HAp/SiO2复合陶瓷材料的制备及体外生物活性

HAp和SiO2的混合粉末压制成型后,在1200℃下烧结得到含5.0%(质量分数)SiO2的HAp/SiO2生物陶瓷复合材料。烧结体的XRD及FT-IR分析结果表明,SiO2的添加促进了HAp发生热分解。其主要物相为α-TCP、HAp、Ca2P2O7以及生物玻璃(bioglass,BG)等。体外生物活性实验结果显示,样品浸泡在模拟体液(SBF)中24h后,表面出现花瓣状磷灰石沉积物,72h后进而生成板状沉积物,120h后在样品表面覆盖了较厚的类骨磷灰石层,经XRD测试分析表明,该层主要为碳酸羟基磷灰石(HCA)。制备的HAp-5.0%(质量分数)SiO2生物陶瓷复合材料具有比纯HAp更加优越的体外生物活性,可期待作为一种新的骨修复材料。     

液相法在Gd2O3:Eu表面包覆SiO2的研究

采用液相法成功的在球形Gd2O3Eu荧光粉颗粒表面包覆一层纳米SiO2保护膜.扫描电镜分析可见包覆SiO2后颗粒粒径略微变大说明表面包覆一层纳米级的包覆层.XPS分析表明SiO2包覆层与Gd2O3Eu颗粒表面以Gd(Eu)-O-Si化学键的方式键合在一起的.荧光光谱分析表明包覆后的Gd2O3Eu3+颗粒仍旧是一种很好的发光材料.     

CaO-P2O5-SiO2系统溶胶-凝胶玻璃的生物矿化行为

利用体外实验方法(in vitro)以及XBD、SEM、FTIR、BET、ICP等手段研究了两种溶胶一凝胶生物活性玻璃的显微结构及其在模拟生理溶液(SBF)中的降解过程、表面反应产物和生物矿化机理．结果表明，两种生物活性玻璃都具有较高的生物活性，均具有由纳米尺寸颗粒相互连接而成的微孔结构和较大的比表面积，在模拟生理溶液(SBF)中浸泡后可形成表面类似天然骨中无机矿物的碳酸经基磷灰石层(HCA)，说明两者均具有较高的生物活性和生理环境相应特性．材料表面的硅酸凝胶层及其硅经基团的形成对碳酸经基磷灰石(HCA)微晶的成核有重要作用。     

生物活性陶瓷材料表面碳酸羟基磷灰石形成及其微观结构的研究

制备了羟基磷灰石(HAP)、生物活性玻璃、硅灰石以及羟基磷灰石和硅灰石的复合陶瓷等几种不同的生物活性陶瓷材料,在同一条件下对材料进行模拟体液(SBF)浸泡实验并用傅立叶红外光谱(FTIR)和场发射扫描电镜(FESEM)对试样表面进行了表征.结果显示,几种生物陶瓷材料经模拟体液浸泡后,表面都沉积了碳酸羟基磷灰石(HCA).不同的材料,表面沉积HCA的速度和微观结构有所差异.在硅灰石表面沉积HCA的速度最快,而在HAP表面沉积HCA的速度为最慢.HAP和硅灰石表面沉积的HCA层较为疏松,与此相比生物活性玻璃表面沉积的HCA层较为致密.这几种生物活性陶瓷材料表面沉积的HCA基本上都为光滑的球形颗粒.羟基磷灰石与硅灰石复合后不仅沉积HCA的速度发生很大变化,而且表面生成的HCA的微观结构也发生了改变.我们的结果显示,在模拟体液中材料表面HCA沉积速度和微观结构可以作为评价无机生物材料体外生物活性的一个重要方法,而通过羟基磷灰石和硅灰石复合可以调控材料的生物活性。     

SiO2-Ag纳米复合颗粒自组装的制备与表征

利用自组装法在空气-水界面制备了SiO2薄膜粒子,将所制薄膜粒子先后用AgNO3溶液与Na2S2O3溶液浸泡,并充分曝光,形成了一种形状如"西瓜"的SiO2-Ag纳米复合颗粒.采用X射线衍射(XRD)、透射电子显微镜(TEM)、紫外可见吸收光谱(UV-Vis)对其结构进行了表征和分析,并初步探讨了其结构的形成机理.结果表明,纳米Ag"瓜子"均匀地分散于SiO2"瓜瓤"颗粒中,形成的复合颗粒呈球形,粒径均匀.     

溶胶-凝胶生物活性玻璃超细粉体的制备与生物矿化性能研究

通过溶胶-凝胶和湿法研磨工艺制备了粒径分布在1μm以下的生物活性玻璃超细粉体. 采用XRD、FTIR、SEM测试方法对研磨前后粉体在模拟生理溶液(SBF)中的生物矿化性能进行了对比分析与表征, 结果表明: 在SBF中两种粉体表面都生成了碳酸羟基磷灰石(HCA), 并且经湿法研磨后的溶胶-凝胶生物活性玻璃超细粉体的生物矿化速度显著提高. 通过对不同浸泡时间SBF溶液的pH值测定可知, 在同样反应时间情况下, 超细粉体浸泡液的pH值低于研磨前颗粒. 浸泡液的ICP测试也表明研磨前后玻璃样品的离子溶出规律有所不同.     

PbBr2-PbF2-P2O5玻璃的结构研究

采用红外光谱（IR）和X射线光电子能谱（XPS）等方法研究了PbBr2-PbF2-P2O5系铅卤磷酸盐玻璃的结构。结果表明，Pb^2 离子在玻璃中起着网络修饰阳离子和网络形成体的双重作用。当P2O5含量为60mol%时，Pb^2 离子主要是作为网络修饰体；当P2O5含量降低到50mol%时，一部分Pb^2 离子能够进入玻璃网络形成[PbO4]四面体或P－O－Pb键。Br^-和F^-离子达到一定浓度时就会进入玻璃网络，形成[PO4-nXn](X=Br或F，n=0-4)四面体使磷酸盐链长变短。玻璃中P2O5的含量不变时P－O－P键的比例也基本保持不变；当P2O5的含量降低时，P－O－P键和P－O^-键的含量都减少，P－O－Pb键的含量则明显增加。     

SiO2/Al2O3复合包覆TiH2颗粒的制备及释氢性能的研究

采用非均匀成核法,通过控制滴加反应物的速度、pH值等,实现SiO2和Al2O3在TiH2颗粒表面形核,制备包覆有SiO2和Al2O3的复合型TiH2发泡剂.观察了包覆层形貌,进行了释氢试验.实验结果表明:SiO2/Al2O3包覆层平滑、分布均匀,形成内松外紧的结构,使得释氢时间达到120s.     

后处理工艺对阳极氧化钛生物活性的影响

钛及钛合金由于具有良好的力学、生物学性能,已成为良好的骨修复和替换材料。为了改善钛的生物活性,首先采用两步电化学阳极氧化法对金属纯钛进行表面改性,即使之表面形成多孔纳米结构,然后对样品进行不同的后处理,如450℃热处理,NaOH处理,NaOH-CaCl2处理,最后将后处理样品浸泡在人体模拟液(SBF)中,研究磷灰石在样品表面的生长情况。采用X射线衍射(XRD)、带能量散射谱(EDS)的场发射扫描电子显微镜(FE-SEM)、傅里叶变换红外光谱(FT-IR)、电感耦合等离子体发射光谱仪(ICP-OES)等对生成的磷灰石的物相、形貌、元素组成等进行表征。结果表明,非晶TiO2纳米管阵列不能诱导磷灰石在其表面生成,而经450℃退火处理后形成的结晶良好的锐钛矿相TiO2纳米管阵列具有一定生物活性,即可诱导部分磷灰石颗粒在其表面生成。进一步经NaOH-CaCl2溶液后处理可加速羟基磷灰石在样品表面的形成速度,样品在模拟体液(SBF)中浸泡8d后,表面生成的磷灰石厚度约为5μm,磷灰石层是由大量球形颗粒堆积而成的,而球形颗粒是由无数纳米薄片组成的花状结构。     

介孔SiO2负载和包覆的纳米金属颗粒的制备与研究

制备了以SiO2为核、介孔SiO2为壳的核-壳颗粒负载纳米金属颗粒以及介孔SiO2壳层包覆SiO2负载的纳米金属颗粒。结果表明,十六烷基三甲基溴化胺(CTAB)作为模板剂,有助于介孔SiO2壳层包覆SiO2核的结构形成,介孔SiO2壳层的孔径方向垂直于SiO2核的表面;在聚乙烯吡咯烷酮(PVP)的稳定作用下,Pt纳米颗粒能均匀地分布在介孔SiO2壳层的表面。单分散SiO2颗粒经过3-氨丙基三乙氧基硅烷(APS)功能化后,可负载纳米金属颗粒。进一步研究表明,以SiO2负载纳米金属颗粒为核,NH3.H2O,乙醇和水为分散剂,CTAB为模板剂,正硅酸乙酯(TEOS)为硅源,还能制备介孔SiO2壳包覆SiO2负载的纳米金属颗粒,而且介孔SiO2壳层的厚度可通过TEOS的含量调节。     

Comparison of the Electronic Structures of La2CuO4, Sr2CuO2Cl2, and Sr2CuO2F2

First-principles cluster calculations are reported of the local electronic structure of the three compounds: La₂CuO₄, Sr₂CuO₂Cl₂, and Sr₂CuO₂F₂. The copper and the planar oxygen 2p atomic orbitals exhibit a similar degree of covalency. The out-of-plane orbitals, however, are quite different with the atomic orbital lowered significantly in energy for chlorine and fluorine apical positions.     

Magnetic properties of quaternary compounds on the Cu2GeSe3-Cr2Se3 join of the Cu2Se-GeSe2-Cr2Se3 system

We have synthesized two quaternary compounds, Cu₂GeCr₄Se₉ and Cu₂GeCr₆Se₁₂, with compositions on the Cu₂GeSe₃-Cr₂Se₃ join of the Cu₂Se-GeSe₂-Cr₂Se₃ system. Their composition stability limits and the lattice parameters of Cu₂GeCr₄Se₉ have been determined, and their magnetic properties (magnetic moments, temperatures and types of magnetic transitions) have been investigated. Ferromagnetic samples with Curie temperatures from 95 to 135 K have been identified in the homogeneity ranges of the two compounds. Original Russian Text ? T.G. Aminov, G.G. Shabunina, E.V. Busheva, 2009, published in Neorganicheskie Materialy, 2009, Vol. 45, No. 3, pp. 283–287.     

Reactivity of the H2O2/TiO2 system

The reactivity of the H₂O₂/TiO₂ system for samples treated at atmospheric pressure is studied by means of Auger Electron Spectroscopy. The most significant changes on the TiO₂ ‘final’ state are: (i) The I(O)/I(Ti) peak-to-peak ratio is diminished by 15%. (ii) The LMV transition suffers an energy shift of +2 eV, whereas the peak-to-peak width diminishes 1.5 eV. (iii) Its structure changes with respect to that of the TiO₂ ‘initial’ state although it is not identified with any one of the known stoichiometric oxides. (iv) When the samples that represent the ‘final’ state are heated up to 650 K, the AES spectrum matches quite well that of the TiO₂ ‘initial’ state.     

Nanocrystallization of SrBi2Nb2O9 from glasses in the system Li2B4O7---SrO---Bi2O3---Nb2O5

Transparent glasses in the system (100−x)Li₂B₄O₇–x(SrO---Bi₂O₃---Nb₂O₅) (10≤x≤60) (in molar ratio) were fabricated by a conventional melt-quenching technique. Amorphous and glassy characteristics of the as-quenched samples were established via X-ray powder diffraction (XRD) and differential thermal analyses (DTA) respectively. Glass–ceramics embedded with strontium bismuth niobate, SrBi₂Nb₂O₉ (SBN) nanocrystals were produced by heat-treating the as-quenched glasses at temperatures higher than 500 °C. Perovskite SBN phase formation through an intermediate fluorite phase in the glass matrix was confirmed by XRD and transmission electron microscopy (TEM). Infrared and Raman spectroscopic studies corroborate the observation of fluorite phase formation. The dielectric constant (_r) and the loss factor (D) for the lithium borate, Li₂B₄O₇ (LBO) glass comprising randomly oriented SBN nanocrystals were determined and compared with those predicted based on the various dielectric mixture rule formalism. The dielectric constant was found to increase with increasing SBN content in LBO glass matrix.     

Thermoelectric properties of the tetradymite-type Bi2Te2S-Sb2Te2S solid solution

The thermoelectric properties of the tetradymite-type Bi_2−xSb_xTe₂S solid solution (0 ≤ x ≤ 2) are reported for the temperature range 5-300 K. The properties of non-stoichiometric, Cl and Sn doped n- and p-type variants are reported as well. The Seebeck coefficients for these materials range from −170 to +270 μV K⁻¹ while the resistivities range from those of semimetals, 2 mΩ cm, to semiconductors, >1000 mΩ cm. Thermal conductivities were low for most compositions, typically 1.5 W m⁻¹ K⁻¹. Nominally undoped Bi₂Te₂S shows the highest thermoelectric efficiency amongst the tested materials with a ZT = 0.26 at 300 K that decreased to 0.04 at 100 K. The crystal structure of Sb₂Te₂S, a novel tetradymite-type material, is also reported.     

Subsolidus phase equilibria in the Al2O3-CeO2-PbO and Al2O3-CeO2-RuO2 systems

The subsolidus phase equilibria in air for the Al₂O₃-CeO₂-PbO and Al₂O₃-CeO₂-RuO₂ systems were studied with the aim of obtaining information on possible interactions between a CeO₂-based solid electrolyte in solid-oxide fuel cells (SOFCs) and other oxides. No ternary compound was found in either of the systems. The tie line in the Al₂O₃-PbO-CeO₂ system is between Al₂Pb₂O₅ and the CeO₂.     

Li2O/K2O物质的量比对P2O5-Al2O3-BaO-Li2O-K2O磷酸盐玻璃热光性能的影响

通过高温熔融法制备了不同Li_2O/K_2O物质的量比的磷酸盐玻璃,研究了其热学性能和热光性能。采用干涉仪法测试了玻璃的折射率温度系数dn/dT,并进一步计算获得了热光系数。结果表明:随着Li_2O/K_2O物质的量比的增大,玻璃的转变温度Tg、软化温度Tf、热膨胀系数α皆出现极值点,呈现明显的混合碱效应;而玻璃的热光系数dS/dT随着Li_2O含量增加而增大,当Li_2O/K_2O物质的量比为9∶6时,玻璃的dS/dT为0.08×10~(-6)/K;在磷酸盐体系中可获得具有零热畸变的光学玻璃。     

Phase relations of the Li2O-Ta2O5-B2O3 and Li2O-WO3-B2O3 systems and promising nonlinear optical compounds in K2O-Ta2O5-B2O3 system

The subsolidus phase equilibria of the Li₂O-Ta₂O₅-B₂O₃, K₂O-Ta₂O₅-B₂O₃ and Li₂O-WO₃-B₂O₃ systems have been investigated mainly by means of the powder X-ray diffraction method. Two ternary compounds, KTaB₂O₆ and K₃Ta₃B₂O₁₂ were confirmed in the system K₂O-Ta₂O₅-B₂O₃. Crystal structure of compound KTaB₂O₆ has been refined from X-ray powder diffraction data using the Rietveld method. The compound crystallizes in the orthorhombic, space group Pmn2₁ (No. 31), with lattice parameters a = 7.3253(4) Å, b = 3.8402(2) Å, c = 9.3040(5) Å, z = 2 and D_calc = 4.283 g/cm³. The powder second harmonic generation (SHG) coefficients of KTaB₂O₆ and K₃Ta₃B₂O₁₂ were five times and two times as large as that of KH₂PO₄ (KDP), respectively.     

Photoluminescence of lanthanide-doped CaSi2O2N2 phosphors and the energy-level diagram of lanthanide ions in CaSi2O2N2

Lanthanide-doped CaSi₂O₂N₂ phosphors were synthesized by solid-state reaction. Their photoluminescence (PL) properties were investigated and analyzed systematically. Energy transitions attributed to electron transfers from 4f to 4f (ff), from 4f to 5d (fd), from 5d to 4f (df) and charge transfer (CT) transition were obtained and classified. Finally, an energy-level diagram of lanthanide-ions in CaSi₂O₂N₂ was proposed. The diagram matches perfectly with the experimental results and explains the luminescence properties of lanthanide-doped CaSi₂O₂N₂ phosphors. The electron-vibrational interaction in 4f-5d optical transitions of CaSi₂O₂N₂:Eu²⁺ was also studied.     

掺杂不同量Nd2O3对CeO2-ZrO2-Al2O3材料性能的影响

采用共沉淀法制备了一系列Nd2O3含量为0～13wt%的CeO2-ZrO2-A12O3(CZA)复合氧化物,并通过X射线衍射(XRD)、低温N2吸附–脱附、氧脉冲吸附(OSC)、H2–程序升温还原(H2-TPR)及扫描电子显微镜(SEM)等方法对所制备的材料进行了表征.研究结果表明,Nd2O3在CZA固溶体中的溶解限约为10wt%,过量Nd的添加会出现分相形成Nd0.5Ce0.5O1.75氧化物.掺杂适量Nd能有效抑制氧化物晶粒的长大,提高材料的热稳定性和氧化还原性能.Nd2O3的掺杂量为10wt%时,样品的织构稳定性最好,1000℃老化5 h后,比表面积和孔容分别达97.14 m2/g和0.44 mL/g.Nd2O3的掺杂量为7wt%时,样品有高的储氧量,经600℃和1000℃焙烧后储氧量分别为938.01μmol/g和821.72μmol/g;体相氧的移动能力最强,还原性能最佳,老化后还原峰温由465℃升高到483℃.SEM结果表明,所制备的材料均为球形颗粒,Nd2O3的添加可以有效阻止高温焙烧过程中粒子的团聚.