常压下纳米级羟基磷灰石针状晶体的合成

通过使用一种易于重复的合成工艺,在常压下制备了纳米级羟基磷灰石针状晶体,这种纳米级针状晶体在形态,结构和组成上与人骨组织中纳米针晶非常相似,利于发挥羟基磷灰石优良的生理相容性,能用于研制一种类骨的高强柔韧的复合人工骨修复材料,所用的制备工艺有助于简化这种类骨复合材料的合成。     

羟基磷灰石/纤维素复合材料在骨组织工程中的研究进展

自从使用羟基磷灰石复合材料作为生物医用替代材料以来,其制备原料和制备工艺不断得到优化,现已制备出性能接近于天然骨的复合材料。但是羟基磷灰石复合材料还存在很多不足,例如抗压强度和弹性模量达不到天然骨的要求而导致其骨兼容性和骨整合较差,这些缺点严重阻碍了它作为骨替代物的发展。羟基磷灰石/纤维素复合材料不仅具有二者的特点,而且两材料协同产生的优异性能使其更加适用于生物组织工程材料。相比传统的骨替代材料,羟基磷灰石/纤维素复合材料在力学性能、生物活性、生物相容性、生物降解性等方面都有不同程度的改善,并且具有更好的成骨活性,已经基本达到理想组织工程应用的支架材料的要求。在以纤维素为基底材料制备羟基磷灰石复合材料中,已经成功应用的纤维素类包括纳晶纤维素、细菌纤维素、羧甲基纤维素(CMC)等。但是不同的纤维素/羟基磷灰石复合材料之间也存在性能差异,有的纳米复合材料抗压强度较低,只有(1.57±0.09) MPa/cm~3,但是有的纳米复合材料的抗压强度和模量都能接近天然骨。因此近几年来,研究者们除了不断优化制备工艺,主要还在选择合适的纤维素方面不断尝试,并取得了很大的进步。目前,已经有研究者发现CMC/明胶/羟基磷灰石纳米复合材料的抗压强度和模量与人松质骨和皮质骨相似,并且它也能促进细胞的高碱性磷酸酶活性和细胞外矿化,可作为主要承载区的再生骨移植材料。本文介绍了羟基磷灰石与纤维素的特点,综述了各类羟基磷灰石/纤维素复合材料的制备方法以及研究现状,并对其性能进行了探讨,进而对羟基磷灰石/纤维素复合材料的研究发展前景予以展望,希望为制备性能更加良好的骨替代材料提供参考。     

羟基磷灰石/胶原类骨仿生复合材料的制备及表征

通过体外模拟天然骨生物矿化和材料自组装的形成机制, 研究制备了类骨羟基磷灰石/ 胶原仿生复合材料并对材料进行了表征。结果表明: 纳米羟基磷灰石均匀分布在胶原基质上并择优取向排列, 该复合材料的成分和微观结构与天然骨类似。     

纳米羟基磷灰石与有机物复合的研究进展

综述了近年国内外纳米羟基磷灰石与有机物复合的研究进展。分析了纳米羟基磷灰石与聚乳酸、聚酰胺、聚乙烯与聚己丙脂等人工合成有机物,及纳米羟基磷灰石与胶原、壳聚糖、人骨形成蛋白、明胶等天然有机物复合材料的复合方法、力学性能、生物相容性等的研究进展。并对未来的发展做了展望。     

国家“863”“973”攻关项目“纳米人工骨”获美国专利

经过近两年的审核和考察，由清华大学材料系崔福斋教授课题组研究的纳米人工骨，日前获得美国专利局颁发的专利批准通知，这为拓展海外市场奠定了基础。作为国家“863”、“973”计划支持的攻关项目，纳米人工骨(NB系列纳米晶胶原基骨材料)与原有传统人工骨材料的最大区别在于，修复后的骨头和人体骨完全一样，不会在体内留下植入物。它仿照人类的骨头生成的机理，采用自组装方法制备纳米晶羟基磷灰石／胶原复合的生物硬组织修复材料，使复合材料具有纳米有序结构的天然骨分级和多孔结构。     

纳米羟基磷灰石/壳聚糖复合生物材料研究

骨的特殊性能决定了其在人体中起重要的功能作用,人工骨材料对骨缺损的治疗有重要意义。羟基磷灰石是人和动物骨骼的主要无机成分;壳聚糖是天然可降解多糖,降解产物为对人体组织无毒、无害的氨基葡萄糖。纳米羟基磷灰石/壳聚糖复合生物材料可以实现羟基磷灰石和壳聚糖两者的优势互补,具有优良的生物活性、生物相容性和力学性能。介绍了近年来纳米羟基磷灰石/壳聚糖复合生物材料的主要合成方法(如共混法、共沉淀法、原位沉析法、交替沉积法和模拟体液法等),并在此基础上介绍了基于纳米羟基磷灰石/壳聚糖的三元复合材料的研究及发展情况;最后,展望了纳米羟基磷灰石/壳聚糖复合生物材料未来的发展方向。     

超声辅助湿法合成纳米HA及MWNT/HA复合材料

以Ca(NO3)2·4H2O、(NH4)2HPO4和NH3·H2O为原料,在超声波辅助下,湿法合成了羟基磷灰石,用FTIR、XRD和TEM对产物进行了分析,结果表明:合成的羟基磷灰石为纳米级纺缍状晶体,不用烧结即具有较高晶化度,且为单一的羟基磷灰石晶相。以此制备条件为基础,采用原位合成的方法制备了多壁碳纳米管/羟基磷灰石复合材料,FTIR、XRD和TEM的分析结果表明:碳纳米管能较好的分散于羟基磷灰石基体中,部分碳纳米管表面可被反应生成的羟基磷灰石所包覆,二者之间有着较好的相容性,可作为一种新型的生物复合材料应用。     

n-HA/PA66/HDPE复合生物材料的制备和性能研究

应用纳米羟基磷灰石(n-HA)、聚酰胺66(PA66)和高密度聚乙烯(HDPE)制备了生物医用复合材料。用化学分析法、燃烧实验、热分析、AFM、IR、XRD对复合材料的组成和结构进行了分析,并对复合材料的力学性能进行了研究。结果表明所制备的复合材料组成均一,具有高强柔韧的力学性能,纳米羟基磷灰石、聚酰胺66、高密度聚乙烯三者之间产生了一定的相互作用,形成了稳定的界面结合。因此,该三元复合材料可能成为一种新型的骨修复材料,在生物医学材料的开发和应用研究中具有重要意义。     

n-HA/PA66复合材料中两相间作用机理研究

采用红外光谱(IR)、X射线衍射(XRD)和差示扫描量热仪(DSC)从分子水平上分析了纳米羟基磷灰石／聚酰胺66生物复合材料中纳米羟基磷灰石(n-HA)和聚酰胺66(PA66)之间的相互作用机理。结果表明，纳米羟基磷灰石与聚酰胺66之间主要通过氢键结合，而氢键作用主要发生在纳米羟基磷灰石的羟基和聚酰胺的仲氨基之间。氢键的方向性，削弱了PA66的β结晶取向，复合材料中PA66的结晶形态主要是α晶型。纳米羟基磷灰石和聚酰胺66之间的氢键作用，增加了成核点，起到了异相成核剂的作用，虽然加快了PA66的成核速率，但同时会使体系的粘度增加，影响PA66的有序排列而导致PA66的结晶度降低。     

纳米羟基磷灰石/壳聚糖/羧甲基纤维素三元复合骨修复材料的制备和性能研究

用溶液共混法在常温常压下制备了不同比例的纳米羟基磷灰石/壳聚糖/羧甲基纤维素三元复合骨修复材料.用燃烧实验、IR、XRD、SEM及TEM对复合材料的组成结构及形貌进行了分析和观察,并初步研究了其力学性能.结果表明该复合材料中纳米羟基磷灰石均匀分散在壳聚糖和羧甲基纤维素网络结构中,三组分间还产生了一定的相互作用,其形态、尺寸及结构与自然骨类似,且其抗压强度比纳米羟基磷灰石/壳聚糖二元复合材料更高;同时,通过调节各组分比例,可制得不同抗压强度的复合材料.因此,该三元复合材料可望作为一种新型可降解的非承重部位骨修复材料,在生物医学材料的研究中具有重要意义.     

Reinforcing hydroxyapatite/thermosetting epoxy composite with 3-D carbon fiber fabric through RTM processing

Bioactive ceramic/polymer composites have been developed in the orthopaedic field in recent years. In this work, three-dimensional (3-D) carbon fiber fabric is used to reinforce hydroxyapatite (HA)/thermosetting epoxy composite and epoxy resin through resin transfer molding (RTM) processing. It is found that the 3-D carbon fiber fabric can be impregnated with epoxy and HA-containing epoxy resin, and HA is distributed gradually along the depth direction in fiber-reinforced HA/epoxy composite, although HA is dispersed evenly in epoxy resin by surface modification of silane coupling agent. The impact toughness and flexural strength of fiber-reinforced epoxy and fiber-reinforced HA/epoxy composites are much higher than those of epoxy and HA/epoxy composite. The impact toughness of both fiber-reinforced composites decreases while the flexural strength and the flexural modulus increase with fiber volume ratio. The impact toughness of the fiber-reinforced HA/epoxy composite is higher, while the flexural strength and modulus are lower than those of the fiber-reinforced epoxy composite at the same fiber volume ratio. The flexural strength of the both composites is higher than, and their flexural modulus is close to, those of the human cortical bone. The in vitro cytotoxicity test with L929 fibroblasts shows that the addition of HA diminished the toxicity of epoxy resin.     

碳纤维增强羟基磷灰石/环氧树脂复合材料的制备与力学性能

采用树脂传递模塑(RTM)工艺制备了碳纤维增强环氧树脂以及碳纤维增强羟基磷灰石(HA)/环氧树脂两种复合材料，并测试了其力学性能。结果表明，RTM工艺可以基本保证环氧基体均匀浸入碳纤维织物内部。碳纤维增强HA，环氧复合材料的冲击韧性高于碳纤维增强环氧复合材料，而弯曲强度和弯曲模量低于碳纤维增强环氧复合材料。两种复合材料的弯曲强度远高于人体皮质骨，弯曲模量与皮质骨非常接近。动态力学分析(DMA)表明加入HA后，复合材料的贮存模量和内耗降低，玻璃化转变温度升高。     

Nano iron oxide–hydroxyapatite composite ceramics with enhanced radiopacity

Hydroxyapatite has been widely used for a variety of bone filling and augmentation applications. But the poorly resolved X-ray image of certain hydroxyapatite (HA) based implants such as porous blocks and self setting HA cements is a radiological problem to surgeons for monitoring of the implant and early diagnosis complications. In the present work the practical difficulty related to the reduced X-ray opacity was overcome by exploiting the contrast enhancement property of iron oxide nano particles. Sintered nano iron oxide–HA composite ceramics were prepared from powders produced through a co-precipitation route. The phase purity and bioactivity of the composites were analyzed as a function of percentage iron oxide in the composite. The X-ray attenuation of dense and porous composites was compared with pure HA using a C-arm X-ray imaging system and micro computed tomography. In all the prepared composites, HA retains its phase identity and high X-ray opacity as obtained for a composition containing 40 wt% iron oxide. The increased cell viability and cell adhesion nature depicted by the prepared composite offers considerable interest for the material in bone tissue engineering applications.     

Structure and properties of hydroxyapatite-bioactive glass composites plasma sprayed on Ti6Al4V

Hydroxyapatite (HA)-coated Ti6Al4V has recently been used as a bone substitute in orthopaedic and dental applications because of its favourable bioactivity and mechanical properties. Studies in the literature have shown that the bioactivity of calcium phosphate bioactive glass (BG) is higher than that of HA. In an attempt to increase the bioactivity of Ha-coated Ti6Al4V and enhance the bonding strength between coating and substrate, in the present study, HA/BG composites are applied onto Ti6Al4V using a plasma spraying technique. Microstructure and phase changes of the composite coating after plasma spraying are studied. The coating-substrate bonding strength is evaluated using an Instron, following the ASTM C633 method. Results indicate that the average bonding strengths of BG, HA/BG and HA coatings are 33.0±4.3, 39.1±5.0, and 52.0±11.7 MPa, respectively. Open pores with sizes up to 50 m are found in both BG and HA/BG coatings, which are probably advantageous in including mechanical interlocking with the surrounding bone structure, once implanted. These HA/BG composites could provide a coating system with sufficient bonding strength, higher bioactivity, and a significant reduction in cost in raw materials. The future of this HA/BG composite coating system seems pretty bright.     

Sol-gel原位相转变矿化制备纳米羟基磷灰石/壳聚糖复合支架材料

为了模拟天然骨组织的结构和成分,以羟基磷灰石（HA）为钙磷源,以壳聚糖（CS）为大分子基质材料,在酸性环境中形成均相溶液,通过Sol-gel相转变矿化方法和陈化处理,原位构建了纳米HA/CS复合多孔支架材料,研究了共沉积时体系的pH值和陈化时间对支架压缩强度、晶相组成及形貌等的影响。结果表明体系pH为10和11时,支架...     

Biodegradable and semi-biodegradable composite hydrogels as bone substitutes: morphology and mechanical characterization

Biodegradable and semi-biodegradable composite hydrogels are proposed as bone substitutes. They consist of an hydrophilic biodegradable polymer (HYAFF 11) as matrix and two ceramic powders (α-TCP and HA) as reinforcement. Both components of these composites have been of great interest in biomedical applications due to their excellent biocompatibility and tissue interactions, however they have never been investigated as bone substitute composites. Morphological and mechanical analysis have shown that the two fillers behave in a very different way. In the HYAFF 11/α-TCP composite, α-TCP is able to hydrolyze in contact with water while in the HYAFF 11 matrix. As a result, the composite sets and hardens, and entangled CDHA crystals are formed in the hydrogel phase and increases in the mechanical properties are obtained. In the HYAFF11/HA composite the ceramic reinforcement acts as inert phase leading to lower mechanical properties. Both mechanical properties and microstructure analysis have demonstrated the possibility to design hydrophilic biodegradable composite structures for bone tissue substitution applications.     

Preparation and bioactivity evaluation of hydroxyapatite-titania/chitosan-gelatin polymeric biocomposites

Biocomposites consisting of hydroxyapatite (HA) and natural polymers such as collagen, chitosan, chitin,and gelatin have been extensively investigated. However, studies on the combination of HA and titania with chitosan and gelatin have not been conducted yet. Novel biodegradable hydroxyapatite-titania/chitosan-gelatin polymeric composites were fabricated. In this work, our results are concerning with the preparation and characterization of HA powder and HA filler containing titania powder (10 and 30%) with a chitosan and gelatin copolymer matrix. The present research focuses on characterizing the structure of this novel class of biocomposites. Thermogravimetric analysis (TGA), X-ray diffraction (XRD), and Fourier Transformed Infrared Spectroscopy (FT-IR), Scanning electron microscopy (SEM-EDAX) were employed to assess the produced composites. The mechanical properties in terms of compressive strength and hardness test were also investigated. The in vitro study in simulated body fluid (SBF) was performed to assess the bioactivity of composites. The results proved that apatite resembling natural bone are formed faster and greater in the case the composite of HA containing 10% titania into chitosan-gelatin polymeric matrix when they are soaked in a simulated body fluid (SBF) than the composite containing 30% titania. The biocomposites containing HA with 10% titania are expected to be attractive for bioapplications as bone substitutes and scaffolds for tissue engineering in future.     

Ti35Nb7Zr-xHA生物复合材料的微观组织与性能研究

为了改善Ti-Nb-Zr合金的生物活性,采用放电等离子烧结(SPS)技术制备了不同羟基磷灰石(HA)含量的Ti35Nb7Zr-xHA(x=0、5、10、20(质量分数,%))生物复合材料,研究了HA含量对复合材料微观组织、力学性能及体外生物活性的影响。结果表明,复合材料主要由β-Ti、α-Ti、HA及陶瓷相(Ti_xP_y、CaTiO_3、Ti_2O、CaO)组成;HA含量增加会导致β-Ti减少而α-Ti和陶瓷相明显增多;与Ti-35Nb-7Zr合金(E:45GPa,σ:1 736 MPa)相比,HA含量为5%和10%时,复合材料的抗压强度分别为1 662MPa和1 593MPa,弹性模量分别为48GPa和49GPa,综合力学性能与Ti-35Nb-7Zr合金接近,展现出良好的力学性能,而过高的HA含量(20%)会导致复合材料弹性模量明显升高(E:55GPa)、抗压强度急剧下降(σ:958 MPa),复合材料的力学性能降低;体外生物活性实验表明,加入10%HA的复合材料在人工模拟体液(SBF)中浸泡7d后表面生成了大量的类骨磷灰石层,与Ti-35Nb-7Zr合金相比,其显示出更优异的体外生物活性。     

Improve the Strength of PLA/HA Composite Through the Use of Surface Initiated Polymerization and Phosphonic Acid Coupling Agent

Bioresorbable composite made from degradable polymers, e.g., polylactide (PLA), and bioactive calcium phosphates, e.g., hydroxyapatite (HA), are clinically desirable for bone fixation, repair and tissue engineering because they do not need to be removed by surgery after the bone heals. However, preparation of PLA/HA composite from non-modified HA usually results in mechanical strength reductions due to a weak interface between PLA and HA. In this study, a calcium-phosphate/phosphonate hybrid shell was developed to introduce a greater amount of reactive hydroxyl groups onto the HA particles. Then, PLA was successfully grafted on HA by surface-initiated polymerization through the non-ionic surface hydroxyl groups. Thermogravimetric analysis indiated that the amount of grafted PLA on HA can be up to 7 %, which is about 50 % greater than that from the literature. PLA grafted HA shows significantly different pH dependent ζ-potential and particle size profiles from those of uncoated HA. By combining the phosphonic acid coupling agent and surface initiated polymerization, PLA could directly link to HA through covalent bond so that the interfacial interaction in the PLA/HA composite can be significantly improved. The diametral tensile strength of PLA/HA composite prepared from PLA-grafted HA was found to be over twice that of the composite prepared from the non-modified HA. Moreover, the tensile strength of the improved composite was 23 % higher than that of PLA alone. By varying additional variables, this approach has the potential to produce bioresorbable composites with improved mechanical properties that are in the range of natural bones, and can have wide applications for bone fixation and repair in load-bearing areas.     

Relationship between processing and mechanical properties of injection molded high molecular mass polyethylene + hydroxyapatite composites

We apply a macromolecular-orientation approach to produce high molecular weight polyethylene (HMWPE) + hydroxyapatite (HA) ductile composites with the stiffness and strength within the range of human cortical bone. Our composites are produced with different amounts (10 to 50% by weight) of the reinforcement by two procedures: bi-axial rotating drum and twin screw extrusion (TSE). The processing is by conventional injection molding and by Scorim (shear controlled orientation in injection molding) under a wide range of processing windows. Tensile testing is performed and the corresponding performance related to the morphology evaluated by polarized light microscopy and scanning electron microscopy. The control of the processing parameters led to significant improvements of the tensile properties. Compounding by TSE and then processing by Scorim produces the maximum modulus of 7.4 GPa and the ductility as high as 19%, for the HA weight fraction of 30%. These mechanical properties match those of bone, and were obtained with much smaller amounts of HA reinforcement then has been previously reported in literature. Our PE + HA composites present the additional benefit of being ductile even for 50% HA amounts. The use Scorim is a unique way of inducing anisotropy to thick sections and to produce very stiff composites that may be used in biomedical applications with important mechanical loads. This fact, combined with the bioactive behavior of the HA phase, makes our composite usable for orthopedic load-bearing implants. Received: 9 October 2000 / Reviewed and accepted: 10 October 2000