Synthesis, Processing, Mechanical, and Biological Property Characterization of Hydroxyapatite Whisker-Reinforced Hydroxyapatite Composites

Effects of hydroxyapatite (HA) whiskers addition on densification, mechanical, and biological properties of HA compacts were studied for their use as an implant material for orthopedic and dental applications. HA nanopowder was synthesized using reverse micelle as template system, and urea hydrolysis synthesis route was used to prepare micrometer-sized HA whiskers. Poly (oxyethylene)₁₂ nonylphenol ether (NP12) and cyclohexane were used as surfactant and organic solvent, respectively, for the reverse micelle microemulsion system. Desired microstructure in sintered HA composite was obtained by mixing Mg²⁺ as a dopant in HA nanopowders, and Al³⁺ as a dopant in HA whiskers. Compacts were processed using pressureless sintering. With an increase in whisker content from 0 to 10 wt%, the average compressive strength of HA compacts decreased from 120 to 90 MPa. HA composite processed with 10 wt% HA whisker showed a microhardness of 3.6 GPa and an average indentation fracture toughness of 1.5 MPa·m^1/2. Mineralization study in simulated body fluid showed deposition of octacalcium phosphate on sintered HA compacts. In vitro cytotoxicity tests with human osteoprecursor cell line confirmed excellent osteoblast cell attachment and growth on the sintered HA compacts with 0, 10, and 20 wt% HA whiskers.     

Synthesis and characterization of neodymium doped ceria nanocrystalline ceramic structures

In this study, a new method to synthesize neodymium doped ceria ceramic nanopowders by the electrospinning of the hybrid polymers solution of their composite precursor was put forward. Calcined and sintered nanopowders were characterized by FT-IR, XRD, BET, SEM, and AFM techniques. According to the XRD analysis, the obtained powders are single phase and independent of the dopant concentration in the range investigated. The crystallite sizes were calculated using Scherrer equation. Moreover, lattice parameters, dislocation densities and microstrain values were calculated. BET results show that the increase of the neodymium doped content decrease the surface area of the composite powders, confirming the highly ordered micro and mesostructure. SEM and AFM results show that the samples have spherical grains. According to the surface roughness measurements, the increase in the amount of neodymium and the decrease in the amount of cerium decreased the surface roughness.     

Dependence of optical properties on doping metal, crystallite size and defect concentration of M-doped ZnO nanopowders (M = Al, Mg, Ti)

ZnO, Al-, Mg- and Ti-doped ZnO nanopowders were synthesized from CTAB-assisted oxalate intermediate by thermal decomposition method at 600 °C in air. All samples presented a hexagonal wurtzite structure. The spherical nanoparticles assembled in a porous octahedron-like shape for all samples. The size of Al-doped ZnO nanopowders increased as a function of Al ion concentration whereas the size of Mg- and Ti-doped ZnO nanopowders decreased when Mg and Ti ion concentrations were increased. The increment and reduction of their sizes can be explained by the Zener pinning effect. The E_g value of Al-doped ZnO nanopowders slightly decreased when Al ions were increased due to the crystallite size and defect concentration increased. In contrast, the E_g value of Mg- and Ti-doped ZnO nanopowders increased as a function of Mg and Ti ion concentration which can be explained by the Moss-Burstein effect.     

Fe掺杂对纳米晶SnO_2粉体结构的影响(英文)

采用共沉淀法制备了一系列Fe掺杂含量由低到高的纳米晶SnO2粉体。采用X射线衍射、透射电镜、X射线光电子谱分析等测试手段对其进行了表征。结果表明:当Fe掺杂含量(摩尔分数)低于15%时,晶粒大小随掺杂含量的增加显著下降,从无掺杂的5.2nm到掺杂15%Fe的2.4nm,随后继续增加Fe掺杂含量对晶粒大小无影响。而当Fe掺杂量大于20%时,Fe在SnO2晶粒表面才出现较为明显的偏析。掺杂物对SnO2晶粒长大的阻碍作用主要归因于掺杂物与SnO2体相形成固溶体,产生的溶质拖曳和晶格畸变效应,掺杂物在晶粒表面偏析所起作用较小。     

Wet chemistry approach to the preparation of tantalum-doped hydroxyapatite: Dopant content effects

Tantalum-doped hydroxyapatite (Ta-doped HA) nanopowders with different Ta contents were synthesized by a wet-chemical precipitation route. The structure modification and charge compensation mechanism were investigated by various characterization techniques. Due to the smaller size of tantalum ions compared to the Ca²⁺ size, it was assumed that the tantalum ions occupy either the Ca²⁺ and/or the interstitial positions in the HA lattice, where the charge imbalance from to this substitution was compensated by the Ca²⁺ vacancies. From the XRD patterns, the as-synthesized nanopowders were poorly crystalline apatite in the absence and presence of different dopant contents. The hexagonal HA and tricalcium phosphate (β-TCP) phases as biphasic calcium phosphate mixtures were formed after heating at 900 °C. In addition to the β-TCP phase, minor extra phases such as calcium oxide (CaO) and calcium pyrophosphate (Ca₂P₂O₇) were identified from the HA decomposition. The FTIR results indicated that the decrease of structural hydroxyl groups depended on both tantalum oxyanions and carbonate contents. In the XPS profile, the Ta 4 f peak of the doped sample could be decomposed into four main components, which showed different oxidation states for tantalum (TaO₂ oxide). According to the TEM observations, the doped calcined powder at 900 °C was composed of uniform nanoneedles with an average length and width of 120 ± 50 and 10 ± 5 nm, respectively.     

水热法合成ATO纳米粉体的研究

以SnCl4·5H2O和SbCl3为锡源和锑源,采用水热法制备锑掺杂氧化锡（ATO）纳米粉体,分析了锑掺杂量、水热时间、水热温度对ATO纳米粉体的影响。研究结果表明：在180℃的温度下水热反应16 h后,Sb元素全部固溶进SnO2的晶格,且分布比较均匀,ATO颗粒径在10 nm左右;粉体的晶粒径随锑掺杂量的增加而逐渐减小,但随水热时间的延长而逐渐增大;随着水热温度的升高,所得粉体由无定形向晶形转变,粉体的结晶性变好。     

Hazard Characterization of Aluminum Nanopowder Compositions

The thermal behaviour in air of two Al nanopowders, Alss and Alsstef, a Teflon coated version of Alss, was determined using DSC, TG‐DTA and accelerating rate calorimetry (ARC). Compared to two larger Al nanopowders, for which hazards results have been reported, Alss and Alsstef are less reactive in air, possibly due to the nature of the passivating and coating layers. The stability of Alss and Alsstef in a wet environment was also investigated using ARC. Alss is very reactive with water, which could lead to a problem of aging in a humid atmosphere. The ”coating” of Alsstef significantly reduces the reactivity of Alss with water. Outgassing behaviour of mixtures of ADN, GAP and various Al powders was investigated using TG‐DTA‐FTIR‐MS. No chemical interactions were observed between ADN/Al, GAP/Al and ADN/GAP. The effect of the addition of Al nanopowders on the thermal decomposition of ADN and GAP was studied using ARC. Al nanopowders had a minor effect on the thermal stability of ADN, while the addition of Alss and Alsstef lowered the onset temperature of GAP. The electrostatic discharge (ESD), impact and friction sensitivities of Al nanopowders and their mixtures with ADN and GAP were also determined. Al nanopowders appear to sensitize ADN to ESD, impact and friction.     

不同佐剂流感疫苗的小鼠免疫效果

目的评价不同佐剂流感疫苗的小鼠免疫效果。方法培养并纯化流感病毒鼠肺适应株PR/8/34,制备流感病毒裂解液。将BALB/c小鼠随机分为5组:流感病毒PR/8/34裂解液(HA)组、HA+大肠杆菌不耐热肠毒素b亚单位(Heat-labile exterotoxin B subunit,LTB)组、HA+弗氏不完全佐剂(FIA)组、HA+A(lOH)3组和生理盐水对照组,HA+LTB组采用滴鼻黏膜免疫,免疫剂量为50μl/只,其余各组均采用肌肉注射,免疫剂量为100μl/只,共免疫2次,间隔2周。于初次免疫后28 d,经小鼠眼内眦采血,分离血清,检测各组小鼠血清IgG抗体效价、血凝抑制效价及攻毒后保护力及鼠肺病毒RNA载量,评价不同佐剂对流感疫苗的免疫增强作用。结果各佐剂组小鼠血清IgG抗体水平及血凝抑制效价均显著高于HA组,且差异均有统计学意义(P均<0.01);HA+FIA组小鼠血清IgG抗体水平及血凝抑制效价均显著高于HA+LTB组和HA+A(lOH)3组(P均<0.01);HA+LTB组与HA+A(l OH)3组抗体效价差异无统计学意义(P>0.05)。各佐剂组和HA组小鼠攻毒后均存活,HA+FIA组鼠肺病毒RNA载量最低,HA+LTB组与HA+A(lOH)3组相当。结论不同佐剂对流感疫苗均有一定的免疫增强作用,其中LTB滴鼻免疫和A(lOH)3肌肉注射对流感疫苗的免疫增强作用相当。     

表面引发剂对熔融铝合金直接氧化生长的影响

为了控制熔融铝合金直接氧化法制备Al2O3/Al复合材料的氧化生长,采用ZnO,SiO2和MgO3种表面引发剂,研究它们对Al-Si-Zn合金氧化生长过程及Al2O3/Al复合材料组织形貌的影响.结果表明:与未使用引发剂时相比,使用SiO2,ZnO或MgO表面引发剂制备的粉末都能显著地缩短Al-Si-Zn合金的氧化生长孕育期,提高合金氧化生长速率,改善复合材料的胞状生长方式,提高复合材料的组织均匀度和致密度,为实际生产应用提供了依据.实验发现:ZnO表面引发剂的使用效果最为突出,其最佳添加量为12mg/cm2.     

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.     

Structural Stability and Conductivity of Phase-Stabilized Cubic Bismuth Oxides

Bismuth oxide, when stabilized in the face-centered cubic phase by lanthanide doping, has one of the highest oxygen-ion conductivities among all solid oxide electrolytes. We previously reported a time-dependent aging phenomenon in phase-stabilized bismuth oxides that involves ordering of the anion sublattice, as distinct from a crystallographic phase change, and results in decreased conductivity. In this paper, we report on the structural stability of the disordered lattice in terms of aging, as a function of both dopant species and dopant concentration. The aging rate decreases with both increased dopant cation radius and increased dopant concentration.     

纳米级金属和金属复合物粉末对高氯酸铵和高氯酸铵/聚合丁二烯复合固体推进剂热分解特性的影响

Effects of metal (Ni, Cu, Al) and composite metal (NiB, NiCu, NiCuB) nanopowders on the thermal decomposition of ammonium perchlorate (AP) and composite solid propellant ammonium perchlorate/hydroxyterminated polybutadiene (AP/HTPB) were studied by thermal analysis (DTA). The results show that metal and composite metal nanopowders all have good catalytic effects on the thermal decomposition of AP and AP/HTPB composite solid propellant. The effects of metal nanopowders on the thermal decomposition of AP are less than those of the composite metal nanopowders. The effects of metal and composite metal nanopowders on the thermal decomposition of AP are different from those on the thermal decomposition of the AP/HTPB composite solid propellant.     

Synthesis and dissolution behavior of nanosized silicon and magnesium co-doped fluorapatite obtained by high energy ball milling

Nanosized hydroxyapatite (HA) powders exhibit a greater surface area than coarser crystals and are expected to show an improved bioactivity. In addition, properties of HA can be tailored over a wide range by incorporating different ions into HA lattice. The aim of this study was to prepare and characterize silicon and magnesium co-doped fluorapatite (Si–Mg–FA) with a chemical composition of Ca_9.5Mg_0.5 (PO₄)_5.5(SiO₄)_0.5F₂ by the high-energy ball milling method. Characterization techniques such as X-ray diffraction analysis (XRD), Fourier transformed infrared spectroscopy (FTIR), energy dispersive X-ray spectroscopy (EDX) and transmission electron microscopy (TEM) were utilized to investigate the structural properties of the obtained powders. Dissolution behavior was evaluated in simulated body fluid (SBF) and physiological normal saline solution at 37 °C for up to 28 days. The results of XRD and FTIR showed that nanocrystalline single-phase Si–Mg–FA powders were synthesized after 12 h of milling. In addition, incorporation of magnesium and silicon into fluorapatite lattice decreased the crystallite size from 53 nm to 40 nm and increased the lattice strain from 0.220% to 0.296%. Dissolution studies revealed that Si–Mg–FA in comparison to fluorapatite (FA), releases more Ca, P and Mg ions into SBF during immersion. 175 ppm Ca, 33.5 ppm P and 48 ppm Mg were detected in the SBF containing Si–Mg–FA after 7days of immersion, while for FA, it was 75 ppm Ca, 21.5 ppm P and 29 ppm Mg. Release of these ions could improve the bioactivity of the obtained nanopowder. It could be concluded that the prepared nanopowders have structural properties such as crystallite size (~40 nm), crystallinity degree (~40%) and chemical composition similar to biological apatite. Therefore, prepared Si–Mg–FA nanopowders are expected to be appropriate candidates for bone substitution materials and also as a phase in polymer or ceramic-based composites for bone regeneration in tissue engineering applications.     

Morphological Control of Centimeter Long Aluminum-Doped Zinc Oxide Nanofibers Prepared by Electrospinning

Centimeter long aluminum-doped zinc oxide (AZO) nanofibers were prepared by electrospinning from polyvinyl alcohol (PVA) aqueous solutions, and the fibers with controlled morphology were expected to have potential applications in gas-sensing and optoelectronic devices. In our research, the diameter and morphology of the nanofibers can be controlled by the applied voltage, the concentration of PVA, and the aluminum (Al) dopant. The introduction of Al resulted in a decrease of the zinc oxide lattice constant by 0.41% and uniform distribution of the nanofiber diameters. Possible mechanisms were proposed to discuss the variations of diameter and morphology.     

掺杂对巨磁电阻钙钛矿La1-xAx(MnB)O3 Curie温度的影响

测定了La1-xAx(MnB)O3（A为二价元素）型巨磁电阻钙钛矿化合物在不同组成的Curie温度。钙钛矿锰氧化物La1-xAx(MnB)O3的A位离子掺杂引起的晶格畸变可以用晶格能来表示，晶格能的大小能很好解释A位离子掺杂引起的Curie温度变化；B位离子掺杂引起的晶格畸变可用极化力来表示，极化力的大小很好解释了B位离子掺杂引起的Curie温度变化。钙钛矿锰氧化物的A，B位离子同时掺杂引起晶格畸变，可以用晶格能和极化力的综合判断系数（晶格能／极化力）来表示，它能很好解释A和B位离子同时改变引起的Curie温度变化，理论与实验结果一致。     

Na2SO4掺杂含MgO铝酸钙熟料的结构表征及浸出性能

使用分析纯MgO、CaCO₃、SiO₂、Al₂O₃与Na₂SO₄在1350℃保温1 h合成了掺杂Na₂SO₄的含MgO铝酸钙熟料,在Na₂CO₃溶液体系下研究了其氧化铝浸出性能,通过XRD等分析手段对其晶体结构和自粉化性能进行了研究。结果表明,Na₂SO₄可以显著提升铝酸钙熟料的浸出性能,Na₂SO₄掺杂量由0%提高到4%,熟料的氧化铝浸出率由61.89%提高到92.01%,继续添加Na₂SO₄,浸出性能趋于稳定。由XRD结果可知,Na₂SO₄促使20CaO·13Al₂O₃·3MgO·3SiO₂（Q相）发生分解并使其转变为12CaO·7Al₂O₃（C₁₂A₇）。Na⁺进入C₁₂A₇晶格引起晶格畸变,从而提高C₁₂A₇的氧化铝浸出性能。Na₂SO₄的加入降低了熟料的自粉化性能,Na₂SO₄掺杂量由0%提高到6%,熟料的自粉率由97.46%下降到85.34%,当Na₂SO₄掺杂量达到10%后,熟料自粉率仅为36.3%。     

Al-doped ZnO varistors prepared by a two-step doping process

ABSTRACT

It is difficult to dope Al into main grains of ZnO varistor ceramics, especially for small doping amount. Generally, all raw materials including Al dopant are directly mixed together and sintered into ceramics. However, in this direct doping process, Al is apt to stay in grain boundaries, and almost does not enter grains. This does harm to the electrical properties of ZnO varistors. In this paper, we proposed a two-step doping process. Al₂O₃ powder was first mixed only with a part of the ZnO powder and pre-sintered. The pre-sintered powder was mixed with other additives such as Bi₂O₃ and the rest ZnO. Then ZnO varistor ceramics were prepared via solid state sintering processes. Results showed that two-step doped ZnO varistors exhibited improved electrical properties with a significant increased nonlinear coefficient and a great decreased leakage current compared to directly doped ones because more Al was incorporated into ZnO grains.     

Characterization of Aluminum Nanopowder Compositions

The thermal behaviour of two different Al nanopowders and a micron‐sized Al powder was studied using DSC, simultaneous TG‐DTA, and accelerating rate calorimetry (ARC). The results show that the reactivity of Al powder increases as the particle size decreases. The thermal stability of the smaller Al nanopowder (Als) in water and in a humid atmosphere was determined using ARC and TG‐DTA, respectively. Atomic Absorption Spectrometry (AAS), X‐Ray Photoelectron Spectrometry (XPS) and Auger Electron Spectrometry (AES) were used to characterize the surface chemistry of Alex. The outgassing behaviour for mixtures of RDX and the various Al powders was investigated using TG‐DTA‐FTIR‐MS. Evolution of NO₂ and N₂O from a chemical interaction between Al nanopowders and RDX was observed. The effect of Als and Alex on the thermal stability of TNT, RDX, Comp B, and AP was determined using ARC. Addition of Als significantly lowered the onset temperature for TNT and RDX decomposition. Electrostatic discharge (ESD) sensitivities of Al nanopowders and their mixtures with TNT, Comp B, RDX and AP were determined. The results show that the AP/Als mixture is very sensitive to ESD. Standard dust explosibility tests demonstrated that Alex is highly explosible.     

Effects of Nanometer Ni,Cu, Al and NiCu Powders on the Thermal Decomposition of Ammonium Perchlorate

A study of the decomposition behaviour for Ammonium Perchlorate(AP) was carried out by differential thermal analysis and the two decomposition peaks were observed. The high temperature peak was found to shift to lower temperatures, but the corresponding shift in the low temperature peak was smaller due to the effect of nanometer metal powders. Results shows that Cu and NiCu nanopowders decreased both the high and low decomposition temperature, while Ni and Al nanopowders just decreased the high decomposition temperature and increased the low decomposition temperature. Metal micron‐sized powders show catalytic effects on the thermal decomposition of AP, but their effects are less than that of nanometer metal powders. With the increase in content, nanometer metal powders enhanced their catalytic effect on the high temperature decomposition of AP, however their effect was weakened on the low temperature decomposition.     

Investigation on the structural and microstructural properties of copper-doped hydroxyapatite coatings deposited using solution precursor plasma spraying

Structural and microstructural investigation of solution precursor plasma sprayed copper-doped hydroxyapatite coatings with different Cu dopant concentration was carried out. Scanning electron micrographs did not show any significant morphological changes at the surface and cross-section of the coatings as copper content increases. X-ray diffraction results showed the decrease in the HA phase content from 93 wt.% to 14 wt.% and its degree of crystallinity from 94% to 85% with increasing copper concentration. Raman and IR spectra revealed the broadening and red-shifting of the phosphate bands due to the distortion of the HA structure caused by possible insertion of copper. X-ray photoelectron spectroscopy identified Cu and Cu²⁺ as copper species incorporated in HA. Rietveld refinement showed an increase in the lattice a and c parameter and expansion of the unit cell volume associated to an interstitial insertion of Cu along the hexagonal channel of the HA structure.