Temperature dependent structural and vibrational properties of hydroxyapatite: A theoretical and experimental study (original) (raw)
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Structure and stability of hydroxyapatite: Density functional calculation and Rietveld analysis
A study on the structure and energetics of hydroxyapatite has been carried out using generalized gradient approximation density functional theory. The previously proposed P6 3 / m and P6 3 hexagonal structural models have been found to be energetically unfavorable as compared with the previously proposed P2 1 / b symmetry and a newly proposed monoclinic P2 1 structural model. A detailed analysis of the symmetry restrictions and inconsistencies between the reported physical properties, such as diffraction and birefringence, with hexagonal symmetry question the validity of these models. Rietveld analysis carried out on a synthetic sample, reported to be predominantly hexagonal at room temperature, shows that the diffraction pattern of this material can be interpreted as a mixed monoclinic phase, 23% monoclinic P2 1 / b and 77% monoclinic P2 1 . This interpretation reconciles many anomalies in reported experimental observations.
A Computational Study of the Properties and Surface Interactions of Hydroxyapatite
Ferroelectrics, 2013
Hydroxyapatite (HAP, Ca 10 (PO 4 ) 6 (OH) 2 ) was studied from first principles approaches using the local density approximation (LDA) method in combination with various quantum-chemical (QM) and molecular mechanical (MM) methods from HypemChem 7.5/8.0. The data then were used for studies of HAP structures, and the interactions of HAP clusters with ionic species such as citrates. Computed data show that HAP can co-exist in different phases at room temperature, as both hexagonal and monoclinic. Special interest is connected with the ordered monoclinic structure, which could reveal piezoelectric properties. Obtained data on HAP interactions with citrates show the formation of differing HAP nanostructure forms, depending upon the concentration of citrate present.
Computational study of hydroxyapatite structures, properties and defects
Hydroxyapatite (HAp) was studied from a first principle approach using the local density approximation (LDA) method in AIMPRO code, in combination with various quantum mechanical (QM) and molecular mechanical (MM) methods from HypemChem 7.5/8.0. The data obtained were used for studies of HAp structures, the physical properties of HAp (density of electronic states—DOS, bulk modulus etc) and defects in HAp. Computed data confirmed that HAp can co-exist in different phases—hexagonal and monoclinic. Ordered monoclinic structures, which could reveal piezoelectric properties, are of special interest. The data obtained allow us to characterize the properties of the following defects in HAp: O, H and OH vacancies; H and OH interstitials; substitutions of Ca by Mg, Sr, Mn or Se, and P by Si. These properties reveal the appearance of additional energy levels inside the forbidden zone, shifts of the top of the valence band or the bottom of the conduction band, and subsequent changes in the width of the forbidden zone. The data computed are compared with other known data, both calculated and experimental, such as alteration of the electron work functions under different influences of various defects and treatments, obtained by photoelectron emission. The obtained data are very useful, and there is an urgent need for such analysis of modified HAp interactions with living cells and tissues, improvement of implant techniques and development of new nanomedical applications.
Study of polar and electrical properties of Hydroxyapatite: Modeling and data analysis
2013
The results are based on the first principal modeling and calculations for HAP nanostructures as native as well surface modified, charged and having various defects (H and OH vacancies, H inter-nodes). HAP structures were studied using Local Density Approximation (LOA) method with calculations of Density of States (DOS) allow us analyzes the experimental work function data. Molecular modeling by HyperChem is confirmed by photo-electron monochromatic measurements up 6.5 eV and photo-luminescence data from synchrotron DESY experimental data up 30 eV values. Brief analysis of the influence of heating, microwave radiation, hydrogenation, x-rays and synchrotron radiation on Hydroxyapatite (HAP) surface is presented in this work. New data of the structure of hydroxyapatite are obtained.
Hydroxyapatite (HAp), a primary constituent of human bone, is usually nonstoichiometric with varying Ca/P molar ratios, with the well-known fact that Ca deficiency can cause marked reductions in its mechanical properties. To gain insights into the mechanism of this degradation, we employ first-principles calculations based on density functional theory and determine the effects of Ca deficiency on structure, vibrational, and elastic properties of HAp. Our simulation results confirm a considerable reduction in the elastic constants of HAp due to Ca deficiency, which was experimentally reported earlier. Stress-induced transformation of the Ca-deficient defected structure into a metastable state upon the application of stress could be a reason for this. Local structural stability of HAp and Ca-deficient HAp structures is assessed with full phonon dispersion studies. Further, specific signatures in the computed vibrational spectra for Ca deficiency in HAp can be utilized in experimental characterization of different types of defected HAp.
Molecular Dynamics Simulation of the Thermal Behavior of Hydroxyapatite
Nanomaterials
Hydroxyapatite (HAP) is the main mineral component of bones and teeth. Due to its biocompatibility, HAP is widely used in medicine as a filler that replaces parts of lost bone and as an implant coating that promotes new bone growth. The modeling and calculations of the structure and properties of HAP showed that various structural defects have a significant effect on the properties of the material. By varying these structural heterogeneities, it is possible to increase the biocompatibility of HAP. An important role here is played by OH group vacancies, which are easily formed when these hydroxyl groups leave OH channels of HAP. In this case, the temperature dependence of the concentration of OH ions, which also determines the thermal behavior of HAP, is important. To study the evaporation of OH ions from HAP structures with increasing temperatures, molecular dynamics simulation (MDS) methods were used in this work. As a program for MDS modeling, we used the PUMA-CUDA software packag...
Ferroelectrics 509 (2017) 105-112, 2017
Hydroxyapatite (HAp) has structural features that define its basic physical properties, which have an important role at the surface, and it is one of the most used materials in bone implants. In this work, we present a density functional modeling (DFT) study of HAp both as bulk and with special HAp models with various defects, especially oxygen vacancies in HAp surface layers, which can also determine photocatalytic properties, confirmed experimentally. The first-principles calculations of bulk and modified HAp were carried out using local basis (AIMPRO) and plane-wave (VASP) codes. Data obtained are analyzed using both approaches, and compared.
Quantum chemical and spectroscopic analysis of calcium hydroxyapatite and related materials
Journal of Solid State Chemistry, 2007
Amorphous calcium hydroxyapatite was examined by vibrational spectroscopy (Raman and infra-red (IR)) and quantum chemical simulation techniques. The structures and vibrational (IR, Raman and inelastic neutron scattering) spectra of PO 4 3À ion, Ca 3 (PO 4 ) 2 , [Ca 3 (PO 4 ) 2 ] 3 , Ca 5 (PO 4 ) 3 OH, CaHPO 4 , [CaHPO 4 ] 2 , Ca 3 (PO 4 ) 2 Á H 2 O, Ca 3 (PO 4 ) 2 Á 2H 2 O and Ca 3 (PO 4 ) 2 Á 3H 2 O clusters were quantum chemically simulated at ab initio and semiempirical levels of approximation. A complete coordinate analysis of the vibrational spectra was performed. The comparison of the theoretically simulated spectra with the experimental ones allows to identify correctly the phase composition of the amorphous calcium hydroxyapatite and related materials. The shape of the bands in the IR spectra of the hydroxoapatite can be used in order to characterize the structural properties of the material, e.g., the PO 4 3À ion status, the degree of hydrolysis of the material and the presence of hydrolysis products. r .ua (V.D. Khavryuchenko), alexk@univ.kiev.ua (O.V. Khavryuchenko), lisnyak@chem.univ.kiev.ua (V.V. Lisnyak).
Nanomaterials
Simulation and computer studies of the structural and physical properties of hydroxyapatite (HAP) with different defects are presented in this review. HAP is a well-known material that is actively used in various fields of medicine, nanotechnology, and photocatalytic processes. However, all HAP samples have various defects and are still insufficiently studied. First of all, oxygen and OH group vacancies are important defects in HAP, which significantly affect its properties. The properties of HAP are also influenced by various substitutions of atoms in the HAP crystal lattice. The results of calculations by modern density functional theory methods of HAP structures with these different defects, primarily with oxygen and hydroxyl vacancies are analyzed in this review. The results obtained show that during the structural optimization of HAP with various defects, both the parameters of the crystallographic cells of the HAP change and the entire band structure of the HAP changes (change...
Experimental and theoretical characterization of Dy-doped hydroxyapatites
The effects of adding Dy to the hydroxyapatite (HAp) structure were investigated experimentally and theoretically. The as-obtained experimental results with an increasing amount of Dy are as follows. X-ray diffraction, Raman, and Fourier transform infrared measurements verified the HAp structure for each specimen. The crystallinity, lattice parameters, lattice stress, strain, and anisotropic energy density were affected. Thermal stability and stoichiometry were not affected. It was observed that all the Dy-doped HAps have smaller crystallite size values compared to the un-doped HAp. The cell viability obtained from mouse fibroblast cell (L929) was higher than 82%, indicating all the samples were biocompatible. The theoretical findings, obtained from the density functional theory (DFT) calculations, exhibited a continuous decrease in the bandgap from 4.7109 to 3.7982 eV, an increase in the density from 3,155 to 3,189 kg m −3 , and an increase in the linear absorption coefficient.