纤维增强磷酸钙骨水泥生物复合材料初探

目的采用羟基磷灰石包裹的聚乙烯纤维增强α-TCP生物骨水泥,以提高复合材料的强度. 方法利用X射线衍射和扫描电镜,对水化后的复合材料进行成份分析和组织观察,用CMT系列微机控制电子万能(拉力)试验机测其抗折强度,压汞法测气孔率. 结果水化产物主要为羟基磷灰石,形成的针状晶体在纳米尺度,抗折强度为8.20 MPa ,气孔率为45.8%.结论经过处理的聚乙烯纤维分散均匀与基体结合良好;纤维的加入可提高α-TCP骨水泥生物复合材料的强度;裂纹在纤维处被转向或钉扎.     

特色羟基磷灰石生物材料的发展

目的指出特色羟基磷灰石生物材料的发展趋势。方法综述羟基磷灰石复合生物陶瓷、水化产物为羟基磷灰石的生物骨水泥以及功能羟基磷灰石复合材料的发展。结果结论1、羟基磷灰石多相复合生物陶瓷的发展，在现有工作的基础上进一步提高强度、断裂韧性以适应承重及大面积的骨修复：2、利用骨水泥的可塑性及自固化性发展羟基磷灰石为主体的骨水泥复合材料，以提高临床应用性及手术的可操作性；3、通过在羟基磷灰石中添加少量的特殊物质，使复合材料具有某种预期的功能。     

特色羟基磷灰石生物材料的发展

目的指出特色羟基磷灰石生物材料的发展趋势.方法综述羟基磷灰石复合生物陶瓷、水化产物为羟基磷灰石的生物骨水泥以及功能羟基磷灰石复合材料的发展.结果结论1、羟基磷灰石多相复合生物陶瓷的发展,在现有工作的基础上进一步提高强度、断裂韧性以适应承重及大面积的骨修复;2、利用骨水泥的可塑性及自固化性发展羟基磷灰石为主体的骨水泥复合材料,以提高临床应用性及手术的可操作性;3、通过在羟基磷灰石中添加少量的特殊物质,使复合材料具有某种预期的功能.     

α-TCP骨水泥体外溶解动力学研究

研究了α-磷酸三钙(α-TCP)骨水泥在生理盐水体外的溶解动力学。实验结果表明，α-TCP骨水泥静态溶解过程符合Avrami动力学模型方程式：-In(1-x)=kt^1/2，并计算出溶解过程的表观活化能约为9．87kJ／mol．此过程由沉积的羟基磷灰石(HA)固膜扩散控制。     

聚磷酸钙纤维增强α-磷酸三钙/纳米羟基磷灰石骨水泥复合材料的力学性能

背景:利用纤维增强磷酸钙骨水泥的机制很早就被人们认识和利用。由于非吸收性纤维存在生物相容性低及应力遮挡等问题,近期的研究热点主要是可降解吸收的生物活性纤维对磷酸钙骨水泥性能的影响。目的:制备聚磷酸钙/(α-磷酸三钙/纳米羟基磷灰石)骨水泥复合材料,观察聚磷酸钙对磷酸钙骨水泥力学性能的增强效果。方法:利用固相反应法和湿法反应法分别制得α-磷酸三钙和纳米羟基磷灰石粉末,再将2种粉末按不同比例混合进行高温处理,然后将其与不同质量比、不同长度的聚磷酸钙纤维复合制成骨水泥试样。对试样进行凝固时间、力学性能测试,利用扫描电镜观察试样微观结构。结果与结论:聚磷酸钙长度为3mm、含量为10%时,抗压强度为66.43MPa,抗弯强度为13.86MPa。扫描电镜显示聚磷酸钙在磷酸钙骨水泥基体中分布均匀,结合性能好。在Ringer’s溶液中浸泡3个月,纤维仍具有一定的增强效果。提示聚磷酸钙纤维对α-磷酸三钙/纳米羟基磷灰石骨水泥有一定的增强作用,聚磷酸钙/(α-磷酸三钙/纳米羟基磷灰石)骨水泥复合材料具有良好的力学性能。     

不同条件煅烧牛骨物理性能差异分析

寻找煅烧牛骨的合适条件,为骨缺损的修复治疗提供一种较理想的异种生物材料。方法：将４０ｍｍ×５ｍｍ×２．５ｍｍ骨条按不同温度、时间进行烩煅烧处理后,进行气孔率、吸水率、体积密度、抗折强度的测定,以及差热分析、材料矿物组成分析。结果：牛煅烧骨的成分为结晶程度不高的羟基磷灰石,煅烧时间和温度以４５０℃,３２小时为较合适,此时气孔率５０．６４％,抗折强度１７．５７Ｍｐａ,低于或高于这种条件则会使其物理性能降低,及残留一定的免疫性。结论：煅烧条件以４５０℃,３２ｈ为宜,该异种生物骨成分为羟基磷灰石,保留了牛骨的原有框架和一定的力学强度,具有潜在的传导性修复骨缺损的能力。     

明胶溶胀行为对自固化多孔骨水泥性能和结构的影响

目的 研究明胶溶胀行为对多孔骨水泥性能和结构的影响。方法 在α-磷酸钙骨水泥体系中加入生物明胶，研究明胶对骨水泥水化产物、抗压强度和产物微结构所产生的影响。结果利用明胶的溶胀行为与水化过程中体系pH值变化的相关性，可制备具有大孔和微孔结构的骨水泥。结论加入明胶促进羟基磷灰石的成核，提高骨水泥的抗压强度。     

碳纤维增强α-磷酸三钙骨水泥的研究

为提高α-磷酸三钙（α—TCP）骨水泥的强度及降低其脆性，将表面改性后的碳纤维（CF）与α—TCP粉复合，制备成α—TCP／CF复合增强骨水泥。通过Ringer’s体液浸泡观察骨水泥快速结晶自固化能力，运用扫描电子显微镜（SEM）及抗压强度测试仪对复合材料浸泡后试样进行断面显微结构分析及抗压强度测试。结果显示，α—TCP骨水泥块浸泡5d后即转化生成片状羟基磷灰石晶体；适量的碳纤维在骨水泥基体中分布均匀，与基体结合性好，可得到抗压强度增强的骨修复材料；当碳纤维的加入重量百分数为0．5％时，复合材料抗压强度达到46．7MPa，比未增强的α—TCP材料提高了22％。     

α-磷酸三钙/HA晶须/羧甲基壳聚糖-明胶复合增强多孔骨水泥的制备研究

为研究羟基磷灰石(HA)晶须和羧甲基壳聚糖-明胶(CMC-Gel)对多孔磷酸钙骨水泥(CPC)力学性能的影响,将α-磷酸三钙(α-TCP)粉、HA晶须和致孔剂L-谷氨酸钠按一定的质量比进行混合,加入调和液制备成α-TCP/HA晶须复合多孔骨水泥,然后将其浸润到一系列不同CMC和Gel质量比的溶液中以制备α-TCP/HA晶须/CMC-Gel复合增强多孔骨水泥,对其进行抗压强度测试和扫描电镜观察。结果显示,当HA晶须含量为4%,未添加CMC和Gel时,α-TCP/HA晶须复合多孔骨水泥的抗压强度达到2.57MPa,与未复合HA晶须的骨水泥相比提高了81%;当CMC和Gel的质量比为50∶50时,α-TCP/HA晶须/CMC-Gel复合多孔骨水泥的抗压强度达到最大值3.34MPa,与单纯的多孔α-TCP骨水泥相比提高了135%,同时韧性也有较大改善。     

纳米羟基磷灰石骨修复复合材料的研究进展

羟基磷灰石（Hydroxyapatite，HA）是一种性能良好的骨修复材料，但是由于脆性而限制了它在承力部位的应用。天然骨本身是纳米羟基磷灰石（Nanohydroxyapatite，n．HA）和胶原的复合材料，从仿生的角度看，n—HA与其它材料复合可以提高生物相容性和力学性能。目前研究的纳米羟基磷灰石复合材料可分为两类：非降解的纳米羟基磷灰石复合材料和可降解的纳米羟基磷灰石复合材料。前者包括n—HA/聚乙烯、n-HA／尼龙以及n—HA／聚丙烯酸。后者主要有n—HA与胶原、明胶、壳聚糖、聚乳酸和聚酸酐等的复合材料。本文详细综述了近年来纳米羟基磷灰石复合材料的制备、力学性能以及生物学性能的研究进展。     

可注射聚富马酸丙二醇酯/β-磷酸三钙骨水泥的体外生物活性及其降解性

BACKGROUND: Poly(propylene fumarate) (PPF) can crosslink at room temperature, and β-tricalcium phosphate (β-TCP) has good biocompatibility, but PPF/β-TCP composite bone cement has not yet been systematically studied. OBJECTIVE: To prepare PPF/β-TCP composite bone cement and to explore its in vitro bioactivity and degradability. METHODS: β-TCP and PPF were respectively synthesized by liquid-phase precipitation and a two-step method, and PPF/β-TCP composite bone cement was prepared through mixing PPF with β-TCP. The    in vitro bioactivity of PPF/β-TCP was compared with the commercial poly(methyl methacrylate) (PMMA) through the ability of forming hydroxyapatite after immersed in simulated body fluid for 7 days. The in vitro degradability of PPF/β-TCP was studied via investigating the transformation of pH values, water uptake and mass loss, compressive strength and morphology at each time point. RESULTS AND CONCLUSION: There were hydroxyapatites formed on the PPF/β-TCP material, but none on the commercial PMMA material. The pH values of the PPF/β-TCP were stable in PBS for 63 days, indicating its degradation is moderate; the mass loss was up to 13.5% after 84 days. Scanning electron microscope displayed the degraded PPF/β-TCP surface, and its compressive strength was decreased gradually, which good for the integrity and sustainability of mechanical properties during degradation. These results suggest that PPF/β-TCP bone cement holds mineralization and degradability in vitro.     

新型可吸收骨水泥的制备及其应用于小牛椎体标本压缩性骨折椎体成形术的生物力学研究

目的 探讨聚富马酸丙二醇酯（PPF）/β-磷酸三钙（β-TCP）制备新型可吸收骨水泥的配方及其应用于小牛椎体标本压缩性骨折椎体成形术的生物力学性能研究。方法 采用两步法制备PPF,使用凝胶渗透色谱仪测量PPF的数均分子量、重均分子量及聚合度分布指数,使用MR氢谱对PPF进行结构分析。将制备好的PPF与β-TCP按照10∶1、5∶1、3∶1、2∶1配制不同热交联反应体系,制备4种不同配方的PPF/β-TCP可吸收骨水泥,选择抗压强度和压缩模量均较高的骨水泥进行后续实验。选取2~3岁健康小牛腰椎L₁~L₄节段标本4具,分离出16个椎体,使用牙托粉填平每个椎体的椎板凹陷部位,测量每个椎体的受力面积。选择椎体受力面积相近的10个椎体,按数字表法随机分为PPF/β-TCP组和甲基丙烯酸甲酯（PMMA）组,每组5个。PMMA组和PPF/β-TCP组椎体使用MTS-858力学机器制备压缩性骨折模型,对比2组完成模型制备时的椎体高度、抗压强度和刚度。PPF/β-TCP组和PMMA组分别使用PPF/β-TCP骨水泥和标准PMMA骨水泥对压缩骨折模型行椎体成形术,对比2组骨水泥注入量,术后椎体高度、椎体恢复百分比,椎体抗压强度、刚度。结果 PPF数均分子量为1 637±55,重均分子量为1 741±68,聚合分布指数为1.06。MR氢谱结构分析提示反应产物为PPF。配方1~4 PPF/β-TCP可吸收骨水泥抗压强度分别为（53.5±1.5）、（63.2±0.4）、（97.9±5.5）、（100.8±3.2）MPa,压缩模量分别为（0.97±0.04）、（1.05±0.05）、（1.10±0.10）、（0.45±0.18）GPa。选取压缩模量与抗压强度均高的配方3 PPF/β-TCP可吸收骨水泥用于椎体成形术。PPF/β-TCP组和PMMA组小牛椎体标本的椎体体积、高度、受力面积差异均无统计学意义（P值均>0.05）。PPF/β-TCP组和PMMA组的椎体压缩性骨折后高度、椎体成形术后椎体高度以及椎体高度恢复百分比差异均无统计学意义（P值均>0.05）。组内比较：PPF/β-TCP组椎体压缩性骨折椎体成形手术前后椎体抗压强度分别为（2 282±341）N和（1 848±219）N,椎体刚度分别为（215±27）N/mm和（182±15）N/mm,差异均无统计学意义（t=2.14、2.13,P值均>0.05）;PMMA组压缩性骨折椎体成形手术前后抗压强度分别为（2 350±289）N和（3 105±452）N,椎体刚度分别为（221±26）N/mm和（296±37）N/mm,差异均有统计学意义（t=2.81、3.21,P值均<0.05）。组间比较：PPF/β-TCP组与PMMA组术中骨水泥注入量差异无统计学意义（P>0.05）;PPF/β-TCP组与PMMA组发生压缩性骨折时椎体抗压强度和刚度差异均无统计学意义（P值均>0.05）,椎体成形术后椎体抗压强度和刚度PMMA组均大于PPF/β-TCP组,差异均有统计学意义（t=4.99、5.61,P值均<0.05）。结论 PPF与β-TCP按照3∶1配制的可吸收骨水泥具有与人椎体力学性能相近、交联温度低等特点。在治疗小牛椎体压缩性骨折模型时,PPF/β-TCP可吸收骨水泥与PMMA骨水泥术中注入量相近,两者恢复椎体高度的效果相当;且PPF/β-TCP可吸收骨水泥注入后椎体力学性能优于注入PMMA骨水泥者,具有替代PMMA骨水泥治疗椎体压缩性骨折的潜力。     

Carvable calcium phosphate bone substitute material

This study investigated the use of partially set hydroxyapatite forming calcium phosphate cement as a carvable and mechanically stable bone substitute material. Hydroxyapatite-forming cements were made of either mechanically activated alpha-tricalcium phosphate or a mixture of tetracalcium phosphate and dicalcium phosphate anhydrous and setting was arrested up to 4 h post setting. The study showed that these partially set rigid samples of defined geometry could be carved into a desired shape when the degree of reaction was 30-40% and the relative porosity between 40 and 50%; samples are then expected to set completely after implantation in the presence of water or serum, having the same compressive strength as a continuously set calcium phosphate cement (up to 36 MPa). The development of compressive strength, phase composition, and crystallinity when varying production parameters of these partially "preset" bone substitute materials are presented for both cement systems.     

Foamed surfactant solution as a template for self-setting injectable hydroxyapatite scaffolds for bone regeneration

The application of minimally invasive surgical techniques in the field of orthopaedic surgery has created a growing need for new injectable synthetic materials that can be used for bone grafting. In this work a novel fully synthetic injectable calcium phosphate foam was developed by mixing α-tricalcium phosphate (α-TCP) powder with a foamed polysorbate 80 solution. Polysorbate 80 is a non-ionic surfactant approved for parenteral applications. The foam was able to retain the porous structure after injection provided that the foamed paste was injected shortly after mixing (typically 2.5 min), and set through the hydrolysis of α-TCP to a calcium-deficient hydroxyapatite, thus producing a hydroxyapatite solid foam in situ. The effect of different processing parameters on the porosity, microstructure, injectability and mechanical properties of the hydroxyapatite foams was analysed, and the ability of the pre-set foam to support osteoblastic-like cell proliferation and differentiation was assessed. Interestingly, the concentration of surfactant needed to obtain the foams was lower than that considered safe in drug formulations for parenteral administration. The possibility of combining bioactivity, injectability, macroporosity and self-setting ability in a single fully synthetic material represents a step forward in the design of new materials for bone regeneration compatible with minimally invasive surgical techniques.     

Osseointegration of composite calcium phosphate bioceramics

The resistance of macroporous calcium phosphate ceramics to compressive strength generally is low and depends on, among other factors, porosity percentage and pore size. A compromise always is adopted between high porosity, required for a good integration, and mechanical strength, which increases with material density. We improved the strength of macroporous calcium phosphate ceramics of interconnected porosity by filling the pores with a highly soluble, self-setting calcium phosphate cement made of TCP and DCPD. Cylinders of the resulting material were implanted in sheep condyles and subjected to histological analysis after 20, 60, and 120 days. Microradiographs were made of the histological sections. The control material consisted of ceramic that had not been loaded with cement. Progressive ingrowth of bone into the ceramic pores occurred as the cement was degraded during the first implantation period. Marked degradation of the cement was apparent after 2 months, with fragmentation of the cement in most of the pores and the presence of bone tissue between the fragments. All the cement had been replaced by bone after 4 months. Some fragments of cement still were embedded in the newly formed bone. There was no significant difference between the integration of loaded and nonloaded ceramics. Filling the macroporous ceramic pores with a calcium phosphate cement significantly improved the mechanical strength of these ceramics without modifying their integration in the healing bone.     

经表面修饰的-TCP对BMSCs细胞增殖及分化作用的研究

目的研究三种材料,材料一：β-磷酸三钙支架（β—TCP）;材料二：明胶／1氐结晶度羟基磷灰石涂层-磷酸三钙支架（gel／lc—HA．β-TCP）;材料三：明胶／高结晶度羟基磷灰石涂层-β-磷酸三钙（gel／he-HA-β-TCP）。三种材料的细胞毒性及兔骨髓基质细胞（BMSCs）与材料共培养增殖的情况。方法取兔股骨骨髓腔细胞,进行贴壁培养BMSCs。在成骨诱导液中诱导BMSCs。将诱导后的BMSCs与三种支架材料在培养板内共培养1、3、5、7、9d。采用形态学观察、MTT法及ALP检测试剂盒等方法检测材料的BMSCs细胞毒性及BMSCs细胞在材料表面的增殖和分化能力。结果光镜及电镜下观察各组无显著差异。细胞毒性在0-1级。与细胞共培养,β-TCP组在第7．9天与阴性对照组差异有统计学意义。ALP检测,β-TCP组在第7、9天与阴性对照组差异有统计学意义（P〈0．05）,gel／lc—HA-β-TCP在第9天与阴性对照组差异有统计学意义（p〈0．05）。结论新型明胶／高结晶度羟基磷灰石涂层-β-磷酸三钙支架和明胶／低结晶度羟基磷灰石涂层-β-磷酸三钙支架与BMSCs生物相容性好,适合作为支架材料负载BMSCs构建组织工程骨。     

Mechanical characterization of brushite and hydroxyapatite cements

Compression, tension and torsion tests were designed and completed successfully on a brushite and a precipitated hydroxyapatite cement in moist condition. Elastic and strength properties were measured for these three loading cases. For each cement, the full set of strength data was fitted to an isotropic Tsai-Wu criterion and the associated coefficients identified. Since the compressive Young's moduli were about 10% larger than the tensile moduli, the full set of elastic data of each cement was fitted to a conewise linear elastic model. Hysteresis of the stress-strain curves was also observed, indicating dissipation mechanisms within these cement microstructures. A comparison of the measured mechanical properties with human cancellous bone confirmed the indication of brushite as a bone filling material and the potential of the hydroxyapatite cement as a structural biomaterial.     

α-Tricalcium phosphate: synthesis, properties and biomedical applications

Nowadays, α-tricalcium phosphate (α-TCP, α-Ca₃(PO₄)₂) is receiving growing attention as a raw material for several injectable hydraulic bone cements, biodegradable bioceramics and composites for bone repair. In the phase equilibrium diagram of the CaO–P₂O₅ system, three polymorphs corresponding to the composition Ca₃(PO₄)₂ are recognized: β-TCP, α-TCP and α′-TCP. α-TCP is formed by heating the low-temperature polymorph β-TCP or by thermal crystallization of amorphous precursors with the proper composition above the transformation temperature. The α-TCP phase may be retained at room temperature in a metastable state, and its range of stability is strongly influenced by ionic substitutions. It is as biocompatible as β-TCP, but more soluble, and hydrolyses rapidly to calcium-deficient hydroxyapatite, which makes α-TCP a useful component for preparing self-setting osteotransductive bone cements and biodegradable bioceramics and composites for bone repairing. The literature published on the synthesis and properties of α-TCP is sometimes contradictory, and therefore this article focuses on reviewing and critically discussing the synthetic methods and physicochemical and biological properties of α-TCP-based biomaterials (excluding α-TCP-based bone cements).     

Toughness,bonding and fluoride-release properties of hydroxyapatite-added glass ionomer cement

Improving the mechanical strength of glass ionomer cement while preserving its favorable clinical properties such as fluoride release, bonding to tooth structure and biocompatibility is desirable. In this study, hydroxyapatite was incorporated into chemically setting glass ionomer cement and its effect on the fracture toughness, bonding to dentin and fluoride release was identified. Commercial glass ionomer cement (Fuji IX GP((R)) ) was the control and base material. Eight weight percent of hydroxyapatite was added into the glass ionomer powder. Specimens were fabricated and the fracture toughness, shear bond strength and eluted fluoride ion concentration were measured. Adding hydroxyapatite into the glass ionomer cement led to significantly higher fracture toughness after 15min and 24h from mixing. The hydroxyapatite-added cement also exhibited bond strength to dentin similar to that of the control from 15min to 56 days and consistent fluoride release for 13 weeks. SEM findings showed a cohesive type of fracture in the material for all specimens in both groups. These results indicate that hydroxyapatite-added glass ionomer cement has a potential as a reliable restorative material with improved fracture toughness, long-term bonding to dentin and unimpeded ability of sustained fluoride release.