Enhanced phase stability in hydroxylapatite/zirconia composites with hot isostatic pressing

Hydroxylapatite (HA) composites with pure zirconia (ZrO₂), and 3 and 8% Y₂O₃ doped ZrO₂ were pressure-less sintered in air and hot isostatically pressed (under 120 MPa gas pressure) at 1100 °C for 2 h. The reactions and phase transformations were monitored by X-ray diffraction, thermal analysis, and Raman spectroscopy. HA/pure ZrO₂ composites were not thermally stable in air sintering; HA dissociated into α and β tricalcium phosphate while monoclinic ZrO₂ was transformed into tetragonal and cubic phases. No decomposition in HA or phase transformation in ZrO₂ were observed in hydroxylapatite/3% Y₂O₃ doped ZrO₂ or HA/8% Y₂O₃ doped ZrO₂ composites. On the other hand, HA and ZrO₂ phases in hot isostatically pressed composites remained stable. The highest densification was found in a composite initially containing 10% monoclinic ZrO₂ among the composites sintered in air. The densification of the composites decreased at lower sintering temperatures and higher ZrO₂ contents upon air-sintering. The HIPped composites were densified to about 99.5% of theoretical densities in all mixing ratios. The reactivity between ZrO₂ and HA was dependent on the amount of air in the sintering environment. Hot isostatic pressing with very limited retained air was proved to be a very convenient method to insure both phase stability and full densification during the production of hydroxylapatite zirconia composites.     

Fabrication of SiO2-ZrO2 composite fiber mats via electrospinning

(1 − x)SiO₂-(x)ZrO₂ (x = 0.1, 0.2) composite fiber mats were prepared by electrospinning their sol-gel precursors of zirconium acetate and tetraethyl orthosilicate (TEOS) without using a polymer binder. The electrospun composite fibers were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), fourier transform infrared spectroscopy (FT-IR) and mercury porosimetry. The composite fibers having a tetragonal crystalline ZrO₂ were obtained by calcining the electrospun composite fibers at high temperatures. The results show that the structure and crystallization of ZrO₂ in the composite fibers can be controlled by sintering temperature, while the porosity and morphology of the fiber mats did not depend on the sintering temperature.     

Properties of hydroxyapatite/zirconium oxide nanocomposites

Effects of zirconium oxide (ZrO₂) nanoparticles additive on the microstructure and physical properties of hydroxyapatite (HA) were investigated. The HA powder was derived from natural bovine bone by a sequence of thermal processes. The composites containing nanoparticles of ZrO₂ (0.2–1.0 vol%) were fabricated by a solid-state reaction mixed oxide method. All samples showed traces of HA, beta-tricalcium phosphate (β-TCP) and alpha-tricalcium phosphate (α-TCP) phases while the x≥0.1 samples also showed ZrO₂ phase. Amount of β-TCP and α-TCP phases tend to decrease with ZrO₂. The additive inhibited grain growth as a result of a decrease in grain size. However, the x=0.2 sample exhibited higher hardness value which is consistent with the density data. In addition, bioactivity test suggested that the additive promoted an apatite forming with the values of Ca/P close to the value obtained from HA.     

Micromechanical properties of hydroxyapatite nanocomposites reinforced with CNTs and ZrO2

This study examined the mechanical properties, wettability, and tribology of hydroxyapatite (HA)–zirconia (ZrO₂)–carbon nanotube (CNTs) ceramic nanocomposites (with various CNT ratios (x): 1, 5, and 10 wt%). HA–ZrO₂–CNT-x powders were hydrothermally synthesized. Hot isostatic pressing (HIP) and cold isostatic pressing were used to manufacture solid and dense tablets; consolidation was performed by sintering the nanocomposites under Ar gas at 1150 °C during HIP. The microstructure and morphology of the nanocomposites were characterized via transmission electron microscopy, energy-dispersive X-ray spectroscopy, powder X-ray diffractometry, Fourier transform infrared (FTIR), and scanning electron microscopy. The effects of ZrO₂ and CNTs on the mechanical characteristics of the nanocomposites were examined via nanoindentation, reciprocating wear, and Vickers hardness tests. The microhardness of HA–ZrO₂–CNT-1% and HA–ZrO₂–CNT-5% increased by 36.8% and 66.67%, respectively, compared with that of pure HA. The nanohardness of the HA–ZrO₂–CNT-1%, HA–ZrO₂–CNT-5%, and HA–ZrO₂–CNT-10% samples was 8.3, 9.65, and 8.02 Gpa, and the corresponding elastic modulus was 83.72, 114.34, and 89.27 GPa, respectively. Both of these parameters were higher than those of pure HA. However, in the nanocomposite reinforced with 10% CNT, as opposed to those with lower CNT ratios, their values were lower. Additionally, HA–ZrO₂–CNT-10% was the most hydrophilic nanocomposite synthesized in this study with a contact angle of 48.8°.     

Mechanosynthesis of hydroxyapatite–ferrite composite nanopowder

In the present work, an investigation of the mechanosynthesis of calcium hydroxyapatite (HA, Ca₁₀(PO₄)₆(OH)₂) from a mixture of calcium oxide (СаО) and ammonium hydrophosphate ((NH₄)₂HPO₄) and mechanotreatment of HA in a planetary mill with the use of steel drums and milling body has been performed. The obtained results have shown that the mechanosynthesis of crystalline nanodisperse HA proceeds through the stage of formation of an amorphous material. The temperature treatment of HA powders at 1000 °C has enabled us to establish the influence of the treatment time on the phase composition of the powders and establish the following sequence of phase transformations: Ca₁₀(PO₄)₆(OH)₂→β-Ca₃(PO₄)₂ (t_milling~2 h), β-Ca₃(PO₄)₂→α-Ca₃(PO₄)₂ (t_milling~5 h), β-,α-Ca₃(PO₄)₂→Ca₁₀(PO₄)₆(OH)₂ (t_milling~7 h).The mechanosynthesis and mechanotreatment of hydroxyapatite in steel drums with steel balls is accompanied by the contamination of hydroxyapatite by their wear debris (iron + manganese). A large part of oxidized iron forms superparamagnetic inclusions distributed in HA powder. A small part of Fe³⁺ and Mn²⁺ ions from the steel wear debris enters into the hydroxyapatite lattice, substituting Ca²⁺ ions. As a result, a nanocomposite powder consisting of hydroxyapatite, alloyed by Fe³⁺ and Mn²⁺ ions and ferrite inclusions forms. The phase composition of HA powders, the degree of their alloying by Fe³⁺ and Mn²⁺ ions, and the content of ferrite inclusions can be controlled by changing the time of mechanotreatment.     

Preparation and properties of β-CaSiO3/ZrO2 (3Y) nanocomposites

β-CaSiO₃/ZrO₂ (3Y) nanocomposites were successfully fabricated by spark plasma sintering (SPS) technique. The addition of nanocrystalline ZrO₂ could inhibit the phase transition of micrometer sized CaSiO₃ and increase its phase transitional temperature. The relative densities of the dense β-CaSiO₃/ZrO₂ nanocomposites were above 98%. Nanocrystalline ZrO₂ has formed a network structure in the nanocomposites, which could improve the mechanical properties of nanocomposites. The fracture strength and fracture toughness of the nanocomposites were as high as 395 MPa and 4.08 MPa m^1/2, respectively. The nanocomposites showed good in vitro bioactivity with hydroxyapatite (HA) layer formation on the ZrO₂ network of the nanocomposites in simulated body fluid. The spark plasma sintered β-CaSiO₃/ZrO₂ (3Y) nanocomposite may provide a new bone graft for load bearing applications.     

A promising sol-gel route based on citric acid to synthesize Li3V2(PO4)3/carbon composite material for lithium ion batteries

Li₃V₂(PO₄)₃/carbon composite material was synthesized by a promising sol-gel route based on citric acid using V₂O₅ powder as a vanadium source. Citric acid acts not only as a chelating reagent but also as a carbon source, which enhance the conductivity of the composite material and hinder the growth of Li₃V₂(PO₄)₃ particles. The structure and morphology of the sample were characterized by TG, XRD and TEM measurements. XRD results reveal that Li₃V₂(PO₄)₃/carbon was successfully synthesized and has a monoclinic structure with space group P2₁/n. TEM images show Li₃V₂(PO₄)₃ particles are about 45 nm in diameter embeded in carbon networks. Galvanostatic charge/discharge and cyclic voltammetry measurements were used to study its electrochemical behaviors which indicate the reversibility of the lithium extraction/insertion processes. Li₃V₂(PO₄)₃/carbon performed in a voltage window (3.0-4.8 V) exhibits higher discharge capacity, better cycling stability and its discharge capacity maintains about 167.6 mAh/g at a current density of 28 mA/g after 50 cycles.     

Improvements on the mechanical properties and thermal shock behaviours of MgO-spinel composite refractories by ZrO2 incorporation

Microstructural features and improvements on the mechanical properties and thermal shock behaviours of MgO-spinel composite refractories with ZrO₂ addition were examined. ZrO₂ incorporation into MgO-spinel led to improvements around ∼1.5-fold ratios on mechanical properties, R_st values and thermal shock results. The basic parameters improving mechanical properties and thermal shock resistance of MgO-spinel-ZrO₂ composite refractories were determined as follows: (i) propagation of microcracks for a short distance by interlinking each other, (ii) stopping or deviation of microcracks when reaching pores or ZrO₂ particles, (iii) concurrent occurrence of mostly intergranular and some transgranular cracks on fracture surfaces, and with the addition of ZrO₂ (iv) the increase in bulk density, and (v) a significant decrease in MgO grain size. The improvements observed in thermo-mechanical properties confirmed that MgO-spinel-ZrO₂ refractories showed a low strength loss and high thermal shock damage resistance at high temperatures, leading to longer service lives for using industrial applications.     

Evaluation of mechanical and biocompatibility properties of hydroxyapatite/manganese dioxide nanocomposite scaffolds for bone tissue engineering application

The aim of this research was to evaluate the mechanical properties, biocompatibility, and degradation behavior of scaffolds made of pure hydroxyapatite (HA) and HA-modified by MnO₂ for bone tissue engineering applications. HA and MnO₂ were developed using sol-gel and precipitation methods, respectively. The scaffolds properties were characterized using X-ray diffraction (XRD), Fourier transform spectroscopy (FTIR), scanning electron microcopy (SEM), energy dispersive spectroscopy (EDS), and transmission electron microscopy (TEM). The interaction of scaffold with cells was assessed using in vitro cell proliferation and alkaline phosphatase (ALP) assays. The obtained results indicate that the HA/MnO₂ scaffolds possess higher compressive strength, toughness, hardness, and density when compared to the pure HA scaffolds. After immersing the scaffold in the SBF solution, more deposited apatite appeared on the HA/MnO₂, which results in the rougher surface on this scaffold compared to the pure HA scaffold. Finally, the in vitro biological analysis using human osteoblast cells reveals that scaffolds are biocompatible with adequate ALP activity.     

Synthesis of porous Al2O3/ZrO2 nanocomposites by chemical vapour deposition

Al₂O₃/ZrO₂ one-dimensional nanocomposite structures were synthesised by chemical vapour deposition using Al₂O₃ nanowires and a ZrCl₄ powder source at a temperature of 800?°C and a pressure of 130?Pa. The samples were characterised using X-ray diffraction, the scanning electron microscopy, the transmission electron microscopy, and N₂ adsorption–desorption. The results revealed that Al₂O₃/ZrO₂ composite nanowires coated with surface-embedded ZrO₂ nanocrystals were formed and that the ZrO₂ macroporous and mesoporous structures changed as the ZrO₂ deposition time increased. The pore structure and surface area were also elucidated from the N₂ adsorption–desorption measurements.     

Thermal conductivity in mullite/ZrO2 composite coatings

Mullite-based multilayered structures have been suggested as promising environmental barrier coatings for Si₃N₄ and SiC ceramics. Mullite has been used as bottom layer because its thermal expansion coefficient closely matches those of the Si-based substrates, whereas Y–ZrO₂ has been tried as top layer due to its stability in combustion environments. In addition, mullite/ZrO₂ compositions may work as middle layers to reduce the thermal expansion coefficient mismatch between the ZrO₂ and mullite layers. Present work studies the thermal behaviour of a flame sprayed mullite/ZrO₂ (75/25, v/v) composite coating. The changes in crystallinity, microstructure and thermal conductivity of free-standing coatings heat treated at two different temperatures (1000 and 1300 °C) are comparatively discussed. The as-sprayed and 1000 °C treated coatings showed an almost constant thermal conductivity (K) of 1.5 W m⁻¹ K⁻¹. The K of the 1300 °C treated specimen increased up to twice due to the extensive mullite crystallization without any cracking.     

Co-precipitated ZnAl2O4 spinel precursor as potential sintering aid for pure alumina system

Ultra-fine ZnAl₂O₄ spinel hydrogel precursor synthesized from mixed salt solutions of Zn²⁺ and Al³⁺ ions using ammonium hydroxide–hexamethylenetetramine as basic media for co-precipitation was used as bonding material and sintering aid for pure alumina system. The hydrogel powder exhibited some well-defined ZnAl₂O₄ spinel phases at 800 °C. Alumina compacts were fabricated by incorporating small proportions of the precursor in alumina powder and firing at different temperatures (1350–1500 °C). The degree of densification was studied by measurement of fired shrinkage, apparent porosity, bulk density and cold crushing strength. Phase compositions and microstructural features of sintered samples were evaluated by XRD and SEM respectively. Addition of 0.2% hydrogel powder to alumina exhibited remarkable influence on development of high mechanical strength. The in situ formed ZnAl₂O₄ spinel dopant acted as a grain growth inhibitor in the alumina system.     

Physicochemical characterization and catalytic applications of MoO3–ZrO2 composite oxides towards one pot synthesis of amidoalkyl naphthols

A series of MoO₃–ZrO₂ composite oxide catalysts were prepared by coprecipitation and impregnation methods and characterized by XRD, Raman, UV–Vis, TEM and sorptometric techniques. Characterization studies indicated the presence of tetragonal zirconia phase and well dispersed MoO₃ species as isolated and polymolybdate clusters in the composite oxide. The MoO₃(20 mol%)–ZrO₂ material was used as efficient catalyst for synthesis of amidoalkyl naphthols under solvent free conditions using conventional as well as microwave heating. The results obtained clearly showed that the composite oxide catalyst was recyclable and highly efficient for the reaction giving good yield and purity of the products.     

Study on impedance spectra of La0.7Sr0.3MnO3 and Sm0.2Ce0.8O1.9-impregnated La0.7Sr0.3MnO3 cathode in single chamber fuel cell condition

Impedance spectroscopy was used to study the electrochemical performance of pure and ion-impregnated La_0.7Sr_0.3MnO₃ (LSM) cathodes on YSZ (Y₂O₃-stabilized ZrO₂) electrolytes in single chamber fuel cell conditions, i.e. a mixture gas with oxygen as oxidant, methane as fuel and nitrogen as dilute gas. Measurements were taken at the furnace temperature range of 550-750 °C and the CH₄/O₂ ratios from 1 to 2. Polarization resistances (R_p) for pure and impregnated LSM cathodes increased obviously as the CH₄/O₂ ratio increased at 650-750 °C. Polarization resistances of Sm_0.2Ce_0.8O_1.9 (SDC) impregnated LSM cathode were much smaller than the ones of pure LSM cathode under the same conditions. Overtemperatures were occurred at both cathodes due to the partial oxidation of methane.     

Effect of Cu powder addition on thermoelectric properties of Cu/TiO2−x composites

Spark plasma sintering was used to fabricate Cu/TiO_2−x composites by adding Cu powder to nonstoichiometric titanium dioxide, TiO_2−x. The composition and crystal forms of the composites were examined. The thermoelectric properties of the composites were measured and the effects of composite formation on these properties were discussed. The rule of mixture (ROM) of composite and general effective medium theory (GEM) were used to investigate the composite effects of the Cu/TiO_2−x composites. The results revealed that the electrical resistivities of the composites was much lower than that of TiO_2−x. As the added amount of Cu powder increased, the electrical properties of the composites shifted from semiconductor behavior to metallic behavior. The thermoelectric performances of the composites improved as a result of composition formation. The thermoelectric performance can be improved by adjusting the balance among electrical resistivity, thermal conductivity and the Seebeck coefficient, based on the composite effects.     

Solubility and diffusivity of CO2 in poly(l-lactide)-hydroxyapatite and poly(d,l-lactide-co-glycolide)-hydroxyapatite composite biomaterials

Solubility and diffusivity of supercritical CO₂ in poly(l-lactide)-hydroxyapatite (PLLA-HA) and poly(d,l-lactide-co-glycolide)-hydroxyapatite (PLGA-HA) composite materials were measured using a magnetic suspension balance at a temperature of 313 K and a pressures range of 10-30 MPa. The effect of the HA concentration on the solubility and diffusivity was investigated by varying filler content in the range of 0-50 wt%. For the PLLA-HA composites the solubility decreases with the increase of filler concentration. Diffusivity of the gas in the substrate is also lower as the HA content increases. In the case of PLGA-HA composites, small filler content favors the solubility and diffusivity of CO₂ due to incomplete wetting of the solid particles by the polymer. As the amount of HA increases solubility decreases. The results suggest that dense CO₂ could be used as a ‘green’ processing agent for composite biomaterials when organic solvents or high temperatures should be avoided.     

Processing of different alumina–zirconia composites by slip casting

Two Al₂O₃–ZrO₂ mixture preparation routes: classical powder mixing and addition of a Zr (IV) precursor solution to a well dispersed Al₂O₃ suspension, were used to produce alumina (Al₂O₃)–zirconia (ZrO₂) slip cast composites. For the conventional powder mixing route, two commercial 3 mol% yttria-partially stabilized zirconia powders, 0.3 wt% Al₂O₃-doped (Al-doped Y-PSZ) and without Al₂O₃ (Y-PSZ), were employed. The influence of the zirconia content and the solid loading on the rheological properties of concentrated aqueous Al₂O₃–ZrO₂ slips were investigated. The density of green samples was studied and related to the degree of slip dispersion. In addition, the influence of the processing conditions on the density and microstructure development of sintered samples were investigated. By using the Zr (IV) precursor route, nano-sized ZrO₂ (ZN) particles homogeneously distributed on the Al₂O₃ particle surfaces were obtained; however, it let to aggregates of some Al₂O₃ particles with very fine ZrO₂ uniformly distributed. The viscosity and yield stress values of Al₂O₃–ZN suspensions were markedly higher than those of Al₂O₃–Al-doped Y-PSZ and Al₂O₃–Y-PSZ ones, for all the compositions and solid loading studied and resulted in a less dense packing of cast samples. However, for the composite with 10.5 vol% ZN a high sintered density and a smaller ZrO₂ grain size distribution compared with the conventional powder mixing route could be obtained.     

Preparation of ZrO2/Gd2O3 composite ceramic materials by coprecipitation method

High burnup is a goal for further development of advanced nuclear power in the future. However, along with the increase of burnup, it becomes more diffidult to control reactor reactivity, which affects the operation safety of the nuclear reactor. Al₂O₃/B₄C burnable poison materials widely used in pressurized water reactor currently will not meet the requirements of burnable poison materials in high burnup nuclear power. Because of the better performance of ZrO₂/Gd₂O₃ burnable poison materials than that of Al₂O₃/B₄C, this paper studies the preparation of ZrO₂/Gd₂O₃ composite ceramic materials by the coprecipitation method. The experimental results show that at the sintering temperature of 1500–1650 °C, ZrO₂/Gd₂O₃ composite ceramic grains are small, compact and uniform with the generation of homogeneous solid solution. At 1600 °C, ZrO₂–10%Gd₂O₃ has the highest density and mechanical strength.     

Enhanced lithium storage in a VO2(B)-multiwall carbon nanotube microsheet composite prepared via an in situ hydrothermal process

A novel VO₂(B)-multiwall carbon nanotube (MWCNT) composite with a sheet-like morphology was synthesized by a simple in situ hydrothermal process. The morphology and structural properties of the samples were investigated by X-ray diffraction (XRD), thermogravimetric analysis (TGA), field emission scanning electron microscopy (FE-SEM), and transmission electron microscopy (TEM). FE-SEM observations demonstrated that the nanosheets are frequently grown together in the form of bundles composed of numerous nanosheets, each with a smooth surface and a typical length of 300-500 nm, width of 50-150 nm, and thickness of 10-50 nm. Electrochemical measurements were carried out using different discharge cut-off voltages. Electrochemical tests show that the VO₂(B)-MWCNT composite cathode features long-term cycling stability and high discharge capacity (177 mAh g⁻¹) in the voltage range of 2.0-3.25 V at 1 C with a capacity retention of 92% after 100 cycles. The electrochemical impedance spectra (EIS) indicate that the VO₂(B)-MWCNT composite electrode has very low charge-transfer resistance compared with pure VO₂(B), indicating the enhanced ionic conductivity of the VO₂(B)-MWCNT composite. The enhanced cycling stability is attributed to the fact that the VO₂(B)-MWCNT composite can prevent the aggregation of active materials, accommodate the large volume variation, and maintain good electronic contact. We strongly believe that the VO₂(B)-MWCNT composite can be considered as a potential cathode material for lithium-ion batteries.     

Fabrication and characterization of sol–gel derived hydroxyapatite/zirconia composite nanopowders with various yttria contents

Homogeneous composite nanopowders of hydroxyapatite/30 wt% yttria-stabilized zirconia (HA–YSZ) containing 0, 3, 5, and 8 mol% Y₂O₃ (namely; HA–0YSZ, HA–3YSZ, HA–5YSZ, and HA–8YSZ) were successfully synthesized using the sol–gel method. Simultaneous thermal analysis (STA), X-ray diffraction (XRD), X-ray fluorescence spectroscopy (XRF), Fourier transformed infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), and transmission electron microscopy (TEM) techniques were utilized to characterize the prepared nanopowders. Analyses of HA–YSZ composite nanopowders showed the successful formation of desirable phases. HA unit cell volume in the composites increased as a result of ion exchange of calcium and zirconium between HA and zirconia. Results revealed the formation of HA particles with irregular morphology (40–80 nm) and spherical yttria-stabilized zirconia particles (20–30 nm). Segregation of yttrium ions at the grain boundaries of ZrO₂ particles retarded the grain growth of zirconia particles and the presence of ZrO₂ nanoparticles among the hydroxyapatite particles resulted in grain growth inhibition of HA particles. This process can be used to synthesize HA–YSZ composite nanopowders with improved properties, which are much needed for hard tissue repair and biomedical applications.