纳米羟基磷灰石球状晶体的合成及其吸附特性的研究

以硝酸钙和磷酸氢二铵为先驱体，通过简易的湿法合成制备了纳米级的羟基磷灰石球状晶体(简称HAP)。在适当的条件下，得到了粒径为20nm左右的球状HAP超细粉体。运用XRD和TEM对HAP结晶的形貌及结构进行分析，同时还运用Zeta电位仪研究了纳米羟基磷灰石表面电位随溶液PO4^3-浓度、Ca^2 浓度、离子强度和pH值的变化规律，并且简要地分析了纳米HAP晶体的形貌和尺寸大小与表面静电位的关系。     

纳米羟基磷灰石与牙无机质的比较研究

用水热合成法制备了纳米磷灰石晶体。用透射电镜(TEM)、X射线衍射(XRD)、傅立叶一红外光谱(FT—IR)、等离子发射光谱(ICP)和X光电子能谱(XPS)分析和表征了纳米羟基磷灰石(n—HA)和牙磷灰石的组成、结构和形貌。结果表明用水热合成法制备的纳米磷灰石晶体有与牙无机质十分类似的组成、结构和形貌,同样含有羟基、碳酸根和钠离子。从仿生学角度出发,在制备纳米羟基磷灰石的过程中,应适当引入CO3^2-、F^-以利于更好地模仿自然牙的组成,制备出高性能的n—HA与高分子或牙科树脂复合材料。     

纳米羟基磷灰石的常压合成与表征

以乙二醇为氢氧化钙的溶剂在常压下合成了一种纳米羟基磷灰石晶体。分析结果表明，以乙二醇为氢氧化钙(Ca(OH)2)的溶剂反应合成的羟基磷灰石为细针状的纳米晶体，具有弱结晶结构，为非化学计量，其钙磷摩尔比约为1．66。这种纳米磷灰石晶体和自然骨中的磷灰石晶体在很多方面有相似之处。     

预处理对云母晶体析出机制的影响

采用高温融熔法制备SiO2-Al2O3-MgO—F系可加工玻璃陶瓷基础玻璃，应用XRD、SEM和EPMA等方法对不同预处理条件下样品晶体种类、显微组织进行分析，研究不同预处理条件下云母晶体的析出机制．结果表明：在相同组成的玻璃体系中，由于预处理条件的不同，导致了云母晶体以不同的析出机制析出，并且在不同的析出机制下，云母晶体的形态有着显著的差异．在快速升温的情况下，针状云母晶体在试样表面直接形核，相互平行的云母晶体几乎垂直于试样表面向中心长大；当试样预先在分相区处理后再加热到析晶温度时，针束状云母晶体以分相时形成的晶体为异质核心，呈相互交错方式长大；而当试样在过渡相析出区处理后再加热到析晶温度时，片状云母晶体呈相互交错状以异质外延长大机制析出。     

反应微环境对掺杂羟基磷灰石晶体性质和晶体形貌的影响

以Ca(NO3)2和(NH4)2HPO4为原料,采用共沉淀法,通过添加AgNO3和Cu(NO3)2合成了掺杂羟基磷灰石(Ag/Cu/HAP)。运用X射线衍射(XRD)和扫描电镜(SEM)分析讨论反应微环境对掺杂羟基磷灰石晶格参数、晶体形貌以及晶体热稳定性的影响。结果表明,磷微环境更有利于掺杂羟基磷灰石晶体沿c轴优先生长,具有更好的晶体热稳定性,且得到的是针状的掺杂羟基磷灰石晶体;而钙微环境下合成的则是特殊的花瓣状掺杂羟基磷灰石晶体。     

大孔孔径对含CO3^2-的双相HA／β-TCP多孔陶瓷表面类骨磷灰石形成的影响

钙磷陶瓷植入生物体内后其表面首先形成一层含CO3^2-的类骨磷灰石层。它对钙磷陶瓷诱导新骨的生成起非常重要的作用。本文以模拟体液SBF9^#为介质。利用体外模拟装置首次研究了以新工艺制备的含CO3^2-的双相HA／β-TCP多孔陶瓷其大孔孔径对表面类骨磷灰石形成的影响。结果表明该陶瓷因CO3^2-的掺入导致类骨磷灰石晶体的形成时间大大缩短(从14d缩短至6d)。且以300～400μm的大孔孔径最有利于类骨磷灰石晶体的形成。此外还有缺钙羟基磷灰石晶体的生成。而最不利于类骨磷灰石晶体形成的大孔孔径为400～500μm。大孔孔径的优化有利于该陶瓷材料骨诱导性的提高，进而有利于骨缺损的快速修复。     

纳米类骨磷灰石晶体合成

采用硝酸钙和磷酸钠水溶液以不同滴定顺序,于70℃下合成了纳米羟基磷灰石(n-HA)沉积物.结果表明,不同的滴定顺序得到的产物都是n-HA晶体,合成的n-HA具有与骨磷灰石晶体十分类似的组成成分、尺寸、结晶度和形貌,因此,合成的n-HA可称为类骨磷灰石晶体.考察了不同滴定顺序对n-HA形貌、结晶度和尺寸的影响;发现相同温度下,磷酸钠滴定硝酸钙得到的磷灰石呈现相对规整的针状晶体,结晶度高,杂质离子少.     

钨酸盐晶体中负离子配位多面体的结晶方位与晶体的形貌

钨酸盐类晶体是重要的闪烁晶体．本文从钨酸盐类晶体中负离子配位多面体的结晶方位和相互联结的稳定性出发，探讨了钨酸盐类晶体中[WO4]2-等负离子配位多面体的结晶方位与晶体结晶形貌之间的关系；认为[WO4]2-四面体与金属阳离子（Ca2＋，Pb2＋，Zn2＋）结合时，由于晶体结构和生长条件（如籽晶取向等）的不同，在晶体各族晶面上的叠合速率和结构取向不同，晶体的结晶形貌迥然有别；四面体的面和梭的法线（L2）所对向的晶面，生长速率慢，顽强显露，均属晶体的板面；四面体的顶角所指向的晶面，生长速率快，显露面积小，经常消失．由此可以合理解释钨酸铅等闪烁晶体的生长特征．最后对ABO4型晶体的结构及习性特征进行了总结归纳．     

磷酸盐晶体中络阴离子结晶方位与晶体形态

研究了磷酸盐类晶体中的络阴离子[PO4]-和[CaP6O24]16-在晶体中的结晶方位,与[ClCa6]11 八面体相互联结的稳定性决定了各个面族的生长速率.根据磷灰石各族晶面显露的习性,提出了采用人工生长的磷灰石做人工关节时,应该注意磷灰石的取向问题．平行于C轴方向生长的磷灰石有利于与人体骨骼的快速愈合．     

Ca2+离子对 KDP晶体生长习性及性能的影响

Ca^2＋是KDP原料中一种常见的杂质离子，通过传统降温法和“点籽晶”快速生长法研究了Ca^2＋离子对KDP晶体生长习性及性能的影响、实验表明，Ca^2＋低浓度掺杂时对溶液的稳定性及生长过程没有明显的影响；高浓度时溶液稳定性有所降低，经常出现杂品；快速生长时，晶体柱面易出现包藏，晶体的紫外透过呈下降趋势，晶体中散射颗粒密度随掺杂浓度的增加而增大、     

Preparation and mechanical property of poly(ε-caprolactone)–matrix composites containing nano-apatite fillers modified by silane coupling agents

This study aims to improve the tensile strength and elastic modulus of nano-apatite/poly(ε-caprolactone) composites by silane-modification of the nano-apatite fillers. Three silane coupling agents were used to modify the surfaces of nano-apatite particles and composites of silanized apatite and PCL were prepared by a technique incorporating solvent dispersion, melting-blend and hot-pressing. The results showed that the silane coupling agents successfully modified the surfaces of nano-apatite fillers, and the crystallization temperatures of the silanized apatite/PCL composites were the higher than that of the non-silanized control material, although the melting temperature of the composites remained almost unaffected by silanization. The ultimate tensile strength and elastic modulus of the silanized composites reached 22.60 MPa and 1.76 GPa, as a result of the improved interfacial bonding and uniform dispersion of nano-apatite fillers. This study shows that the processing technique and silanization of nano-apatite particles can effectively improve the tensile strength and elastic modulus of nano-apatite/PCL composites.     

Comparison of Ca/P mineralization on the surfaces of poly (ε-caprolactone) composites filled with silane-modified nano-apatite

This study aims to comparatively investigate the Ca/P mineralization on the surfaces of poly (ε-caprolactone) (PCL) composites with apatite nano-fillers, which were modified with silane coupling agents. Three kinds of silane coupling agents like 3-Methylacryoxypropyltrimethoxy silane (KH560), γ-Methacryloxypropyltrimethoxy silane (KH570), and N-(β-aminoethyl)-γ-aminopropyltrimethoxy silane (KH792) were firstly employed to modify the surfaces of nano-apatite particles, and then silane-modified nano-apatite/PCL composites were prepared by combining solvent dispersion and melting co-blending with hot-pressing methods. The Ca/P mineralization of the modified PCL-Matrix composites was evaluated by soaking in 2-time simulated body fluid (2SBF) at 36.5 °C and pH 7.40 after 21 days. These results showed that the Ca/P mineralization on the surface of the silane-modified composite was same as not modified composite. Apatite obtained on the surface of the modified composite film was of lower crystallinity, 1.62 Ca/P ratio and carbonate ceramic, similar to inorganic composition of bone in biological body, and not notably different from one of not modified PCL composite. This discussion revealed that as-fabricated silane-modified composite could achieve Ca/P mineralization and exhibited the ability of obtaining like-bone apatite on own surface like other bioactive materials.     

Effect of Crystal Quality on HCP-BCC Phase Transition in Solid 4He

The kinetics of HCP-BCC structure phase transition is studied by precise pressure measurement technique in ⁴He crystals of different quality. An anomalous pressure behavior in bad quality crystals under constant volume conditions is detected just after HCP-BCC structure phase transition. A sharp pressure drop of 0.2 bar is observed at constant temperature. The effect observed can be explained if we suppose that microscopic liquid droplets appear on the HCP-BCC interphase region in bad quality crystals. After the interphase region disappearance, these droplets are crystallized with pressure reduction. It is shown that this effect is absent in high quality thermal-treated crystals.     

Pressure effect on the solid–liquid equilibrium forms of even normal alkanes

This paper describes the changes in equilibrium forms of small even-numbered normal alkane crystals as functions of temperature, pressure and the carbon number of alkane chains. The crystals were grown by increasing pressure of the liquids using a diamond anvil cell (DAC). After single crystals were prepared in the DAC under high pressure, the crystals were maintained for a long period under constant pressure and temperature. During the changes in the shape of the single crystal, a thick plate of {001} plane with sharp edges was obtained within a narrow temperature range. The appearance of the thick plate is discussed with reference to the pressure and temperature dependencies of the anisotropy of the surface energy of the crystals.     

Influence of growth parameters on the fabrication of high-quality colloidal crystals via a controlled evaporation self-assembly method

A controlled evaporation self-assembly method with multiple controllable parameters was used to synthesize high-quality colloidal crystals. The environmental parameters, such as the relative humidity, evaporation temperature and pressure, were studied for the quality controls of colloidal crystals during the formation. In the experimental results, we show how these parameters influence the quality of colloidal crystals significantly. Moreover, it is found that, under the case of the relative humidity of 70%, evaporation temperature of 35 °C and pressure of 6.0 kPa, the fabricating high-quality colloidal crystals is optimal from aqueous solution of monodisperse polystyrene spheres with a diameter of 260 nm in a short time (less than 10 h). Highest possible crystal quality may be obtained after the natural drying in the vacuum chamber.     

Phase transitions in alkali halide crystals

The paper is devoted to the study of the characteristics of structural phase transitions occurring in ionic crystals under an extremely high pressure. The calculations are made for crystals of infinite size at absolute zero temperature. The pressure ofB1-B2 polymorphic transformation is calculated for a number of alkali halide crystals using pair interaction potentials obtained self-consistently within the framework of inhomogeneous electron gas theory. In so doing, the effects of seven coordination spheres are taken into account in the thermodynamic potential. The changes of the cohesion characteristics of crystals (cohesion energy, lattice constant) are calculated for the transition from theB1 structure (NaCl type) to theB2 structure (CsCl type). Based on the obtained results, conclusions are made on the stability of one or another crystal structure in the given range of external pressure. For crystals in the B1 phase, the moduli of elasticity and relative changes of the volume at the phase transition pressure are calculated. It is shown that the inclusion of the effect of higher coordination spheres affects considerably the values of the elastic characteristics of ionic crystals.     

Biomimetic synthesis and biocompatibility evaluation of carbonated apatites template-mediated by heparin

Biomimetic synthesis of carbonated apatites with good biocompatibility is a promising strategy for the broadening application of apatites for bone tissue engineering. Most researchers were interested in collagen or gelatin-based templates for synthesis of apatite minerals. Inspired by recent findings about the important role of polysaccharides in bone biomineralization, here we reported that heparin, a mucopolysaccharide, was used to synthesize carbonated apatites in vitro. The results indicated that the Ca/P ratio, carbon content, crystallinity and morphology of the apatites varied depending on the heparin concentration and the initial pH value. The morphology of apatite changed from flake-shaped to needle-shaped, and the degree of crystallinity decreased with the increasing of heparin concentration. Biocompatibility of the apatites was tested by proliferation and alkaline phosphatase activity of MC3T3-E1 cells. The results suggested that carbonated apatites synthesized in the presence of heparin were more favorable to the proliferation and differentiation of MC3T3-E1 cells compared with traditional method. In summary, the heparin concentration and the initial pH value play a key role in the chemical constitution and morphology, as well as biological properties of apatites. These biocompatible nano-apatite crystals hold great potential to be applied as bioactive materials for bone tissue engineering.     

Saturated vapor pressure over AgGaGeS4 crystals

The vaporization behavior of AgGaGeS₄ crystals has been studied using vapor pressure measurements (gradient heating under dynamic vacuum, frozen equilibrium method, and membrane measurements). AgGaGeS₄ has been shown to vaporize incongruently, losing predominantly GeS₂. The total saturated vapor pressure over AgGaGeS₄ crystals has been measured, and has been represented by a best fit equation. The results are discussed in relation to earlier data on the melting point and melting behavior of AgGaGeS₄ crystals.