Electrostatic Spray Deposition of Biomimetic Nanocrystalline Apatite Coatings onto Titanium

Titanium (Ti) and its alloys are widely used to manufacture orthopedic and dental implants due to their excellent mechanical properties and corrosion resistance. Although these materials are bioinert, improvement of biological properties (e.g., bone implant contact) can be obtained by the application of a coating made of nanostructured apatite. The aim of this study was to investigate the applicability of the electrostatic spray deposition (ESD) technique for the deposition of nanostructured apatite coatings onto commercially pure (cp) Ti substrates at room temperature. To that end, poorly crystalline, nano‐sized, carbonate‐apatite plate‐like particles with dimensions similar to the nanocrystals present in bone were synthesized using wet‐chemical precipitation techniques and their physicochemical properties were subsequently characterized thoroughly. The apatite suspensions were optimized for the ESD process in terms of dispersion, aggregation, and stability. Furthermore, relevant ESD processing parameters, including nozzle‐to‐substrate distance, relative humidity in the deposition chamber and deposition time were varied in order to study their effects on coating morphology. Porous films made of agglomerates of nano‐sized apatite particles of ≈50 nm were generated, demonstrating the feasibility of the ESD technique for the deposition of thin apatite coatings with a nano‐sized surface morphology onto titanium substrates. The ability of these nanocrystals to bind therapeutic agents for bone diseases and the capability of ESD to produce coating at physiological conditions makes this work a first step toward the set‐up of coatings for bone implants based on surface‐activated apatite with improved functionality.     

Structural characterization of silicon-substituted hydroxyapatite synthesized by a hydrothermal method

Silicon-substituted hydroxyapatite (Si-HA) was prepared successfully by hydrothermal method. The crystalline phase, microstructure, chemical composition, morphology and thermal stability of Si-HA were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM) and differential scanning calorimetry (DSC). The results show that the substitution of the silicate groups for the phosphate groups causes some OH^- loss to maintain the charge balance and changes the lattice parameters of HA. Furthermore, the substitution of the silicate groups restrains the growth of Si-HA crystal. DSC analysis shows that the small amount of silicon incorporates into HA lattice does not influence the thermal stability of HA.     

纳米粒子晶格畸变率的数量级研究

晶格畸变率是纳米粒子的一个重要参数。用X射线衍射积分宽度法确定了纳米CeO2粒子的晶格畸变率，研究了晶格畸变与晶粒度之间的关系，结合已有资料讨论了纳米粒子晶格畸变率的数量级大小。结果表明，不合理的计算方法可能导致计算出来的晶格畸变值严重失实。     

Studies on Ag/Polypyrrole composite deposited on the surface of styrene-methyl acrylate copolymer microparticles and their electrical and electrochemical properties

The colloidal dispersion of silver nano particles with different concentration (0.5, 1.0 and 1.5%) were synthesized by chemical reduction method using citrate as reducing agent. Colloidal dispersion of Poly (Styrene-co-methylacrylate) (SMA) was synthesized by mini emulsion polymerization technique. The SMA micro particles were used as template for the polymerization of pyrrole in presence of dispersion of silver nano particles by oxidative coupling method. The Ag nano particles and the final core–shell composite particles were characterized by UV–visible, FTIR, SEM, EDX and TEM analysis. The thermal analysis revealed that the SMA-PPy-Ag core–shell particles possesses better thermal stability in comparision with bare PPy-Ag nano composite. The dc conductivity and the electro chemical behaviour of the particles were studied by using a standard four-probe method. The dependence of electrical conductivity of the composites on the concentration of silver in the polypyrrole shell and the methyl acrylate content in SMA copolymer were also investigated The core–shell particles show reversible electrochemical response as revealed by the cyclic voltammetry study.     

晶格常数的变化对钛酸铝热稳定性的影响

深入研究了晶格常数的变化和钛酸铝热稳定性的关系．通过仔细分析钛酸铝的晶格常数随温度变化的特点,发现钛酸铝的晶格常数Ｃ随温度升高而降低这一反常现象．提出了钛酸铝的稳定性与其晶格常数Ｃ的大小密切相关的论点．在钛酸铝中引入多种添加剂以改变其晶格常数．结果发现晶格常数Ｃ的大小反映了钛酸铝的稳定性．晶格常数Ｃ越大,钛酸铝就越稳定.钛酸铝稳定性提高的原因是：晶格常数ｃ对应于钛酸铝晶体结构中畸变的［ＭｅＯ₆］八面体的高度,Ｃ值增大导致八面体的畸变程度降低,结果就使得钛酸铝更稳定．还研究了不同烧成工艺对钛酸铝的晶格常数和稳定性的影响,结果发现：随着烧成温度的提高和保温时间的延长,钛酸铝的晶格常数Ｃ增大,其稳定性也相应提高．     

硬脂酸凝胶法制备CeO2纳米粉体

采用硬脂酸凝胶法制备了CeO2纳米晶。XRD分析表明,当焙烧温度为450～900℃时,所合成的CeO2纳米晶均属于单相立方晶系,空间群为O5H-FM3M;计算表明,随焙烧温度的升高,平均晶粒度增大,而平均晶格畸变率则随平均晶粒度的增大而减小,表明粒子越小,晶格畸变越大,晶粒发育越不完整。TEM分析表明,CeO2纳米晶呈球形,粒度随焙烧温度的增加而增大。热失重分析表明,当焙烧温度高于750℃时,CeO2中的杂质基本挥发完毕。相对密度分析表明,随CeO2纳米晶粒度的增大,粉末的密度增加。,CeO2 nanocrystalline particulates of different sizes were prepared by stearic acid gel method.XRD patterns showed that the synthesized CeO2 was cubic in structure with single-phase when calcination temperature was 450-900℃,space group was O5H-FM3M.Calcination revealed that the mean crystalline size increased with the increase of calcinstion temperature,but average crystal lattice distortion rate decreased with the increasing in the average crystalline size.This indicated that the smaller the particle size,the bigger crystal lattice distortion,the worse the crystal growed.TEM photos revealed that CeO2 particles were spherical in shape,and the mean sizes of the C eO2 particles increased with the increase of calcination temperatures.Weight loss analysis indicated that the impurity in CeO2 completely volatilized when calcination temperature was above 750℃.The density of nanocrystalline CeO2 powders analysis showed that the density of CeO2 nanocrystalline powders increased with the increasing in CeO2 particles sizes.     

纳米氮化钛粉体的制备及其影响因素

以纳米TiO₂为原料,采用氨气氮化法制备了纳米TiN粉体。研究了制备过程中的影响因素。实验结果表明:在800℃下,氮化反应5h,纳米TiO₂全部转化成纳米TiN,制备的纳米TiN粉体的粒径为20nm左右,采用化学分析法分析了纳米TiN的纯度,采用DTA-TG技术研究了纳米TiN的热稳定性。     

Nanostructured CaWO4, CaWO4 : Pb2+ and CaWO4 : Tb3+ particles: polyol-mediated synthesis and luminescent properties

Nano-submicrostructured CaWO4, CaWO4 : Pb2+ and CaWO4 : Tb3+ particles were prepared by polyol method and characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), Fourier transform infrared spectra (FT-IR), thermogravimetry-differential thermal analysis (TG-DTA), photoluminescence (PL), cathodo-luminescence (CL) spectra and PL lifetimes. The results of XRD indicate that the as-prepared samples are well crystallized with the scheelite structure of CaWO4. The FE-SEM images illustrate that CaWO4 and CaWO4 : Pb2+ and CaWO4 : Tb3+ powders are composed of spherical particles with sizes around 260, 290, and 190 nm respectively, which are the aggregates of smaller nanoparticles around 10-20 nm. Under the UV light or electron beam excitation, the CaWO4 powders exhibits a blue emission band with a maximum at about 440 nm. When the CaWO4 particles are doped with Pb2+, the intensity of luminescence is enhanced to some extent and the luminescence band maximum is red shifted to 460 nm. Tb(3+)-doped CaWO4 particles show the characteristic emission of Tb3+ 5D4-7FJ (J = 6 - 3) transitions due to an energy transfer from WO4(2-) groups to Tb3+.     

Composition and structure of apatite formed on organic polymer in simulated body fluid with a high content of carbonate ion

Apatite layer was formed on polyethyleneterephthalate (PET) substrate by the following biomimetic process. The PET substrate was placed on granular particles of a CaO, SiO₂-based glass in simulated body fluid (SBF) with ion concentrations nearly equal to those of human blood plasma to form apatite nuclei on their surfaces. The apatite nuclei was then grown into a continuous layer by subsequently soaking the substrate in SBF under air or CO₂ atmosphere in which CO₂ partial pressure in the ambient was adjusted to 14.8 kPa to increase the content of carbonate ion to a level nearly equal to that of blood plasma. The increase in the content of carbonate ions in SBF changed the Ca/P atomic ratio of the apatite from 1.51 to 1.63, content of CO₃ ^2- ions from 2.64 to 4.56 wt %, and lattice constants a from 94.32 to 94.23 nm and c from 68.70 to 68.83 nm, respectively. The Ca/P ratio and lattice constants of the apatite formed in SBF under CO₂ atmosphere were approximately identical to those of bone apatite, i.e. Ca/P atomic ratio 1.65, content of CO₃ ^2- ion 5.80 wt % and lattice constants a 94.20 and c 68.80 nm. This indicates that an apatite with composition and structure nearly identical to those of bone apatite can be produced in SBF by adjusting its ion concentrations including the content of carbonate ions to be equal to those of blood plasma.     

纳米Al2O3的晶型对聚酰亚胺杂化薄膜性能的影响

将经偶联剂处理的纳米Al2O3粉体,借助超声波以一定方式均匀分散于聚酰胺酸溶液中,制备出Al2O3不同晶型、不同含量的PI/纳米Al2O3杂化薄膜,并对杂化薄膜微观形貌、聚集态结构、光透过率、热稳定性、电击穿场强进行研究,分析Al2O3晶型和含量对PI/纳米Al2O3杂化薄膜的结构和性能的影响.结果表明:PI/纳米Al2O3杂化薄膜的热稳定性,电击穿场强均高于纯PI薄膜,且随着纳米Al2O3含量的提高热稳定性也随之提高,电击穿场强先升高后降低;填充Al2O3粉体的晶型对PI薄膜分子链堆积密度有较大的影响,导致添加不同晶型Al2O3的杂化薄膜性能的差异.     

The preparation of thin films of zinc sulphide-telluride alloys

Thin films of ZnS-Te alloys have been grown over the whole composition range. Electron microscopy and X-ray diffraction studies have shown that single phase alloys have been produced with average crystalline sizes of 0.1–0.5 microm with some crystallites up to 5 microm. The lattice constants of the ZnS and ZnTe films agreed with bulk single crystal values to within two decimal places.     

Effects of oxygen or nitrogen doping on the microstructures, bonding, electrical, thermal properties and phase change kinetics of GeSb9 films

This study investigated the phase change kinetics, thermal, structural, electrical properties, and chemical bonding state of 50-nm-thick oxygen or nitrogen doped GeSb₉ films prepared by sputtering. Up to 6.8 at.% O or 8.7 at.% N doping, as measured by secondary ion mass spectrometry, the crystallization temperatures, lattice constants, and the resistivity of both crystalline and amorphous films increased with oxygen or nitrogen concentration , while the grain sizes decreased. Nitrogen atoms bonded to Ge and formed GeN₄ nitrides, and both the GeO₂ and Sb₂O₃ co-existed when oxygen concentration reached 8.5 at.%. Crystallization could be triggered by a laser pulse of duration 12 ns for all films. Both GeSb₉-O and GeSb₉-N films had fast crystallization speed, good thermal stability, and improved resistivity and are therefore potential candidates as active layers for phase-change memory.     

纳米Mg(OH)2-ZnO/聚酰亚胺复合薄膜的介电和热性能

采用反向沉淀法制备了Mg（OH）₂-ZnO纳米粒子,通过原位聚合和热亚胺化的方法成功制备了不同纳米Mg（OH）₂-ZnO粒子质量分数的纳米Mg（OH）₂-ZnO/聚酰亚胺（PI）复合薄膜,通过SEM、热重分析、介电谱测试仪和击穿场强测试仪对薄膜的表面形貌、热稳定性、介电性能和击穿强度进行表征和测试。结果表明：Mg（OH）₂-ZnO纳米粒子均匀地分散在PI基体中,Mg（OH）₂-ZnO/PI热稳定性下降,介电常数、介电损耗和电导率增加,击穿场强随纳米粒子增加先增加后减小,在纳米粒子含量为2%时,达到最大值296 kV/mm。     

无机纳米ZnO或蒙脱土颗粒掺杂对低密度聚乙烯介电性能的影响

选择在低密度聚乙烯（LDPE）中掺杂无机纳米ZnO和蒙脱土（MMT）颗粒,探讨不同形态无机纳米颗粒对LDPE介电性能的影响。利用熔融共混法配合不同冷却方式制备不同结晶形态的纳米ZnO/LDPE和MMT/LDPE复合材料。通过FTIR、偏光显微镜（PLM）、SEM、DSC和热刺激电流（TSC）对试样进行表征,并。研究了纳米ZnO/LDPE和MMT/LDPE复合材料的交流击穿特性,结果表明：掺杂适当质量分数并经表面修饰的无机纳米颗粒可有效的避免其团聚现象,提高纳米ZnO/LDPE和MMT/LDPE复合材料的结晶速率,使结晶结构更完善,同时无机纳米颗粒掺杂使LDPE的陷阱密度和深度均有所增加,载流子入陷在试样内部形成界面"局域态"。经油冷却方式制备的纳米ZnO/LDPE和MMT/LDPE复合材料击穿场强比空气自然冷却分别高13.6%和14.4%,当掺杂纳米粒子质量分数为3wt%时,复合材料击穿场强出现最大值,其中纳米ZnO/LDPE复合材料比MMT/LDPE复合材料的击穿场强值高0.68%;电导率试验结果表明：纳米ZnO/LDPE复合材料电导率比MMT/LDPE复合材料低。介电性能测试表明,在1~10⁵ Hz的测试频率范围内,纳米ZnO/LDPE复合材料和MMT/LDPE复合材料介电常数降低,介质损耗角正切值有所提高。     

铈掺杂钛酸钡微粉制备与微波吸收特性研究

采用溶胶一凝胶法制备了稀土铈掺杂钛酸钡纳米晶粉体,借助XRD、Raman、SEM以及矢量网络分析仪等分析测试手段对样品晶相、晶格常数、粒径、表面形貌及微波吸收特性进行了研究.结果表明:铈掺杂样品均形成四方相钛酸钡微晶,晶粒发育良好.随着铈掺杂量增大,晶粒逐渐细化,晶格常数a变大,晶格常数c减小;与未掺杂钛酸钡相比,在2-18GHz频率范围内,稀土铈掺杂材料(掺杂量0.2%)的反射损耗明显地提高,反射峰发生蓝移,尤其5.8GHz和7GHz处反射损耗分别提高了15dB和30dB,频带拓宽近2倍.由此可见铈掺杂有利于改善钛酸钡材料的微波吸收特性.     

新型GYSGG(GdxY3-xSc2Ga3O12)晶体的生长、结构及透过光谱研究

采用提拉法成功生长出高质量的GYSGG(Gd_0.63Y_2.37Sc₂Ga₃O₁₂)晶体, 对其结构及透过光谱进行了研究。GYSGG晶体的晶格常数大于目前常用的GGG 和CaMgZr:GGG,介于YSGG与GSGG之间。可通过改变晶体中Gd与Y的比例, 获得应用中所需不同晶格常数的晶体基片。另外, 晶体三个结晶面的摇摆曲线有对称的形状和较小的半高宽, 表明晶体有较好的结晶完整性。观察分析了晶体三个结晶面的位错腐蚀图。透过光谱分析表明晶体有宽的透光波段, 将计算得到的折射率曲线拟合得到了折射率塞米尔方程系数。因此, GYSGG不仅是一种优良的激光基质晶体, 也是一种宽波段窗口材料和潜在的具有较大晶格常数, 并且晶格常数可调的新型磁泡应用衬底材料。     

Development of Biomimetic Needle-like Apatite Nanocrystals by a Simple New Method

A new method of calcium nitrate and sodium phosphate as reactants was employed to prepare biomimetic apatite nanocrystals by a simple heating treatment in water. The structure and properties of the apatite crystals were investigated by TEM, XRD, IR, ICP and TG. It is found that the apatite nanocrystals contain OH-, CO32-, Na+ and HPO42- ions in their crystal structure. The crystal water is removed during heating from 200℃ to 400℃. CO32-and HPO42- are decomposed at 600℃ to 800℃, also there is lattice vvater lost at this temperature stage. The morphology of the apatite nanocrystals is needle-like with a length less than 80 nm. The size and crystallinity of the apatite nanocrystals increase with vvater treatment temperature and time. Compared to the apatite crystals sintered at 800℃, water treated apatite nanocrystals are poorly crystallized apatite. The results indicate that the apatite nanocrystals have similarity in composition, structure, morphology and crystallinity to that of bone apatite crystal     

纳米ZnO/低密度聚乙烯复合材料的介电特性

为探讨纳米ZnO/低密度聚乙烯（LDPE）复合材料的介电特性,首先,采用硅烷偶联剂和钛酸酯偶联剂对纳米ZnO进行改性,并利用两步法制备了不同纳米ZnO质量分数、不同纳米ZnO粒径、不同纳米ZnO表面修饰方式和不同冷却方式的纳米ZnO/LDPE复合材料;然后,通过FTIR、SEM、DSC和热激电流（TSC）测试了纳米ZnO在基体中的分散情况、复合材料的等温结晶过程参数变化及陷阱密度;最后,在不同实验温度下分别进行了交流击穿、绝缘电导率、介电常数和空间电荷实验。结果表明:纳米ZnO的加入使纳米ZnO/LDPE复合材料内部陷阱深度和密度均有所增加;当纳米ZnO的粒径为40 nm且质量分数为3%时,复合材料的结晶速度最快,纳米ZnO在基体中的分散性较好,击穿场强达到最高值133.3 kV/mm,电导率及介电常数也相对较低,加压时复合材料内部空间电荷少,短路时释放电荷速度快,介电性能较好;由于纳米粒子增加了材料内部的热传导速率,降低了复合材料随着温度升高而降解的速度,因而相对于纯LDPE,随着实验温度的提高,纳米ZnO/LDPE复合材料的击穿场强下降幅度及电导率上升幅度均较小。      

Enhanced hydrothermal stability of ZSM-5 formed from nanocrystalline seeds for naphtha catalytic cracking

We successfully synthesized hydrothermally stable ZSM-5 with crystalline nano seeds. We employed a template-free method using ZSM-5 crystalline nano seeds and sodium silicate as a silica source. The prepared ZSM-5 exhibited uniform crystal size and relative crystallinity greater than 100 %. The size of the crystalline nano seed in the scale of 100 nm was found to be the optimum size for obtaining uniform, highly crystalline ZSM-5 with structural stability. After P-modification, the synthesized ZSM-5 with the optimally sized seed showed high hydrothermal stability and improved catalytic naphtha cracking activity compared to a commercial ZSM-5 catalyst. In order to find the elements for the increased hydrothermal stability, the samples were evaluated by studying crystallinity, aluminum spectrum, and acidity using XRD, solid-state NMR, and NH₃-TPD, respectively after steaming at 800 °C for 24 h. It is speculated that the increased hydrothermal stability of the ZSM-5 resulted mainly from the increased aluminum structural stability.     

Synthesis,growth and structural perfection of nonlinear optical material of glycine hydrofluoride (GHF)

In the present communication, we have successfully synthesized the efficient NLO material of glycine hydrofluoride (GHF) by conventional chemical reaction, and grown the single crystal by adopting slow evaporation solution growth technique. In order to know its suitability for device fabrication, different characterization analyses have been performed. The lattice constants have been determined from powder X-ray diffraction (PXRD) method and found that it crystallizes in orthorhombic crystal system. Its crystalline perfection was evaluated by high-resolution X-ray diffraction technique (HRXRD) and the value of FWHM indicates the presence of low angle structural grain boundaries. Its luminescence behaviour has been analysed by photoluminescence (PL) analysis and found maximum luminescence in the lower wavelength region. Its relative second harmonic generation efficiency was evaluated from Kurtz powder technique. The phase matching angle of GHF was determined by using Nd:YAG laser as a source. Its thermal, mechanical and electrical properties were examined by TG/DTA, Vickers microhardness tester and dielectric measurements, respectively.