Preparation and optical characterization of hydroxyapatite and ceramic systems with titanium and zirconium formed by dry high-energy mechanical alloying

Calcium phosphate-based bioceramics, mainly in the form of hydroxyapatite, Ca₁₀(PO₄)₆(OH)₂—HAP, is the main mineral constituent of teeth and bones with excellent biocompatibility with hard and muscle tissues. These materials exhibit several problems of handling and fabrication, which can be overcome by mixing them with a suitable binder. The dry milling process of fabrication of HAP presents the advantage that melting is not necessary and the powder obtained is nanocrystalline. The high efficiency of the dry milling process opens a new way to produce commercial amount of nanocrystalline HAP and others bioceramic. In this work dry mechanical alloying has been used to produce nanocrystalline powders of HAP using three different experimental procedures (HAPA: Ca(H₂PO₄)₂ + Ca(OH)₂; HAPB: Ca(H₂PO₄)₂ + CaCO₃; and HAPC: CaHPO₄ + CaCO₃). HAP was obtained after 5, 10 and 15 h of milling in the reactions HAPA and HAPB, but it is necessary 15 h of milling in the reaction HAPC to obtain HAP. In order to improve the mechanical properties of HAP calcium phosphate ceramics, with titanium (CaP-Ti) and zirconium (CaP-Zr), have been prepared by dry ball milling using two different experimental procedures: CaP-Ti1: Ca(H₂PO₄)₂ + TiO₂; CaP-Ti2: CaHPO₄ + TiO₂; and CaP-Zr1: Ca(H₂PO₄)₂ + ZrO₂, CaP-Zr2: CaHPO₄ + ZrO₂. The calcium titanium phosphate phase, CaTi₄P₆O₂₄, was obtained in the reaction CaP-Ti1. In the reactions CaP-Ti2, CaP-Zr1 and CaP-Zr2, it was not observed the formation of any calcium phosphate phase even after 15 h of dry mechanical alloying. The milled HAP and the ceramics systems obtained were characterized by X-ray powder diffraction, infrared and Raman scattering spectroscopy.     

非化学计量比SnO~2~-~x纳米微晶材料的XRD,XPS和ESR研究

采用溶胶凝胶法, 以无水四氯化锡及异丙醇为原料, 制得非化学计量比的SnO~2~-~x纳米微晶材料。透射电镜图片显示700℃焙烧2h得到的粉体的粒度为20nm,由X射线衍射及X射线光电子能谱的分析可知, 300℃焙烧2h得到颗粒边界部分原子无规排布的纳米粉体, 而700℃焙烧2h得到的是晶格趋于完整的纳米微晶,它们都存在氧空位及晶格缺陷, 利用这些结论可以解释SnO~2~-~x纳米微晶材料中出现的顺磁信号。     

Modeling and optimization of densification of nanocrystalline Al<Subscript>2</Subscript>O<Subscript>3</Subscript> powder prepared by a sol–gel method using response surface methodology

Response surface methodology (RSM) based on central composite design (CCD) was successfully applied to the optimization and modeling of densification of nanocrystalline Al₂O₃ powder prepared by sol–gel method. The effects of three operating variables, sintering temperature, calcination temperature and milling time on the densification of nanocrystalline Al₂O₃ were systematically evaluated. A quadratic model for densification was proposed. Analysis of variance (ANOVA) indicated that the proposed quadratic model could be used to navigate the design space. The simulated values obtained from the statistical model were in conformity with the experimental results within an average error of ±1.5%. The optimum operating conditions for densification were found to be 1,579 °C of sintering temperature, 909 °C of calcination temperature and 117 min of milling time. The obtained density under the optimum conditions determined by RSM was 98.5%. The results confirmed that RSM based on central composite design was an accurate and reliable method to optimize the densification conditions of nanocrystalline Al₂O₃ powder.     

Hydroxyapatite gels and nanocrystals prepared through a sol-gel process

We have investigated the effect of the Ca/P molar ratio on the structural and morphological properties of hydroxyapatite (HA) gels and nanocrystals. The sol-gel process was carried out in aqueous, and alternatively in alcoholic medium (50% water-50% ethanol), at 37°C. Gel samples were obtained by drying the sols at 37°C or at 80°C, whereas powder samples were obtained by filtering the sols. Heat treatment at temperatures as low as 300°C is enough to obtain pure HA from the gels with a Ca/P molar ratio of 1.00 and 1.67. At variance, heat treatment of the gels with a Ca/P of 2.55 always produces secondary phases. The degree of crystallinity of HA increases with the Ca/P molar ratio of the sols, and it is slightly affected by the presence of ethanol in the precipitation medium. Filtering of the sols provides powders constituted of nanocrystalline HA that exhibit degree of crystallinity, crystal morphology and thermal stability closely related to the sols composition.     

Sol-gel modified Pechini method for obtaining nanocrystalline KRE(WO4)2 (RE = Gd and Yb)

KRE(WO₄)₂ (RE = Gd and Yb) nanocrystalline powder was obtained by the modified sol-gel Pechini method. The precursor powder was calcined between 923 and 1023 K for a maximum of 6 h at air atmosphere. DTA-TG of the precursor powder shows that the temperature for total calcination is around 800–850 K. Molar ratio between the complexing agent and the metal ions in the first step of the method and molar ratio between the complexing agent and the ethylene glycol in the second step of the method were studied to optimize the preparation process. X-ray diffraction and IR spectroscopy were used to study the transformation from precursor powder into a crystalline monoclinic phase. Raman spectroscopy was used to study the vibrational structure of the nanoparticles. The Scherrer formula was used to confirm the grain sizes visualized by SEM and TEM techniques. Small nanoparticles in the range of 20–50 nm of monoclinic KREW have been successfully obtained by this methodology.     

Fabrication of Single-Phase BaTi4O9 Nanocrystalline Powder by Sol-Gel Process

BaTi₄O₉ nanocrystalline powder was prepared by sol-gel method using Ti(OC₄H₉)₄ and Ba(CH₃COO)₂ as raw materials. The optimum process was obtained by analyzing the synthesis condition of the single-phase BaTi₄O₉ nanocrystalline powder as follows: the content of acetyl-Titanium = 1 mol/L. pH = 4.2, molar ratio of water/alkoxide = 15, and the powder is kept at 1200°C for 2 h. The XRD and TEM analysis showed that the single-phase BaTi₄O₉ nanocrystalline powder of 30 nm in size was well prepared.     

Thermal behavior of nickel–metal hydride battery during charging at a wide range of ambient temperatures

In this study, hydoxyapatite (HA) prepared from calcined bovine bone was studied. Two methods were used for HA sintering: conventional sintering (CS) and microwave sintering (MS). HA was obtained by calcination of bovine bone at 800 °C for 4 h followed by wet ball milling. Afterwards, the powder was compacted under 75 MPa and sintered for 2 h at different temperatures, from 1050 to 1200 °C. It has been found that the bulk density of HA increases by increasing sintering temperature when both CS and MS were used. Nevertheless, at the same temperature and for a shorter time (15 min), the HA sintered by microwave were characterised by a density relatively higher than that of sintered by conventional furnace. For example, at 1100 °C the bulk densities of samples using CS and MS were about 2.49 (for 120 min) and 2.93 (for 15 min) g/cm³, respectively. Furthermore, a near theoretical density (98.6%) was obtained when HA samples were sintered at 1200 °C for 15 min only but using the proposed MS, which was much higher than that (89.7%) of HA samples sintered at the same temperature for longer holding time (120 min). Besides this, the X-ray analyses have shown that heat-treatment, using these two processes, has lead to HA decomposition into tricalcium phosphate and/or tetracalcium phosphate.     

Elaboration by high-energy ball milling of copper/palladium composite materials – characterization and electrocatalytic activity for the reduction of nitrate in alkaline medium

In this study, an original approach was explored to decorate copper particles with palladium and well-defined bimetallic copper/palladium powders were elaborated through a two-step ball milling procedure. First, copper powder was milled with previously determined optimal conditions (ball-to-powder mass ratio of 2, milling duration of 6 h under argon) in order to obtain spherical nanocrystalline copper particles with an average diameter of 800 μm. Then, an additional milling in presence of 1 at.% of palladium powder was performed, leading to the formation of Cu–Pd composite materials. Palladium surface concentrations from 3 to 62 at.% were obtained by varying both the ball-to-powder mass ratio (2:1 or 10:1) and the milling duration (from 5 to 30 min). Scanning electron microscopy, optical microscopy, X-ray photoelectron spectroscopy and X-ray diffraction analyses confirmed that the more intense the milling is, the easier the palladium diffuses into the copper matrix and smaller the palladium concentration on copper particles is. Cyclic voltammetry and electrolysis experiments showed that palladium inclusions on copper improve greatly the electrocatalytic activity for nitrate reduction in alkaline media. The key role of Pd in the Pd–Cu composite electrodes is to accelerate the reduction of nitrite, formed by the electrochemical reduction of nitrate on Cu sites. Also different nitrate electroreduction behaviors were observed at copper and copper–palladium electrodes leading to the preferential formation of nitrite or ammonia depending on the applied potential and the Pd surface concentration.     

Preparation by high-energy milling, characterization, and catalytic properties of nanocrystalline TiO2

Titanium dioxide (TiO2) is widely used for applications in heterogeneous photocatalysis. We prepared nanocrystalline powders of the anatase as well as the rutile modification by high-energy ball milling of the coarse grained source materials for up to 4 h. The resulting average grain size was about 20 nm. The morphology of the powders was investigated with transmission electron microscopy, X-ray powder diffraction, and BET surface area determination. Measurements of the catalytic activity reveal a maximum as a function of the milling time at about 40 min. This maximum could be explained by a superposition of two counteracting effects. The first one is the increase of the specific surface area resulting in an increase of the catalytic activity, and the second one is a change of the electronic structure at the surface of the TiO2 particles corresponding to a reduction of the surface. The latter one was confirmed by light absorption experiments, X-ray photoelectron spectroscopy, and electron paramagnetic resonance spectroscopy.     

Effect of ZrC Nanopowders on Enhancing the Hydro/Dehydrogenation Kinetics of MgH2 Powders

Hydrogen has been receiving great attention as an energy carrier for potential green energy applications. Hydrogen storage is one of the most crucial factors controlling the hydrogen economy and its future applications. Amongst the several options of hydrogen storage, light metal hydrides, particularly nanocrystalline magnesium hydride (MgH₂), possess attractive properties, making them desired hydrogen storage materials. The present study aimed to improve the hydrogen storage properties of MgH₂ upon doping with different concentrations of zirconium carbide (ZrC) nanopowders. Both MgH₂ and ZrC were prepared using reactive ball milling and high-energy ball milling techniques, respectively. The as-prepared MgH₂ powder was doped with ZrC (2, 5, and 7 wt%) and then high-energy-ball-milled for 25 h. During the ball milling process, ZrC powders acted as micro-milling media to reduce the MgH₂ particle size to a minimal value that could not be obtained without ZrC. The as-milled nanocomposite MgH₂/ZrC powders consisted of fine particles (~0.25 μm) with a nanosized grain structure of less than 7 nm. Besides, the ZrC agent led to the lowering of the decomposition temperature of MgH₂ to 287 °C and the reduction in its apparent activation energy of desorption to 69 kJ/mol. Moreover, the hydrogenation/dehydrogenation kinetics of the nanocomposite MgH₂/ZrC system revealed a significant improvement, as indicated by the low temperature and short time required to achieve successful uptake and release processes. This system possessed a high capability to tackle a long continuous cycle lifetime (1400 h) at low temperatures (225 °C) without showing serious degradation in its storage capacity.     

Solid state reactions in Al based composites made by mechanofusion

Mixtures of aluminium and other metal powders were milled in a Hosokawa AM-15F mechanofusion system in order to produce composite materials with coated or layered microstructure. These composites were then annealed or used in plasma spraying experiments. The intermetallic phases produced in the consecutive steps of the treatment were investigated by different methods.In the case of the Al-Ni powder system the presence of intermetallic phases confirmed that phase forming solid state reactions start during the first, mechanofusion step. After milling the powder mixture in the Hosokawa equipment, crystalline Al₃Ni could be detected by TEM. A second intermetallic phase, Al₃Ni₂ was also observed after a heat treatment at 750 K. In Al-Cu-Fe and Al-Cu-Co powder composites, produced by milling, binary and ternary phases could be found only after plasma spraying. That means that in these cases the thermodynamic and kinetic requirements of the reactions could not be fulfilled by this mild milling. Nevertheless, the considerably large specific surface of the metal-metal interfaces, formed during the milling process in the ternary composites, makes it possible to produce multi-phase coatings from these composites. It means that only two technological steps are required (milling — plasma spraying). All of the other known technologies consist of three steps: alloy preparation — milling — plasma spraying or alloy preparation —atomisation — plasma spraying.Similarities and differences between the reactions taking place in thin films and thin and/or small milled particles are discussed.Dedicated to Professor Dr. rer. nat. Dr. h.c. Hubertus Nickel on the occasion of his 65th birthday     

Influence of the dehydration procedure on the physicochemical properties of nanocrystalline hydroxylapatite xerogel

The influence of various dehydration procedures on the physicochemical properties of hydroxylapatite gel was examined. The best dehydration procedure is freezing, leading to the formation of a nanocrystalline hydroxylapatite powder without intermediate formation of a monolithic xerogel. Examination by the layer self-arrangement method, scanning electron microscopy, and atomic-force microscopy showed that the powder particles are spherical aggregates from 0.4 to 2.0 μm in size, consisting of nanoparticles 16–30 nm in diameter.     

Synthesis and characterization of nanocrystalline α-Al2O3 using Al and Fe2O3 (hematite) through mechanical alloying

In this present work, the synthesis of nanocrystalline α-Al₂O₃ using pure aluminum (Al) and Fe₂O₃ (hematite) as the precursors by mechanical alloying technique has been studied. The formation of α-Al₂O₃ nanocrystallites occurs during the solid-state reaction and through the reduction treatment. Also in this paper, effects of milling time on particle size and the lattice strain nanocrystalline α-Al₂O₃ have been investigated. Obtained powders were evaluated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), differential thermal analysis (DTA), thermal gravimetric analysis (TGA) and X-ray diffraction (XRD). The obtained results indicated that a reduction reaction was completed after 2 h milling in a planetary mill. The crystallite size of obtained α-alumina (α-Al₂O₃) was in general about 12 nm. Finally, the results showed appropriate homogeneity and dispersion of related nanocrystalline.     

Point of zero potential of single-crystal electrode/inert electrolyte interface

In this work, a method to prepare a thermally stable QDs/clay powder is reported. First, several water soluble CdTe QDs characterised by different size-dependent emission wavelengths were synthesised through wet chemistry. Montmorillonite-Na(+) clay in water was dispersed into a muddy suspension by sonication. Then, the clay-water suspension was used as the host media for CdTe QDs to prepare the QDs/clay powder by freeze drying. The experiments showed that QDs/clay powder could be re-dispersed in water without changing the luminescent property of the QDs; this process was reversible. EDX showed that Cd and Te elements existed in the QDs/clay powder and the XRD tests showed that the clay [001] reflection peaks for raw clay, QDs (λ(em)=514 nm)/clay and QDs (λ(em)=560 nm)/clay were the same, namely 2θ=7.4°. Finally, QDs/clay powder was applied to the HDPE polymer extrusion process at 200 °C to produce thin films; the resultant QDs-polymer nanocomposite film exhibited strong fluorescence.     

电化学溶解钛金属直接水解法制备纳米TiO2

Metallic titanium was electrochemically dissoluted in absolute ethanol in the presence of Et4N•Br(as electro conductive additive),The electrolyte solution was then directly hydrolysized to obtain nanocrystalline TiO2.The powder obtained was calcined at 720℃ for 1 h.FT IR,Raman spectra,XRD and TEM were used to investigate the structure and particle size of the powder.Studies showed that the nanocrystalline TiO2 prepared by this method was of monocline structure with high textural stability and narrow size distribution of 10－20 nm,and its Raman spectra showed a shift of about 25 cm－1.The experiments also showed that the product yield could be improved by controlling the temperature under 50－60℃,selecting R4N•Br as conductive additive and preventing titanium anode from being passivated.The electrochemical dissolution of metal anode may be recommanded as a promising technique for the synthesis of nanomaterials.     

Bimodal meso/macro porous hydroxyapatite coatings

Bimodal porous nanocrystalline hydroxyapatite (HA) coatings with pore sizes in the range of meso/macro meter scale have been deposited onto Ti6Al4V substrates by sol–gel method using nonionic surfactant as porous former agent. By increasing the molar ratio between phosphorous source and surfactant to 0.006, a very homogeneous bimodal distribution of pores in the range of 4.5–10 nm and 0.2 μm have been obtained.     

Phase transformations in nanocrystalline TiO2 milled in different milling atmospheres

The structural evolution of nanocrystalline TiO₂ milled in different milling atmospheres was studied by X-ray diffraction (XRD), Raman spectroscopy and X-ray photoelectron spectroscopy. Rietveld refinements of the XRD data showed that high-energy ball milling induced the transformations from anatase to srilankite and rutile at room temperature and ambient pressure. The milling atmospheres with different oxygen partial pressures had an influence on the transformation kinetics of anatase. When the nanocrystalline TiO₂ powders were, respectively, milled in oxygen, air and nitrogen atmospheres, the transformation rates of anatases in turn increased with a decrease in oxygen partial pressure of the milling atmosphere, due to the reducing concentration of oxygen vacancies in the milled TiO₂ lattice.     

Optical and electrical properties of barium titanate-hydroxyapatite composite screen-printed thick films

In this paper we will study the effect of the presence of hydroxyapatite (HA—Ca₁₀(PO₄)₆(OH)₂) on the dielectric permittivity and losses of the barium titanate (BTO—BaTiO₃) thick films. These films were prepared in two layers geometry using the screen printing technique on Al₂O₃ substrates. Mechanical alloying has been used successfully to produce nanocrystalline powders of hydroxyapatite (HA) used in the films. We also look for the effect of the grain size of the BTO and HA on the final properties of the film. The samples were studied using X-ray diffraction, scanning electron microscopy (SEM), Raman and infrared spectroscopies, dielectric permittivity and losses measurements. The study of the dielectric permittivity and losses was done in the radio-frequency range (100 Hz–10 MHz). The role played by the firing process in the film preparation and the crystallite size of HA and BTO on the dielectric constant and structural properties of the films are discussed.     

On the influence of the milling time in the Curie temperature of Fe56Co7Ni7Zr10B20 investigated by magnetic thermogravimetric analysis

Magnetic thermogravimetric analysis (TGM) was used to investigate the influence of the milling time (t _mill) in the Curie temperature (T _C) of nanocrystalline powders and of a melt-spun amorphous ribbon with composition Fe₅₆Co₇Ni₇Zr₁₀B₂₀. The TGM analysis was carried in a continuous flow of 99.99% pure argon from room temperature up to 1250?K. A magnetic field of 100?Oe was applied throughout the measurements. Nanopowders of Fe₅₆Co₇Ni₇Zr₁₀B₂₀ were produced by mechanical alloying the samples in an argon atmosphere for milling times ranging from 1 to 100?h. The samples were characterized by X-ray diffraction and by scanning electron microscopy. The average particle size decreased from 45.4?nm for a powder milled for 1?h to 5?nm after being milled for 100?h. Moreover, T _C (=1126.4?±?4.4?K) was found to be nearly independent of t _mill while for the melt-spun amorphous ribbon it was found to be substantially smaller (T _C?=?482?K). This is a clear indication that T _C is quite sensitive to the degree of amorphosity present in the sample. The activation energy associated to the crystallization process was estimated from DSC data by using the Kissinger??s method to be 193?kJ/mol.     

Application of focused ion beam to atom probe tomography specimen preparation from mechanically alloyed powders.

Focused ion-beam milling has been applied to prepare needle-shaped atom probe tomography specimens from mechanically alloyed powders without the use of embedding media. The lift-out technique known from transmission electron microscopy specimen preparation was modified to cut micron-sized square cross-sectional blanks out of single powder particles. A sequence of rectangular cuts and annular milling showed the highest efficiency for sharpening the blanks to tips. First atom probe results on a Fe95Cu5 powder mechanically alloyed in a high-energy planetary ball mill for 20 h have been obtained. Concentration profiles taken from this powder sample showed that the Cu distribution is inhomogeneous on a nanoscale and that the mechanical alloying process has not been completed yet. In addition, small clusters of oxygen, stemming from the ball milling process, have been detected. Annular milling with 30 keV Ga ions and beam currents >or=50 pA was found to cause the formation of an amorphous surface layer, whereas no structural changes could be observed for beam currents 相似文献