纳米羟基磷灰石/胶原复合材料制备方法比较研究

低温下,通过将水热合成的纳米羟基磷灰石浆料与中性胶原溶胶共混和在中性胶原中原位形成羟基磷灰石两种方法制备羟基磷灰石／胶原复合材料,采用XRD、FTIR、扫描电镜、透射电镜和力学性能测试等方法对两种复合材料的特性进行了表征。通过对两种方法制备的复合材料的特性进行比较,发现两种方法均制备得到了纳米羟基磷灰石／胶原复合材料,复合材料在晶相组成、化学组成、纳米羟基磷灰石晶体尺寸、胶原纤维的结构等方面都与天然骨相似。但原位合成纳米羟基磷灰石晶体的结晶度比水热合成的纳米羟基磷灰石更接近于自然骨,原位合成的羟基磷灰石／胶原复合材料的均匀性、界面结合紧密度、力学性能等方面均优于共混法。原位合成法是改善纳米羟基磷灰石／胶原复合材料均匀性和力学性能的有效方法。     

水热合成微孔纳米羟基磷灰石

以Ca(NO3)2·4H2O、P2O5为原料,水-乙醇为溶剂,在碱性介质中,采用水热法合成微孔纳米羟基磷灰石晶体(HAP),研究了水-乙醇的体积比对产物组成、晶体结构的影响. 利用X射线衍射(XRD)、红外光谱(FTIR)、热分析(TG/DTA)、透射电镜(TEM)等检测技术对HAP的晶相、化学组成和形貌进行了表征和分析. 结果表明,当V(水):V(乙醇)=1:1时,可得到晶体发育完整、晶体表面孔洞分布均匀(孔密度约为3×109个/cm2)和孔径约为1～2 nm的六方柱状纳米羟基磷灰石晶体(60 nm×100 nm).     

聚乙烯醇/纳米羟基磷灰石复合材料微型注塑研究

结合固相剪切碾磨和分子复合技术制备了适合于微型注塑加工的聚乙烯醇/纳米羟基磷灰石(PVA/n-HA)复合材料,实现了n-HA含量达30%的PVA/n-HA复合材料的微型注塑加工。采用差示扫描量热法(DSC)、热重分析仪(TGA)和高压毛细管流变仪研究了PVA/n-HA复合材料的热性能和流变性能,结果表明:改性PVA/n-HA复合材料的熔点降低,热分解温度升高,获得120℃以上的热塑加工窗口;PVA/n-HA复合材料呈现剪切变稀特性,在高剪切速率下具有较低的熔体粘度,适合微型注塑加工,具有良好的充模性能。采用扫描电子显微镜(SEM)和X射线衍射(XRD)研究了PVA/n-HA微型注塑样品的结构与性能,结果表明n-HA均匀分散于PVA基体中,提高了复合材料的尺寸稳定性;受微型注塑过程中高剪切应力诱导结晶作用的影响,PVA/n-HA微型注塑样品的结晶度高于常规注塑样品的结晶度。     

纳米羟基磷灰石复合材料在硬组织工程领域中的应用研究

人体骨骼的晶体成分主要是纳米羟基磷灰石(n-HA),n-HA具有优良的生物相容性、骨传导性和骨结合能力,被广泛应用于硬组织修复材料中。本文综述了纳米羟基磷灰石在构建人体骨修复支架材料、骨替代材料和口腔医用材料方面的应用研究。     

纤维素调控合成羟基磷灰石纳米带

本文通过氨水扩散共沉淀法,在可溶纤维素的调控作用下制备得到了纳米带状羟基磷灰石。在120℃下加热回流高浓度氯化钙溶液和纤维素,作为后续合成羟基磷灰石的原料溶液。随后将磷酸二氢钠溶液加入到含有溶解纤维素和Ca2+离子原料溶液中,通过氨水扩散来提高溶液的pH值,从而引发羟基磷灰石从溶液中析出,反应一段时间后,收集析出样品。对照实验样品在不加纤维素条件下反应收集得到。通过扫描电子显微镜(SEM)、透射电子显微镜(TEM)、原子力显微镜(AFM)、傅立叶变换红外仪(FT-IR)和X射线衍射仪(XRD)分析了纤维素对HA晶体形貌和晶体结构的影响。结果显示,实验合成了超薄纳米带状羟基磷灰石晶体,该晶体的合成可能是因为纤维素分子杂化到了HA的晶体中。     

羟基磷灰石/聚乙烯醇/壳聚糖水凝胶在模拟体液中的力学性能

从仿生学角度出发,将自制的人工角膜支架材料羟基磷灰石/聚乙烯醇/壳聚糖(n-HA/PVA/CS)浸泡在模拟体液中,对材料的含水率及力学性能进行了测试,并利用扫描电镜、X射线衍射仪、电感耦合等离子体原子发射光谱仪及热重分析仪研究了材料在模拟体液中的形貌、晶体结构、元素组成及热稳定性.结果表明,在模拟体液中,n-HA/PVA/CS复合水凝胶的含水率为80%~86%,具有较高的拉伸强度,能承受正常眼压,且热稳定性较好.在浸泡后期,n-HA/CS/PVA复合材料对Ca2+的吸附和释放达到动态平衡;而其表面含有微量的纳米羟基磷灰石沉积,有利于纤维细胞的长入.     

纳米羟基磷灰石/聚乙烯醇/明胶复合材料的结构和力学性能

采用机械共混法、原位化学合成法、原位水热法制备了一系列纳米羟基磷灰石/聚乙烯醇/明胶(n-HA/PVA/GEL)复合材料;利用X射线衍射仪、透射电镜及傅立叶变换红外光谱仪等分析了复合材料的结构;利用材料试验机测定了复合材料的力学性能.结果表明,利用原位水热法可使n-HA有效地在PVA高分子中均匀分散,并提高n-HA颗粒...     

纳米羟基磷灰石/聚合物复合骨修复材料

寻找理想的骨修复材料一直是骨科材料领域研究热点。自然骨是由纳米羟基磷灰石和胶原构成的纳米复合材料。源于仿天然硬组织构想的纳米磷灰石-有机高分子复合材料是把高韧性的高分子基质与高刚性的纳米无机磷灰石晶体巧妙结合,使其最大程度地实现两种成分的优势互补和协同优化,赋予仿生纳米复合材料高强韧的力学性能。与组成同样重要的是结构因素,这种材料包括不同尺寸的架构组织和可控取向。纳米羟基磷灰石/高分子复合材料已成为骨组织修复材料领域的研究热点和发展方向。本文综述了近些年用于人体骨组织修复材料的纳米羟基磷灰石/天然(或非天然)高分子材料的制备技术、性能等方面研究进展及现状,并对其发展提出了展望。     

基于硫醇-烯烃Click反应的纳米羟基磷灰石的表面改性

纳米羟基磷灰石(n-HA)是人体骨骼和牙齿的主要无机成分,具有良好的生物相容性。关于n-HA的表面改性研究已有很多报道,本文采用硅烷偶联剂乙烯基三甲氧基硅烷与巯基乙醇两步法对n-HA进行表面改性,并通过TEM,TG,XPS和FTIR等对其进行了表征,接枝量达9.3%。同时,采用该方法,用其他巯基化合物代替巯基乙醇,可使纳米羟基磷灰石功能化具有多样性。     

明胶溶液中沉淀法制备纯相β-磷酸三钙

本文以明胶、硝酸钙Ca(NO₃)₂和磷酸氢二铵(NH₄)₂HPO₄为前驱体,初始Ca/P为1.5,制备了纯相的β-磷酸三钙.红外谱图和X射线晶体衍射结果表明,溶液中直接沉淀得到的产物为缺钙磷灰石,该产物在明胶浓度≥0.22 %(质量分数)时热转化为纯相的β-磷酸三钙.通过晶体尺寸计算和比表面积测定,缺钙磷灰石的晶体大小随着明胶用量的增加而变小.透射电镜结果显示溶液中直接沉淀的缺钙磷灰石呈针状形貌,经过高温煅烧后,针状的缺钙磷灰石将相互融合形成葡萄状的β-磷酸三钙.差热/热重结果表明,明胶与生成的缺钙磷灰石形成了化学键合,这将有助于吸附较多的水分子,随后水分子与缺钙磷灰石发生化学反应生成羟基磷灰石,羟基磷灰石继续与沉淀中的偏磷酸钙反应生成β-磷酸三钙.本文还研究了明胶对纯相β-磷酸三钙的生成机理.     

Effects of sol-gel processing parameters on the phases and microstructures of HA films

Bioactive hydroxyapatite (HA) films were fabricated by a sol–gel method and triethylphosphate and calcium nitrate were used as the phosphorus and calcium precursors, respectively. The effects of the heat treatment temperature, pH level and substrate materials on the phases and microstructures of HA films were studied by X-ray diffraction (XRD), scanning electronic microscopy (SEM) and electronic probe microanalysis (EPMA) and so on. The results show that all the sol–gel films are composed of the phases of HA, CaO, TiO₂ and CaTiO₃. With increasing the calcining temperature, the crystallinity of the films increases, the structure becomes more compact and changes from granular and lamellar to cellular structure, and the Ca/P ratio increases slightly because of the loss of P in the films. The addition of ammonia (adjusting the pH level to be about 7.5) can increase the HA content in the films, and the difference of substrate materials only has a little influence on the microstructure of the sol–gel films.     

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.     

Mechanism of solid-state conversion of non-stoichiometric hydroxyapatite to diphase calcium phosphate

Two non-stoichiometric hydroxyapatites (n-HA) with Ca/P molar ratios of 1.50 and 1.58 and one stoichiometric hydroxyapatite (s-HA) with Ca/P = 1.67 were prepared from chemically pure CaHPO₄·2H₂O and KOH. After sintering at 1050 °C for 4 h, n-HA with Ca/P = 1.50 was transformed into -Ca₃(PO₄)₂, n-HA with Ca/P = 1.58 was converted to diphase calcium phosphate (DCP), while s-HA underwent no chemical transformations. The sintered and unsintered samples of hydroxyapatite were studied by IR spectroscopy, chemical analysis, and X-ray diffraction analysis. The crystallite dimensions were calculated, and a model for the DCP structure was proposed. The mechanism of the solid-state n-HA to DCP conversion was proposed on the basis of this model and published values of the volume diffusion coefficients of the OH^–, Ca²⁺, and PO₄ ^3– ions at 1000 °C.     

Preparation and characterization of new hybrid organic/inorganic systems derived from calcium (alpha-aminoalkyl)-phosphonates and -phosphonocarboxylates

We have studied the phenomenon of calcium complexation by lab synthesized amphiphilic (alpha-aminoalkyl)-phosphonocarboxylic or -phosphonic acids. The electrical conductivity of aqueous solutions of sodium salts of all these acids was measured versus the volume of a calcium salt solution added. It appeared that calcium complexes are formed in a Ca/P atomic ratio close to 1. Calcium phosphonocarboxylates and calcium phosphonates were also precipitated by mixing aqueous solutions of disodium salts of phosphorus amphiphiles and calcium nitrate solutions. Before chemical analysis, these complexes were calcined to remove the organic part. In the mineralized products, calcium and phosphate were assayed: the Ca/P atomic ratio was equal to 1. X-ray diffraction and IR spectroscopy showed that they are made entirely of beta pyrophosphate (Ca2P2O7), a result in agreement with previous chemical analysis. The chemical formula of the starting calcium complexes could be written as CaL2H2O (L=ligand). The SEM micrographs of these complexes show plate-like structures. XRD patterns are characteristic of layered structures. These facts suggest that calcium complexes are composed of alternating bimolecular layers of calcium alkylphosphonocarboxylates or calcium alkylphosphonates, the chains being tilted and partially interdigitated.     

钙磷物质的量比对磷酸钙骨水泥性能的影响

本研究通过在磷酸钙骨水泥(calcium phosphate cement,CPC)固相配方中添加不同量的氯化钙(CaCl2),制备不同钙磷物质的量比的CPC,研究不同钙磷物质的量比对CPC性能的影响。测试CPC的初、终凝时间。将CPC体外模拟浸泡3d和7d,研究模拟生理条件下CPC的性能,分别利用X-射线衍射(XRD)、力学性能实验机、扫描电镜(SEM)等研究CPC相成分、抗压强度和断面微观形貌。通过化学滴定测定浸泡液中氯离子浓度。结果表明:提高钙磷物质的量比不会显著延长CPC凝结时间;模拟浸泡液中的氯离子浓度处于正常生理条件的范围内;随钙磷物质的量比的增加,水化后CPC的抗压强度显著提高,而经过体外模拟浸泡后,钙磷物质的量比为1.67和1.80的CPC的抗压强度明显下降;具有较高钙磷物质的量比的CPC体外模拟浸泡后,形成多孔结构、弱结晶类骨磷灰石的终产物。     

分光光度法测定化学试剂中痕量钙

在pH10.4的NH3 NH4Cl介质中,Ca2+与DBC 偶氮氯膦生成1∶1蓝色络合物.络合物的最大吸收波长位于624nm,方法的表观摩尔吸光系数ε624nm=3.82×104L·mol-1·cm-1,钙量在0～25μg/25mL范围内遵守比尔定律.本法用于化学试剂KCl,NaCl及NaNO3中痕量钙的测定,得到了满意的结果.     

Synthesis and Kinetic Study of Hydroxy/Fluoroapatite Solid Solution Formation by Decomposition of a Ca‐EDTA Complex

Fluoroapatite/hydroxyapatite (FA/HA) solid solutions were synthesized through the decomposition of a Ca(EDTA) complex in presence of phosphate and fluoride ions. Fluorine content and morphology depend on initial pH value. Phase identification, fluorine content, crystallinity and morphology of the obtained products were studied via chemical analysis, FTIR, SEM, XRD, and EDS. The kinetic study shows a catalytic dependence on pH value. The values of k₀, k_H+ and k_OH are reported.     

Controversy about β-tricalcium phosphate

The calcium phosphate which corresponds to the formula Ca₃(PO)₄ · nH₂O (2<n<3) was isolated from solutions with Ca/P molar ratio 0.2 and pH 7. The compound was characterised by chemical and thermogravimetric analyses, Fourier-transform infrared (FTIR) spectroscopy and X-ray diffraction. The FTIR spectra were compared with spectra of β-tricalcium phosphate (β-TCP) in the atlases for analysis of urinary calculi and other literature data.     

Templating route for mesostructured calcium phosphates with carboxylic acid- and amine-type surfactants

Mesostructured calcium phosphates constructed by ionic frameworks were synthesized using carboxylic acid- and amine-type surfactants in mixed solvent systems of ethanol and water. A lamellar mesostructured calcium phosphate was prepared using palmitic acid as an anionic surfactant, as in the case using n-alkylamines. A wormhole-like mesostructured calcium phosphate can be obtained using dicarboxyl N-lauroyl- l-glutamic acid, whose headgroup is larger than that of palmitic acid. Similar mesostructured product was obtained using 4-dodecyldiethylenetriamine with a large headgroup containing two primary amine groups. Interactions of carboxyl and primary amino groups in the surfactant molecules with inorganic species are quite important for the formation of mesostructured calcium phosphates. The Ca/P molar ratio of mesostructured calcium phosphates was strongly affected by the molecular structure of surfactants containing carboxyl and primary amino groups. Ca-rich materials can be obtained using carboxylic acid-type surfactants (Ca/P approximately 1.7) rather than amine-type surfactants (Ca/P approximately 1.0).