非晶钛合金Ti60Zr10Fe5Si9Nb5Mo11的组织及生物相容性研究

通过透射电子显微镜(TEM)对快速凝固合金Ti60Zr10Fe5Si9Nb5Mo11(原子分数,%)的微观形貌进行观察发现,合金晶界模糊,一些数量的纳米粒子沿晶界分布。通过X射线衍射仪(XRD)对合金进行相分析,结果表明,合金的基体组织为非晶态,沿模糊晶界处的析出物分别为纳米的β-Ti和Ti5Si3粒子。在模拟体液中对合金的生物相容性和生物活性进行评估,结果发现,合金表面沉积物的钙磷比与人体自然骨中的磷酸盐的钙磷比1.66:1极为接近,表明其具有良好的生物相容性和生物活性。     

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。     

磷酸镁/PBS/小麦蛋白复合骨修复材料

采用共沉淀法合成磷酸镁, 将磷酸镁(MP)、聚丁二酸丁二醇酯(PBS)和小麦蛋白(WP)进行复合, 制备出MP/PBS/WP复合骨修复材料。通过体外降解、生物活性以及细胞培养等实验对复合材料的理化性能及细胞相容性进行了研究。结果显示: MP/PBS/WP复合材料在Tris-HCl缓冲液中浸泡10 d后, 溶液pH从7.4上升至7.51, 浸泡12 w后, 其降解率达到58.43wt%; 复合材料在模拟体液中浸泡10 d后, 其表面形成磷灰石层; 复合材料能促进MC3T3-E1细胞的增殖与分化。结果表明: MP/PBS/WP复合材料具有优良的降解性、生物活性和细胞相容性, 有望成为一种新型骨修复材料。     

Ti-35Nb-7Zr/10CPP生物复合材料微观组织与性能研究

添加了占钛合金基体10%(质量分数)的焦磷酸钙(CPP)生物活性陶瓷粉末,利用放电等离子烧结(SPS)技术制备了Ti-35Nb-7Zr/10CPP生物复合材料,研究了其物相组成、微观组织形貌、元素分布、力学性能以及生物活性等。结果表明,该复合材料主要由β-Ti相基体、少量的α-Ti相及金属-陶瓷相(CaO、Ti2O、CaTiO3、CaZrO3、TxPy)组成;复合材料具有较低的压缩弹性模量(46 GPa)和较高的抗压强度(1 434 MPa),显示了良好的力学相容性;与Ti-35Nb-7Zr合金相比,复合材料在人工模拟体液(SBF)浸泡7d后表面生成了大量的类骨磷灰石层,显示出良好的生物活性。     

3D打印医用钛合金的抗菌性能和体外生物相容性

应用选择性激光熔融技术(SLM)制备出3D打印医用钛合金Ti-6Al-4V和Ti-6Al-4V-5Cu,用平板共培养法研究测定其抗菌性能,用CCK8细胞增殖测定法、鬼笔环肽细胞骨架染色法和Annexin-V/PI流式细胞术研究了这种合金的抗菌性能和对小鼠胚胎成骨前体细胞(MC3T3-E1)的体外生物相容性影响。结果表明,3D打印Ti-6Al-4V-5Cu合金具有较高的抗菌性能,对金黄色葡萄球菌的抗菌率达到(57.03±1.55)%。在CCK8细胞增殖毒性测定、细胞骨架鬼笔环肽染色实验和Annexin-V/PI双标记法流式分析三种研究中Ti-6Al-4V-5Cu表现的优越,具有更好的体外生物相容性。     

表面多孔Ti-羟基磷灰石/Ti-Ag生物梯度复合材料的制备与性能

采用放电等离子烧结技术制备表面多孔Ti-羟基磷灰石（HA）/Ti-Ag生物梯度复合材料,研究了不同HA含量对复合材料微观结构、界面结合、表面孔隙特征、力学性能及体外生物活性的影响及机制。结果表明,表面多孔Ti-HA/Ti-Ag复合材料中间基体合金主要由α-Ti和Ti₂Ag相组成,表面多孔层主要由α-Ti和HA相组成,同时还存在少量CaO、CaTiO₃、Ti₅P₃等反应相;表面多孔Ti-HA/Ti-Ag复合材料中间基体与表面多孔层形成稳定的冶金结合,但随着HA含量增加,反应相增多,界面结合变差,表面孔隙率和平均孔径呈增大趋势,导致平均抗压强度减小且弹性模量降低,因此过高的HA含量会导致材料力学性能下降;体外生物活性实验表明,表面多孔Ti-HA/Ti-Ag复合材料在人工模拟体液中浸泡7天后表面生成大量类骨磷灰石层,并且随着HA含量的增大,磷灰石形成能力明显增强。      

聚乳酸组织工程支架表面涂覆钙磷盐的工艺研究

提出了以聚乳酸／钙磷盐／胶原的骨组织工程支架快速成形制造的材料系统，对比了两种在聚乳酸(PLA)表面涂覆钙磷盐的工艺．一种是将聚乳酸组织工程支架浸泡在模拟体液中采用平衡反应法沉积钙磷盐；另一种是在聚乳酸薄膜上采用非平衡反应法沉积钙磷盐；系统地研究了沉积时间和沉积量、钙磷摩尔比和相结构演变的关系；通过控制反应时间和调整反应物配比获得磷酸四钙(TetCP)-PLA和无定形磷酸钙(ACP)—PLA等材料组合；并对所获得的复合材料进行生物相容性试验．对比试验证明细胞在材料表面生长良好，采用两种方法涂覆钙磷盐均改进了聚乳酸的生物相容性．     

Ti-27Mo-1.5Nb无磁不锈定膨胀合金研究

研究了一种Ti-27Mo-1.5Nb新型无磁不锈定膨胀合金,该合金的膨胀系数为7.70×10-6/℃,磁导率为1.0003,同时研究了Ti-27Mo-1.5Nb合金的微屈服强度及其它机械性能和物理性能,该合金还是良好的耐腐蚀材料,试验表明,Ti-27Mo-1.5Nb合金是诸如静电陀螺等电真空领域中与高纯Al2O3匹配的良好封接材料。     

二氧化锆梯度复合羟基磷灰石生物材料的制备及其生物相容性

采用干铺2烧结法制备了一种以二氧化锆(ZrO₂ ) 为基体梯度复合羟基磷灰石( HAP) 的新型生物复合材料, 并对其力学性能、微观结构和生物相容性进行了研究。用扫描电镜(SEM) 、X 射线衍射仪(XRD) 、透射电镜( TEM) 和EDAX 能谱仪对粉体和复合材料进行分析。用复合材料的浸提液进行小鼠急性毒性试验、细胞毒性试验、体外溶血试验以及兔肌肉和骨内材料植入试验, 评价复合材料的生物相容性。研究结果表明, 复合材料的表面涂层厚度约80μm , 芯部基体组织与表面均匀过渡结合, 结合良好, 没有明显界面, 涂层结合强度为15. 1 MPa ,最大弯曲强度为1112. 24 MPa , KIC为7. 3～11. 4 MPa·m1/2 。其组织相容性好, 具有良好的骨传导作用, 促进骨组织生长, 是一种较理想的新型骨科植入材料。      

卵磷脂改性磁性碳纳米管的制备及生物相容性

采用生物活性两亲性分子卵磷脂(PC), 对制备的磁性碳纳米管(Fe₃O₄/CNTs)进行非共价修饰, 得到了内部为疏水端、外部为带电亲水基团的类膜结构包覆的改性复合材料Fe₃O₄/CNTs-PC。在溶液中带电基团通过溶剂化作用及亲水作用, 在复合材料表面形成水化层, 提高复合材料的自由水含量。在蛋白质吸附实验与复钙化凝血时间评价中, Fe₃O₄/CNTs-PC对蛋白质吸附量仅为0.1368 mg/mg, 复钙化凝血时间延长至324 s, 具有很好的生物相容性。     

Fabrication and biocompatibility in vitro of potassium titanate biological thin film/titanium alloy biological composite

A potassium titanate biological thin film/titanium alloy biological composite was fabricated by way of bionic chemistry. The biocompatibility in vitro of Ti-15Mo-3Nb and the potassium titanate biological thin film/titanium alloy was studied using simulated body fluid cultivation, kinetic clotting of blood and osteoblast cell cultivation experiments in vitro. By comparing the biological properties of both materials, the following conclusions can be obtained: (1) The deposition of a calcium phosphate layer was not found on the surface of Ti-15Mo-3Nb, so it was bioinert. Because the network of potassium titanate biological thin film could induce the deposition of a calcium phosphate layer, this showed that it had excellent bioactivity. (2) According to the values of kinetic clotting, the blood coagulation time of the potassium titanate biological thin film was more than that of Ti-15Mo-3Nb. It was obvious that the potassium titanate biological thin film possessed good hemocompatibility. (3) The cell compatibility of both materials was very good. However, the growth trend and multiplication of osteoblast cells on the surface of potassium titanate biological thin film was better, which made for the concrescence of wounds during the earlier period. As a result, the potassium titanate biological thin film/titanium alloy showed better biocompatibility and bioactivity.     

Fabrication and biocompatibility in vitro of potassium titanate biological thin film/titanium alloy biological composite

A potassium titanate biological thin film/titanium alloy biological composite was fabricated by way of bionic chemistry. The biocompatibility in vitro of Ti-15Mo-3Nb and the potassium titanate biological thin film/titanium alloy was studied using simulated body fluid cultivation, kinetic clotting of blood and osteoblast cell cultivation experiments in vitro. By comparing the biological properties of both materials, the following conclusions can be obtained: (1) The deposition of a calcium phosphate layer was not found on the surface of Ti-15Mo-3Nb, so it was bioinert. Because the network of potassium titanate biological thin film could induce the deposition of a calcium phosphate layer, this showed that it had excellent bioactivity. (2) According to the values of kinetic clotting, the blood coagulation time of the potassium titanate biological thin film was more than that of Ti-15Mo-3Nb. It was obvious that the potassium titanate biological thin film possessed good hemocompatibility. (3) The cell compatibility of both materials was very good. However, the growth trend and multiplication of osteoblast cells on the surface of potassium titanate biological thin film was better, which made for the concrescence of wounds during the earlier period. As a result, the potassium titanate biological thin film/titanium alloy showed better biocompatibility and bioactivity. Translated from Journal of Functional Materials, 2006, 37(10): 1,638–1,642 (in Chinese)     

Ti-10Mo-XNb合金铸态组织和机械性能的研究

为了研究Nb元素对Ti-10Mo合金组织和性能的影响,采用钨电极熔化、离心浇注工艺制备了4种钛合金(Ti-10Mo-XNb,X=0,3,7,10),分析并测试了Nb元素对Ti-10Mo合金铸态组织和力学性能的影响.研究结果表明:随着Nb含量的增加,3种Ti-Mo-Nb合金的铸态组织和相组成发生了改变,Ti-10Mo-3Nb合金由等轴的α+β晶粒组成,Ti-10Mo-7Nb合金由等轴的β晶粒组成,Ti-10Mo-10Nb合金由少量等轴和大量枝状的β晶粒组成.另外,随着Nb含量的增加,3种Ti-Mo-Nb合金的维氏硬度、压缩强度、弹性模量降低,压缩率和抗弯强度升高,压缩断口和弯曲断口由脆性断裂向韧性断裂转变.Ti-Mo-Nb合金有望成为新型的生物医用材料.     

Influence of noble metals alloying additions on the corrosion behaviour of titanium in a fluoride-containing environment

Titanium alloys exhibit excellent corrosion resistance in most aqueous media due to the formation of a stable oxide film, and some of these alloys (particularly Ti-6Al-7Nb) have been chosen for surgical and odontological implants for their resistance and biocompatibility. Treatment with fluorides (F⁻) is known to be the main method for preventing plaque formation and dental caries. Toothpastes, mouthwashes, and prophylactic gels can contain from 200 to 20,000 ppm F⁻ and can affect the corrosion behaviour of titanium alloy devices present in the oral cavity. In this work, the electrochemical corrosion behaviour of Ti-1M alloys (M = Ag, Au, Pd, Pt) was assessed in artificial saliva of pH = 3.0 containing 910 ppm F⁻ (0.05 M NaF) through open circuit potential, E_OC, and electrochemical impedance spectroscopy (EIS) measurements. The corrosion behaviour of the Ti-6Al-7Nb commercial alloy was also evaluated for comparison. E _OC measurements show an active behaviour for all the titanium alloys in fluoridated acidified saliva due to the presence of significant concentrations of HF and HF₂ ⁻ species that dissolve the spontaneous air-formed oxide film giving rise to surface activation. However, an increase in stability of the passive oxide layer and consequently a decrease in surface activation is observed for the Ti-1M alloys. This behaviour is confirmed by EIS measurements. In fact, the Ti-6Al-7Nb alloy exhibits lower impedance values as compared with Ti-1M alloys, the highest values being measured for the Ti-1Au alloy. The experimental results show that the corrosion resistance of the studied Ti-1M alloys is similar to or better than that of Ti-6Al-7Nb alloy currently used as biomaterial, suggesting their potential for dental applications.     

A study of histological responses from Ti-6Al-7Nb alloy dental implants with and without plasma-sprayed hydroxyapatite coating in dogs

Titanium alloys are hoped to be used much more for applications as implant materials in the medical and dental fields because of their basic properties, such as biocompatibility, corrosion resistance and specific strength compared with other metallic implant materials. Thus, the Ti-6Al-7Nb alloy that has recently been developed for biomedical use, that is, primarily developed for orthopaedic use, is to be studied in this paper, for application in dental implants. The biocompatibility test in vivo was carried out in dogs and the osseointegration was verified through histological analysis of the samples of the Ti-6Al-7Nb alloy with and without hydroxyapatite coating that were inserted in the alveoli. Within the controlled conditions the samples did not show any toxic effects on the cells. © 2001 Kluwer Academic Publishers     

船用Ti-75合金表面微弧氧化研究

采用微弧氧化在船用Ti-75合金表面合成了氧化膜。研究了不同浓度弱酸性的磷酸盐电解液的微弧氧化膜微观结构和显微硬度。结果表明,Ti-75合金微弧氧化膜宏观表面均匀致密,微观呈多孔结构,且氧化膜中明显引入了电解液中的成分,该膜层具有足够的厚度、绝缘电阻,显微硬度明显高于基体的,是提高船用Ti-75合金绝缘性能及抗磨损性能的一种较好的表面处理方法。     

Ti-48Al-2Cr-2Nb钝化膜的电化学性能及形成机理

探究Ti-48Al-2Cr-2Nb合金钝化膜的耐腐蚀性和形成机理对提高电解加工过程中的抗杂散腐蚀具有重要意义。通过极化曲线确定了Ti-48Al-2Cr-2Nb合金的钝化电位,采用X射线光电子能谱确定了钝化膜的成分与结构,并运用电化学阻抗谱和Mott-Schottky理论分析了钝化膜的电化学性能。结果表明,Ti-48Al-2Cr-2Nb合金在NaNO3电解液中钝化电位区间为0.079～1.896V,钝化膜主要成分为Al₂O₃、TiO₂及少量的Nb₂O₅,呈双层多孔结构,具有良好的耐腐蚀性。钝化膜具有n型半导体特性,载流子密度随钝化电位的增加而降低。最后,构建了钝化膜形成示意图,揭示了Ti-48Al-2Cr-2Nb合金钝化膜的形成机理与成相膜理论相符,以半球体模型延展并形成独立的相。     

Biocompatibility studies of human fetal osteoblast cells cultured on gamma titanium aluminide

Ti-48Al-2Cr-2Nb (at. %) (γTiAl), a gamma titanium aluminide alloy originally designed for aerospace applications, appears to have excellent potential for bone repair and replacement. The biological response to γTiAl implant is expected to be similar to other titanium-based biomaterials. Human fetal osteoblast cells were cultured on the surface of γTiAl and Ti-6Al-4V disks with variable surface roughness for both SEM and immunofluorescent analysis to detect the presence of collagen type I and osteonectin, proteins of the bone extracellular matrix. Qualitative results show that cell growth and attachment on γTiAl was normal compared to that of Ti-6Al-4V, suggesting that γTiAl is not toxic to osteoblasts. The presence of collagen type I and osteonectin was observed on both γTiAl and Ti-6Al-4V. The results obtained suggest γTiAl is biocompatible with the osteoblast cells.     

Calcium phosphate coating of Ti–Nb–Zr–Sn titanium alloy

This study focuses on rapid formation of calcium phosphate coating on a β type Ti–Nb–Zr–Sn biomedical titanium alloy by alkali treatment. The results show that a bioconductive surface layer forms on specimens immersed in 1–5 M KOH solution but only treatment in 1 M KOH avoids formation of crevices, producing a potassium titanate layer with porous network structure. Heat treatment at 600 °C after the alkali treatment promotes titanate growth. Following the above treatments, a continuous apatite layer forms within 4 h of soaking in a calcium phosphate solution with high ionic concentration. Such rapid apatite formation is due to high concentration of calcium ions in the solution used in this study and the buffering function of NaHCO₃. Results of dissolution experiment show that Ca and P ions release gradually from the coating during soaking in a 0.9% NaCl solution, which may be helpful to the formation of natural bone if implanted in human body. Cell culture experiment shows that the apatite layer favours adhesion and proliferation of rat osteoblast as compared with coating-free Ti–Nb–Zr–Sn alloy and commercially pure titanium (CP Ti).