Investigation of the Synthesis and Properties of Nano Hydroxyapatite Biomaterials

纳米生物材料是当今材料和医药领域的一个重要组成部分和发展方向，纳米材料将可能成为21世纪生物医学材料的核心。自然骨是由纳米羟基磷灰石（Ca10(PO4)6(OH)2，HAp）晶体和胶原蛋白组成的复合材料，制备与自然骨性能接近的纳米生物材料是人们不懈努力的目标。人工合成的羟基磷灰石材料与人体组织具有良好的相容性，并能与骨组织形成骨性结合，但材料本身的脆性使其不适用于人体强负载部分。本论文的目的是研究在金属钛表面涂覆纳米羟基磷灰石膜层的制备方法和性能，以期获得具有优良力学性能和生物性能的纳米合生物材料。 通过实验比较了沉淀法、沉淀法结合水热处理和溶胶－凝胶法合成纳米HAp粉末的优缺点。结果表明温...Nano biomaterials become a most important branch in the field of materials and medicine, and they are recognized as a nuclear material in biomaterial in the 21th century. Natural bone is a composite material made of nano hydroxyapatite (Ca10(PO4)6(OH)2，HAp) crystals and collagen fibers. Great attempts have been made to prepare the biomaterials with similar composition, structure and properties to ...学位：理学博士院系专业：化学化工学院化学系_物理化学(含化学物理)学号：B20002500

The preparation and characterization of nano-Ag/HAp bioceramic coating on titanium surface

目的:在纯钛表面构筑羟基磷灰石/纳米银涂层并进行各种性能表征。方法:采用恒电位电化学法在纯钛表面构建纳米银/羟基磷灰石(nAnO-Ag/HAP)涂层。采用扫描电子显微镜(SEM),X射线衍射仪(Xrd)、等检测手段对涂层进行理化性能的表征。考察了涂层的结构组分和表面的微观形貌,而后将l-929细胞培养于涂层表面,采用细胞毒性评价,分析比较涂层表面对l-929细胞黏附率及增殖率的影响。结果:涂层纳米银粒子直径在200~400nM时体外细胞培养显示其具有良好的生物活性。结论:本实验构筑的涂层具有良好的性能和应用前景。Objective:This research was aimed at the electrochemical deposition employed to deposit a Nano-Ag/HAp composite coating on titanium surface.Methods:A Nano-Ag/Hap composite coating was deposited on the surface of pure titanium by electrochemical deposition.Scanning electromicroscope(SEM) and X-ray diffraction(XRD) were employed to characterize the obtained coating.In vitro celluar responses of the L-929 to the coating were also evaluated by MTT assay.Conventional Hap coatings and commercially pure titanium were taken as control.Results:The Nano-Ag/Hap bioceramic coating has good crystallization and homogeneous on nano-Scale surface morphology.The L-929 culture exhibits satisfactory bioactivity.Conclusion:The Nano-Ag/HAp bioceramic coating on titanium surface has promising prospects in the future clinical application

The Preparation and Characterization of oyster shell hydroxyapatite and its Composite

羟基磷灰石（Hydroxyapatite，HA）是人体和动物骨骼的主要无机成分，具有优异的生物相容性、生物活性、骨诱导性和骨引导性，在生物材料领域被广泛应用。随着海洋资源的开发与应用，生物质碳酸钙转化HA成为新的研究热点，如珊瑚、乌贼等动物骨骼，但其资源稀缺，获取成本高。因此，寻求一种资源丰富的生物质碳酸钙具有重要的意义。近年来研究表明，牡蛎壳类生物材料资源丰富具有良好的生物相容性，利用废弃牡蛎壳还可解决海域污染，已成为骨组织支架材料研究的热点。 牡蛎壳种类丰富成分复杂。目前，对于牡蛎壳的水热研究大部分仅局限于珍珠层及少量文石型牡蛎壳，为最大限度的有效利用资源，拓宽方解石牡蛎壳的应用，本文以...Nano-hydroxyapatite(HA) is one of the major contents of the inorganic in human and animal bone. Because of its good biocompatibility, bioactivity, osteoinductivity and osteconductivity, it has been widely used in biomaterials. The hydrothermal conversion of natural-biological calcium carbonate (i.e. corals and cuttlebone) to HA has been extensive studied with the utilization and development of Oce...学位：理学硕士院系专业：材料学院生物材料系_☆生物医学工程学号：2452007115250

Study on Electrochemically Controllable Preparation of Nano Hydroxyapapatite Coating and its Formation Mechanism

摘要HA/Ti复合材料可以发挥HA和医用金属的综合优势。已发展了多种制备HA/Ti复合材料的技术，各种方法均有优缺点。电化学沉积法是制备生物陶瓷膜层的一种新方法，其优点是：温和的沉积条件可避免HA晶相的破坏；简单易控的沉积过程易于实现不同性能涂层的可控制备；非线性的涂覆过程，适合于外形复杂的金属基底材料。本文侧重发展电化学沉积法，通过系统研究，实现HA涂层表面形貌结构的可控制备，并探索其结构和性能关系。此外，还对控制条件下羟基磷灰石的电化学沉积机理进行讨论。主要进展和结果如下：1.羟基磷灰石涂层的电化学可控制备发展和完善了从水溶液体系中直接制备结晶完美的纯HA涂层的电化学沉积技术。调节沉积体系...Abstract Hydroxyapatite(HA) coatings can endow the surface metallic materials with bioactivity, thus integrate the proper mechanical properties of the metal substrate with the excellent biological properties of the coating. Many techniques such as plasma spraying, electrophoresis, electrochemical deposition, sol-gel, biomimetic methods, etc. have been developed to prepare HA coatings on metalli...学位：理学硕士院系专业：化学化工学院化学系_物理化学(含化学物理)学号：20022507

Microwave Synthesis and Characterization of Nano-sized Calcium Deficient Hydroxyapatite with Different Ca/P Ratio

通过微波辐射硝酸钙和磷酸的共沉淀物可以快速合成不同CA/P比的缺钙羟基磷灰石,利用fT-Ir、fT-rAMAn和Xrd对产物进行了表征,EdS测定CA/P比,TEM观察其形貌。结果表明,通过控制反应条件能得到不同CA/P比的纳米缺钙羟基磷灰石。Rapid synthesis of calcium deficient hydroxyapatite with different Ca/P ratio was done by precipitation using calcium nitrate and phosphoric acid and subsequently subjecting to microwave irradiation.The synthesized CDHA was characterized by FT-IR, FT-Raman, and XRD.Ca/P ratio was determined by EDS.Transmission electron microscopy analysis showed needle like or stick like morphology of CDHA.In all, nanosized CDHA with different Ca/P ratio can be synthesized by controlling reaction condtion.福建省科技重大专项资助(2005HZ01-3

An Investigation of HAP/Organic Polymer Composite CoatingsPrepared by Electrochemical Co-Deposition Technique

首次提出在 NH4H2 PO4- Ca( NO3) 2 溶液中添加水溶性乙烯类有机高聚物 ,实现了通过电化学共沉积法制备具有生物活性的有机高聚物 /钙磷陶瓷复合膜层。用 XRD、SEM等对膜层的组分和形貌进行表征 ,证明陶瓷膜层表面形貌发生明显的变化。有机高聚物的引入 ,并不影响电沉积制备的羟基磷灰石 ( HAP)晶体在 ( 0 0 2 )晶面生长存在的晶面择优取向。体外细胞实验表明 ,HAP/有机高聚物复合膜层具有优良的生物活性An electrochemical co-deposition technique has been developed to prepare a hydroxyapatite (HAP)/organic polymer composite coating on Ti surface as new biomaterial of hard tissue. The composite coating of organic polymer and calcium phosphate is formed by adding a water soluble polymer of the ethylene series to NH 4H 2PO 4-Ca(NO 3) 2 solution when conducting an appropriate electrochemical co-deposition experiment. The XRD, SEM, XPS, SIMS and nano indent measurements were performed to characterize the morphology, composition, structure and surface stiffness of the composite coating. It was found that the morphology and surface hardness of the coatings showed a remarkable modification when introducing a minor polymer to HAP coatin, and the bonding force between the coating and metal substrate was distinctly increased. The incorporation of minor organic polymer into the HAP compound at molecular level will improve the mechanical properties and morphology of the composite coatings, and this may be helpful to raising its bio-activity.国家自然科学基金资助项目 ( 2 98730 39

Research of Restoration of Tooth Enamel Caries by Hydrolysis of α-TCP

龋病是口腔科的常见病和多发病，发病始于牙冠，如不及时治疗，最终结果是牙齿丧失。龋病是牙齿硬组织逐渐被破坏的一种疾病，在龋病形成的早期，牙釉质表面开始脱矿，溶解破坏，此时若给予积极的治疗能够有效的阻止龋病进一步发展。 本文发展了一种α-磷酸三钙（α-TCP）水解法在牙釉质表面制备缺钙羟基磷灰石（CDHA）涂层的方法，修复早期的釉质龋；并对涂层的性能进行表征，探讨了不同的实验条件对涂层生长的影响；对α-TCP及其水解液进行细胞毒性评价；设计了一种用于牙釉质及龈缘密闭给药的牙套，使这种简便修复龋损的方法，具有潜在应用前景。 本研究结果表明牙釉质表面的酸蚀能够提高牙釉质表面的表面能和亲水性，增强表...Dental caries is a common and frequent disease in department of stomatology, with gradually damage of oral hard tissue. The crown is affected first, if dosn’t treat timely, the whole teeth will lost at last. At the early stage of dental caries, the enamel surface damage is began with by demineralizing and dissolving, active and positive treatment can prevent it from developing further. A novel me...学位：工程硕士院系专业：材料学院生物材料系_☆生物医学工程学号：2402005130254

Preparation of Hydroxyapatite Restoration Coating on Enamel Surface and Its Biocompatibility Evaluation

龋病是一种全世界范围内常见的口腔进行性疾病，龋病导致的牙齿功能的丧失严重影响着人们的生活与健康。阻止龋病发展的关键在于对早期龋齿的及时发现和有效的治疗。目前，对于龋病的治疗主要是通过填充从而达到修补龋洞的目的。但这种治疗方式需要磨除部分健康的牙组织，并且由于填充材料与牙齿具有不同的化学成分和微观结构，填充材料与基底之间难以实现完美的结合，在填充以后可能在牙齿与填充材料的界面上发生继发龋。因此，在发生浅龋的牙釉质表面构建与之成分、结构相仿的羟基磷灰石（HA）修复涂层，以达到对早期浅龋无损修复的目的，是解决这一问题的有效途径。 本文基于涂剂法制备牙釉质仿生修复涂层的思路，利用羟基磷灰石粉末在固化...Dental caries is a prevalent chronic and world-wide oral disease. The loss of teeth as a consequence of serious caries greatly reduces the quality of one’s life. The strategy to prevent the development of caries is the effective treatment of early lesions. Currently, enamel defects are frequently refilled with unstructured substitutes. The problems involved in this repair when it is applied to ear...学位：工学硕士院系专业：材料学院材料科学与工程系_材料学学号：2072008115061

Study on Surface Modification of Biomaterials and

在生理环境中，植入材料与机体组织之间的相互作用总是发生在材料表面。材料表面的物理化学特性必然直接影响到组织的愈合，同时，机体环境也可作用于材料表面，并使之发生腐蚀、降解及变性。植入材料的生物相容性和生物活性与表面理化特性密切相关。因此，控制和改善生物材料的表面特性，是促进材料表面与生物体之间相互作用，提高植入材料生物相容性和生物活性的有效途径。由于医用钛及其合金的结构和性质与自然骨相差很大，加之表面钝态氧化膜的存在，通常不能与骨发生化学键性结合，植入体内后，就被纤维性膜所包围，而与周围的骨组织隔离，从而造成植入治疗的失败。努力发展各种方法对医用钛进行表面改性以提高其生物活性是当前的一个研究热点...In physiological environments, the interactions between implants andcellular tissues mainly take place at the surface of implants. Thephysicochemical properties of surface for the implanting material have a veryclose and direct influence on the recovery of tissues; On the other hand,tissues exert effect on the implants surface, leading to corrosion, degradationor modification. It has been widely a...学位：工学硕士院系专业：化学化工学院材料科学系_材料学学号：20013601

The preparation and biological evalution of Hydroxyapatite/Nanosilver bioceramic coating on Titanium implant surface

目的:在钛种植体表面构筑羟基磷灰石/纳米银涂层并进行生物学评价。方法:采用恒电位电化学法在纯钛表面构建纳米级羟基磷灰石/纳米银(HAP/nAnOSIlVEr)涂层。采用扫描电镜(SEM),检测手段对涂层进行理化性能的表征。考察了涂层的结构组分和表面的微观形貌,而后将人牙周膜成纤维样细胞培养于涂层表面,采用细胞毒性评价及其形态观察,分析比较不同表面涂层对牙周膜成纤维样细胞粘附率及增殖率的影响。结果:羟基磷灰石纳米银涂层体外细胞培养显示其具有良好的生物活性。结论:本实验构筑的涂层具有良好的生物相容性和细胞粘附性,应用前景广阔。Objective:To prepare the composite of Hydroxyapatite/Nanosiliver composite coating on titanium implant surface.Method:A HAp/Nanosiliver composite coating was deposited on the surface of pure titanium by electrochemical deposition.Scanning electromicroscope(SEM)was employed to characterize the obtained coating.The reactions of human pe- riodontal ligament fibroblast-like cells (PDLF)to the coating were also evaluated by MTT assay and SEM observation.Re- sult:The HAp/Nanosiliver bioceramic coating has good crystallization and homogeneousness on nano-scale surface mor- phology.The PDLF growth was tested by MTT assay and the cell relative growth rate (RGR)was calculated.Conclusion: The HAp/Nanosiliver bioceramic coating on titanium surface possesses good biocompatibility and celluar adhesion and has promising prospects in the future clinical application.厦门市科技局资助项目(3502Z20084034