Ljiljana Veselinović

Synthetical bone-like and biological hydroxyapatites: a comparative study of crystal structure and morphology

Phase composition, crystal structure and morphology of biological hydroxyapatite (BHAp) extracted from human mandible bone, and carbonated hydroxyapatite (CHAp), synthesized by the chemical precipitation method, were studied by x-ray powder diffraction (XRD), Fourier transform infrared (FTIR) and Raman (R) spectroscopy techniques, combined with transmission electron microscopy (TEM). Structural and microstructural parameters were determined through Rietveld refinement of recorded XRD data, performed using the FullProf computing program, and TEM. Microstructural analysis shows anisotropic extension along the [00l] crystallographic direction (i.e. elongated crystallites shape) of both investigated samples. The average crystallite sizes of 10 and 8 nm were estimated for BHAp and CHAp, respectively. The FTIR and R spectroscopy studies show that carbonate ions substitute both phosphate and hydroxyl ions in the crystal structure of BHAp as well as in CHAp, indicating that both of them are mixed AB-type of CHAp. The thermal behaviour and carbonate content were analysed using thermogravimetric and differential thermal analysis. The carbonate content of about 1 wt.% and phase transition, at near 790 °C, from HAp to β-tricalcium phosphate were determined in both samples. The quality of synthesized CHAp powder, particularly, the particle size distribution and uniformity of morphology, was analysed by a particle size analyser based on laser diffraction and field emission scanning electron microscopy, respectively. These data were used to discuss similarity between natural and synthetic CHAp. Good correlation between the unit cell parameters, average crystallite size, morphology, carbonate content and crystallographic positions of carbonate ions in natural and synthetic HAp samples was found.

Hydrothermal Synthesis of Nanosized Pure and Cobalt-Exchanged Hydroxyapatite

Pure and cobalt-exchanged hydroxyapatite (HAp and CoHAp) powders were synthesized by hydrothermal method. X-ray diffraction (XRD), Raman spectroscopy, particle size analysis, inductively coupled plasma (ICP) emission spectroscopy, and scanning electron microscopy (SEM) were used to study the microstructural and unit cell parameters, average particle size, particle size distribution, chemical composition, and morphology of the synthesized powders. XRD and Raman spectroscopy confirmed that the samples were free from impurities and other phases of calcium phosphates. It has been found that the increase in the cobalt amount in the crystal structure of HAp reduces unit cell parameters, as well as average crystallite size (from XRD measurements). All of the powders were nano-sized with narrow particle distribution (from particle size analyses). SEM investigations indicated that nano-sized particles were organized in soft micro-sized agglomerates, whose sizes increased with the increase in the content of Co in HAp crystal structure.

Crystal structure of cobalt-substituted calcium hydroxyapatite nanopowders prepared by hydrothermal processing

A series of cobalt-exchanged hydroxyapatite (CoHAp) powders with different Ca/Co ratios and nominal unit-cell contents Ca10−xCox(PO4)6(OH)2, x = 0, 0.5, 1.0, 1.5 and 2.0, were synthesized by hydrothermal treatment of a precipitate at 473 K for 8 h. Based on ICP (inductively coupled plasma) emission spectroscopy analysis, it was established that the maximum amount of cobalt incorporation saturated at ∼12 at.% under these conditions. The effects of cobalt content on the CoHAp powders were investigated using ICP emission spectroscopy, particle size analysis, transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM) analyses as well as X-ray powder diffraction (XRPD) including Rietveld analysis. According to XRPD, all the materials are single-phase HAp and CoHAp of low crystallinity. Rietveld analysis shows that Co enrichment causes the c cell parameter to decrease at a faster rate than the a cell parameter. A microstructural analysis showed anisotropic X-ray line broadening due to crystallite size reduction. In CoHAp there is significant crystal elongation in [001], and the average size decreases with increasing cobalt content. The crystallite morphology transforms from rod-like for the pure HAp to lamellae at the highest degree of Co substitution. The results of Rietveld refinement (symmetry, size and morphology of the crystallites) were confirmed by TEM and HRTEM analysis.

The effect of Sn for Ti substitution on the average and local crystal structure of BaTi1−xSnxO3 (0 ≤ x ≤ 0.20)

The effect of Sn for Ti substitution on the crystal structure of a perovskite, barium titanate stannate (BTS), BaTi1−xSnxO3 for x = 0, 0.025, 0.05, 0.07, 0.10, 0.12, 0.15 and 0.20, was investigated. The powders were prepared by the conventional solid-state reaction technique. The structural investigations of the BTS powders were done at room temperature by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), selected-area electron diffraction (SAED) and Raman spectroscopy analyses. Rietveld refinement of XRD data indicates that gradual replacement of titanium by tin in BaTiO3 provokes a phase transition from tetragonal for 0 ≤ x ≤ 0.07 to cubic for x = 0.12, 0.15 and 0.20. The coexistence of tetragonal (P4mm) and cubic (Pm\overline 3m) crystal phases was established in powder with nominal composition BaTi0.9Sn0.1O3. The crystal phases determined by Rietveld refinement were confirmed by HRTEM and SAED analyses. The crystal structures of the BTS powders at short-range scale were studied by Raman spectroscopy, which shows tetragonal (P4mm) and a small fraction of orthorhombic (Pmm2) crystal phases for all the examined BTS powders, implying a lower local ordering when compared to the average symmetry.

Hydrothermally processed 1D hydroxyapatite: Mechanism of formation and biocompatibility studies

Recent developments in bone tissue engineering have led to an increased interest in one-dimensional (1D) hydroxyapatite (HA) nano- and micro-structures such as wires, ribbons and tubes. They have been proposed for use as cell substrates, reinforcing phases in composites and carriers for biologically active substances. Here we demonstrate the synthesis of 1D HA structures using an optimized, urea-assisted, high-yield hydrothermal batch process. The one-pot process, yielding HA structures composed of bundles of ribbons and wires, was typified by the simultaneous occurrence of a multitude of intermediate reactions, failing to meet the uniformity criteria over particle morphology and size. To overcome these issues, the preparation procedure was divided to two stages: dicalcium phosphate platelets synthesized in the first step were used as a precursor for the synthesis of 1D HA in the second stage. Despite the elongated particle morphologies, both the precursor and the final product exhibited excellent biocompatibility and caused no reduction of viability when tested against osteoblastic MC3T3-E1 cells in 2D culture up to the concentration of 2.6mg/cm(2). X-ray powder diffraction combined with a range of electron microscopies and laser diffraction analyses was used to elucidate the formation mechanism and the microstructure of the final particles. The two-step synthesis involved a more direct transformation of DCP to 1D HA with the average diameter of 37nm and the aspect ratio exceeding 100:1. The comparison of crystalline domain sizes along different crystallographic directions showed no signs of significant anisotropy, while indicating that individual nanowires are ordered in bundles in the b crystallographic direction of the P63/m space group of HA. Intermediate processes, e.g., dehydration of dicalcium phosphate, are critical for the formation of 1D HA alongside other key aspects of this phase transformation, it must be investigated in more detail in the continuous design of smart HA micro- and nano-structures with advanced therapeutic potentials.

Simultaneous enhancement of natural sunlight- and artificial UV-driven photocatalytic activity of a mechanically activated ZnO/SnO2 composite

Mechanical milling of commercial ZnO and SnO2 was used to produce a ZnO/SnO2 composite with a high density of surface defects; in particular, zinc interstitials (Zni) and oxygen vacancies (VO). To determine the impact of surface defects on photocatalytic activity, the relative concentration ratio of bulk defects to surface defects was modified by annealing at 400 and 700 °C. The possible application of the ZnO/SnO2 composite as a natural sunlight and UV-light driven photocatalyst was revealed via de-colorization of methylene blue. In both cases the ZnO/SnO2 composite exhibited enhanced photocatalytic activity as compared to the pristine ZnO. In order to investigate the origin of the enhancement, the pristine metal oxides and composites were characterized using a variety of techniques, including X-ray diffraction (XRD), Raman and Fourier transform infrared (FTIR) spectroscopy, field emission scanning electron microscopy (FESEM), laser diffraction particle size analysis, Brunauer–Emmett–Teller, UV-Vis diffuse reflectance and photoluminescence spectroscopy. High-resolution transmission electron microscopy (HRTEM) and elemental mapping analyses were used to reveal the presence of SnO2 nanocrystallites on the surface of larger ZnO particles. The enhanced photocatalytic activity of the composite can be attributed to the synergetic effect of the surface defects and the ZnO/SnO2 heterojunction particles, which facilitated charge separation, thereby hindering the recombination of photogenerated carriers. This study draws attention to mechanical activation as an inexpensive and environmentally friendly technique for the large-scale production of the composite with an enhanced photocatalytic activity under illumination of either UV or sunlight.

New insights into BaTi1–xSnxO3 (0 ≤ x ≤ 0.20) phase diagram from neutron diffraction data

Neutron powder diffraction (NPD) was employed to further investigate the BaTi1−xSnxO3 (BTS) system previously studied by X-ray diffraction. The room-temperature phase compositions and crystal structures of BTS samples with x = 0, 0.025, 0.05, 0.07, 0.10, 0.12, 0.15 and 0.20 were refined by the Rietveld method using NPD data. It is well known that barium titanate powder (x = 0) crystallizes in the tetragonal P4mm space group. The crystal structures of the samples with 0.025 ≤ x ≤ 0.07 were refined as mixtures of P4mm and Amm2 phases; those with x = 0.1 and 0.12 show the coexistence of rhombohedral R3m and cubic phases, while the samples with x = 0.15 and 0.20 crystallize in a single cubic Pm{\overline 3}m phase. Temperature-dependent NPD was used to characterize the BaTi0.95Sn0.05O3 sample at 273, 333 and 373 K, and it was found to form single-phase Amm2, P4mm and Pm{\overline 3}m structures at these respective temperatures. The NPD results are in agreement with data obtained by differential scanning calorimetry and dielectric permittivity measurements, which show a paraelectric–ferroelectric transition (associated with structural transition) from Pm{\overline 3}m to P4mm at about 353 K followed by a P4mm to Amm2 phase transition at about 303 K.