the exothermic peak at 639.5 °C at the slowest heating regimen of 5 °C min−1, while a combination of different kinetics models, including Augis–Bennett, Borchardt–Daniels, Johnson–Mehl–Avrami, Kissinger, Ozawa and Piloyan, yielded activation energies in the 435–45...0 kJ mol−1 range. Dehydrated ACP required a significant energy input to transform to HAp, thus indirectly proving the key role that structural water plays in this process in a biological setting. The phase transformation at high temperatures involved preformed nuclei and was solely due to their 3D growth, contrasting the edge-controlled nucleation derived earlier as the mechanism of growth in the solution. Crystallization was in both cases accompanied by the formation of needle-shape crystals of HAp through aggregation of ultrafine spherical units of ACP. Relationship between crystallinity and the heating rate was detected only for the initially amorphous structure, indicating a more intense and coherent lattice ordering process in annealed ACP than in HAp. Despite that, crystallization disobeyed the rule of inverse proportionality between the thermal energy required for the relaxation of defects and the level of strain, as the recovery rate of the initially poorly crystalline HAp was higher than that of ACP.

Source:
Physical Chemistry Chemical Physics, 2018, 20, 29221-29235
Publisher:
  • Royal Society of Chemistry (RSC)
Projects:
  • United States National Institutes of Health (NIH) / National Institute of Dental and Craniofacial Research (NIDCR), Grant K99-DE021416
  • Molecular designing of nanoparticles with controlled morphological and physicochemical characteristics and functional materials based on them (RS-45004)
Note:
  • This is the peer-reviewed version of the article: Uskoković, V., Marković, S., Veselinović, L., Škapin, S., Ignjatović, N., Uskoković, D.P., 2018. Insights into the kinetics of thermally induced crystallization of amorphous calcium phosphate. Phys. Chem. Chem. Phys. https://doi.org/10.1039/C8CP06460A

DOI: 10.1039/C8CP06460A

ISSN: 1463-9076; 1463-9084

WoS: 000453935400022

Scopus: 2-s2.0-85057266300
[ Google Scholar ]
23
16
URI
http://dais.sanu.ac.rs/123456789/4514
Collections
  • ITN SANU - Opšta kolekcija / ITS SASA - General collection
Institution
Институт техничких наука САНУ / Institute of Technical Sciences of SASA
TY  - JOUR
AU  - Uskoković, Vuk
AU  - Marković, Smilja
AU  - Veselinović, Ljiljana
AU  - Škapin, Srečo Davor
AU  - Ignjatović, Nenad
AU  - Uskoković, Dragan
PY  - 2018
UR  - http://dais.sanu.ac.rs/123456789/4514
AB  - Transformations between amorphous and crystalline apatite mechanistically govern some of the most essential processes in bone metabolism, including biomineralization and bone remodeling. Fundamental understanding of this phase transition can help us gain control over the formation and dissolution of boney tissues in vivo and utilize that knowledge for various therapeutic ends. Crystallization of hydroxyapatite (HAp) and two tricalcium phosphate (TCP) polymorphs from the metastable precursor, amorphous calcium phosphate (ACP) was here studied kinetically and mechanistically using thermal analyses, X-ray diffraction and Fourier-transform infrared spectroscopy. Crystallization was detected in the differential thermal analysis as the exothermic peak at 639.5 °C at the slowest heating regimen of 5 °C min−1, while a combination of different kinetics models, including Augis–Bennett, Borchardt–Daniels, Johnson–Mehl–Avrami, Kissinger, Ozawa and Piloyan, yielded activation energies in the 435–450 kJ mol−1 range. Dehydrated ACP required a significant energy input to transform to HAp, thus indirectly proving the key role that structural water plays in this process in a biological setting. The phase transformation at high temperatures involved preformed nuclei and was solely due to their 3D growth, contrasting the edge-controlled nucleation derived earlier as the mechanism of growth in the solution. Crystallization was in both cases accompanied by the formation of needle-shape crystals of HAp through aggregation of ultrafine spherical units of ACP. Relationship between crystallinity and the heating rate was detected only for the initially amorphous structure, indicating a more intense and coherent lattice ordering process in annealed ACP than in HAp. Despite that, crystallization disobeyed the rule of inverse proportionality between the thermal energy required for the relaxation of defects and the level of strain, as the recovery rate of the initially poorly crystalline HAp was higher than that of ACP.
PB  - Royal Society of Chemistry (RSC)
T2  - Physical Chemistry Chemical Physics
T1  - Insights into the kinetics of thermally induced crystallization of amorphous calcium phosphate
SP  - 29221
EP  - 29235
VL  - 20
DO  - 10.1039/C8CP06460A
ER  - 
@article{
author = "Uskoković, Vuk and Marković, Smilja and Veselinović, Ljiljana and Škapin, Srečo Davor and Ignjatović, Nenad and Uskoković, Dragan",
year = "2018",
url = "http://dais.sanu.ac.rs/123456789/4514",
abstract = "Transformations between amorphous and crystalline apatite mechanistically govern some of the most essential processes in bone metabolism, including biomineralization and bone remodeling. Fundamental understanding of this phase transition can help us gain control over the formation and dissolution of boney tissues in vivo and utilize that knowledge for various therapeutic ends. Crystallization of hydroxyapatite (HAp) and two tricalcium phosphate (TCP) polymorphs from the metastable precursor, amorphous calcium phosphate (ACP) was here studied kinetically and mechanistically using thermal analyses, X-ray diffraction and Fourier-transform infrared spectroscopy. Crystallization was detected in the differential thermal analysis as the exothermic peak at 639.5 °C at the slowest heating regimen of 5 °C min−1, while a combination of different kinetics models, including Augis–Bennett, Borchardt–Daniels, Johnson–Mehl–Avrami, Kissinger, Ozawa and Piloyan, yielded activation energies in the 435–450 kJ mol−1 range. Dehydrated ACP required a significant energy input to transform to HAp, thus indirectly proving the key role that structural water plays in this process in a biological setting. The phase transformation at high temperatures involved preformed nuclei and was solely due to their 3D growth, contrasting the edge-controlled nucleation derived earlier as the mechanism of growth in the solution. Crystallization was in both cases accompanied by the formation of needle-shape crystals of HAp through aggregation of ultrafine spherical units of ACP. Relationship between crystallinity and the heating rate was detected only for the initially amorphous structure, indicating a more intense and coherent lattice ordering process in annealed ACP than in HAp. Despite that, crystallization disobeyed the rule of inverse proportionality between the thermal energy required for the relaxation of defects and the level of strain, as the recovery rate of the initially poorly crystalline HAp was higher than that of ACP.",
publisher = "Royal Society of Chemistry (RSC)",
journal = "Physical Chemistry Chemical Physics",
title = "Insights into the kinetics of thermally induced crystallization of amorphous calcium phosphate",
pages = "29221-29235",
volume = "20",
doi = "10.1039/C8CP06460A"
}
Uskoković V, Marković S, Veselinović L, Škapin SD, Ignjatović N, Uskoković D. Insights into the kinetics of thermally induced crystallization of amorphous calcium phosphate. Physical Chemistry Chemical Physics. 2018;20:29221-29235
Uskoković, V., Marković, S., Veselinović, L., Škapin, S. D., Ignjatović, N.,& Uskoković, D. (2018). Insights into the kinetics of thermally induced crystallization of amorphous calcium phosphate.
Physical Chemistry Chemical PhysicsRoyal Society of Chemistry (RSC)., 20, 29221-29235. 
https://doi.org/10.1039/C8CP06460A
Uskoković Vuk, Marković Smilja, Veselinović Ljiljana, Škapin Srečo Davor, Ignjatović Nenad, Uskoković Dragan, "Insights into the kinetics of thermally induced crystallization of amorphous calcium phosphate" 20 (2018):29221-29235,
https://doi.org/10.1039/C8CP06460A .

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