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。     

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。     

烧结温度对焦磷酸钙/Ti-35Nb-7Zr复合材料微观组织及力学性能的影响

为改善β型Ti-Nb-Zr合金的生物活性,添加20wt%的焦磷酸钙(CPP)生物陶瓷,利用放电等离子烧结技术制备20CPP/Ti-35Nb-7Zr生物复合材料。借助XRD、SEM及力学测试方法等研究不同烧结温度(1 000~1 200℃)下复合材料的微观组织及力学性能,揭示其组织演变对力学性能的影响机制。结果表明:20CPP/Ti-35Nb-7Zr复合材料主要由β-Ti相基体、少量残留α-Ti相及金属-陶瓷相(CaTiO_3、Ti_2O、CaO、CaZrO_3和TixPy)组成;随着烧结温度升高,复合材料中β-Ti相和金属-陶瓷相逐渐增多;金属与陶瓷之间的剧烈反应导致金属-陶瓷相的形态结构发生变化,复合材料中金属-陶瓷相从颗粒状析出物演变成连续网状组织,起到割裂基体的作用。20CPP/Ti-35Nb-7Zr复合材料的压缩弹性模量和抗压强度随着烧结温度的升高而增大,其中压缩弹性模量从64.0GPa增加至71.4GPa,金属-陶瓷相形态结构变化起主导作用。因此,控制20CPP/Ti-Nb-Zr复合材料中金属-陶瓷相的形态结构将有利于改善其力学性能。     

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。      

羟基磷灰石-二氧化锆生物复合材料的制备及其生物相容性

对适用于人体承重部位的人工种植体羟基磷灰石2二氧化锆生物复合材料的制备工艺、微观结构及生物相容性进行了初步研究。用扫描电镜(SEM) 、X 射线衍射(XRD) 和透射电镜( TEM) 对粉体和复合材料进行分析。用体外检测复合材料浸提液对健康青年人末梢血单个核细胞( PBMC) 的激活来评价其免疫相容性。结果表明:1600 ℃无压烧结3h 后的复合材料表面层主晶相为β-Ca₃ ( PO₄ )₂ (β-TCP) 、α-Ca₃ ( PO₄ )₂ (α-TCP) 和CaZrO₃ 相。单纯复合材料和梯度复合材料的表面粗糙度分别为3. 12μm 和1. 95μm。其弯曲强度分别为732. 85 MPa 和689.04 MPa 。HA/ ZrO₂ 复合材料具有免疫相容性, 梯度复合材料的免疫相容性优于单纯复合材料。      

塑性钛基非晶复合材料的制备及性能

通过铜模喷铸法成功制备了一系列内生β-Ti(Zr, Nb)枝晶增塑的Ti-Zr-Nb-Cu-Be非晶复合材料, 研究了成分对枝晶体积分数及尺寸的影响及其对复合材料力学性能的调节作用。结果表明, Ti₄₈Zr₂₀Nb₁₂Cu₅Be₁₅合金压缩强度达到2061 MPa, 塑性变形高达22.5%, 表现出优异的综合力学性能。 非晶复合材料的塑性不仅与β-Ti(Zr,Nb)枝晶相的体积分数有关, 而且受到枝晶尺寸的强烈影响, 在一定体积分数条件下, 枝晶相的尺寸越大, 对剪切带的阻碍作用越明显, 合金的塑性越高。     

造孔剂对新型医用多孔Ti-14Mo-2.1Ta-0.9Nb-7Zr合金组织性能的影响

合金多孔化是有效降低材料弹性模量的方式之一,采用添加造孔剂的元素粉末冶金法制备了新型医用多孔Ti-14Mo-2.1Ta-0.9Nb-7Zr合金,通过扫描电镜、阿基米德法、X射线衍射和压缩力学性能测试的方法研究了不同造孔剂用量和粒径尺寸对合金形貌特征、孔隙率、物相组成及力学性能的影响规律。结果表明:该方法制备所得多孔Ti-14Mo-2.1Ta-0.9Nb-7Zr合金为近β型钛合金;随着造孔剂用量增加,平均孔径无变化,孔隙率呈线性增长,弹性模量和抗压强度减小,其中弹性模量的变化满足线性关系;随着造孔剂粒径尺寸增加,平均孔径增大而孔隙率基本不变,抗压强度和弹性模量减小;添加20%(质量分数)粒径尺寸为125~200μm的NH4HCO3造孔剂制备多孔Ti-14Mo-2.1Ta-0.9Nb-7Zr合金,于1300℃烧结4h孔隙率达到38.9%并含有贯穿孔结构,抗压强度达到405 MPa,而弹性模量为9.19GPa,能满足医用植入材料的要求。     

多孔ZnO/羟基磷灰石生物复合材料的制备与性能

利用放电等离子烧结技术制备多孔ZnO/羟基磷灰石（HA）生物复合材料,研究不同纳米ZnO含量对ZnO/HA复合材料微观结构、孔隙特征、力学性能、矿化和降解性能的影响。结果表明:烧结后ZnO/HA复合材料主要由HA相和ZnO相组成;随着ZnO含量提高,多孔ZnO/HA复合材料孔隙率缓慢增大,抗压强度略有减小,弹性模量变化不大;多孔ZnO/HA复合材料的孔隙率>40%,孔径在50～500 μm之间,抗压强度>148 MPa,弹性模量为6.5 GPa左右,能够满足骨修复材料的要求;模拟人工体液中矿化和降解实验表明,多孔ZnO/HA复合材料浸泡7天后表面开始形成大量类骨磷灰石层,且随着ZnO含量增加,磷灰石形成能力明显增强而降解速率加快。      

Ti-13Nb-13Zr钛合金板材热处理组织演变分析

对Ti-13Nb-13Zr钛合金板材固溶和时效热处理的组织变化进行了分析,结果表明,为了得到细小等轴β晶粒,推荐固溶处理制度：700℃／0．5h、水冷或空冷。为了保留过冷β相结构,为后续的时效强化做准备,推荐固溶处理工艺为800℃／0．5h、水冷。为使Ti-13Nb-13Zr钛合金达到良好的组织匹配,并且避免产生恶化合金性能的ω相,推荐热处理制度：固溶800℃／0．5h（水冷）＋时效处理560℃／8h。本结果也为Ti-13Nb-13Zr钛合金技术开发和专业生产提供参考。     

Mg-13Gd-1Zn合金的组织与力学性能

研究了铸态、退火态、挤压态和T5时效态Mg-13Gd-1Zn三元合金的显微组织和力学性能。结果表明,合金的铸态组织由α-Mg、(Mg,Zn)₃Gd和14H-LPSO长周期相组成。合金在均匀化退火和热挤压后的直接时效(T5)过程中都发生了晶内14H-LPSO相的沉淀析出,表明合金中14H-LPSO的沉淀相变发生在一个很宽的温度范围(200~510℃)。在挤压后合金的直接时效(T5)过程中发生了β'及β₁相的沉淀析出。在沉淀强化和LPSO强化的共同作用下,合金的屈服强度、抗拉强度和伸长率分别为197 MPa、397 MPa和2.56%。在200℃/80 MPa和200℃/120 MPa两种实验条件下,Mg-13Gd-1Zn合金的抗蠕变性能均优于WE54合金。     

Fibroblast Adhesion and Proliferation on a New β Type Ti-39Nb-13Ta-4.6Zr Alloy for Biomedical Application

Cell attachment and spreading on Ti-based alloy surfaces is a major parameter in implant technology. Ti-39Nb-13Ta-4.6Zr alloy is a new β type Ti alloy developed for biomedical application. This alloy has low modulus and high strength, which indicates that it can be used for medical purposes such as surgical implants. To evaluate the biocompatibility and effects of the surface morphology of Ti-39Nb-13Ta-4.6Zr on the cellular behaviour, the adhesion and proliferation of rat gingival fibroblasts were studied with substrates having different surface roughness and the results were also compared with commercial pure titanium and Ti-6Al-4V. The results indicate that fibroblast shows similar adhesion and proliferation on the smooth surfaces of commercial pure titanium （Cp Ti）, Ti-39Nb-13Ta-4.6Zr, and Ti-6Al-4V, suggesting that Ti-39Nb-13Ta-4.6Zr has similar biocompatibility to Cp Ti and Ti-6Al-4V. The fibroblast adhesion and spreading was lower on rough surfaces of Cp Ti, Ti-39Nb-13Ta-4.6Zr and Ti-6Al-4V than on smooth ones. Surface roughness appeared to be a dominant factor that determines the fibroblast adhesion and proliferation.     

Fibroblast Adhesion and Proliferation on a New β Type Ti-39Nb-13Ta-4.6Zr Alloy for Biomedical Application

Cell attachment and spreading on Ti-based alloy surfaces is a major parameter in implant technology. Ti39Nb-13Ta-4.6Zr alloy is a new β type Ti alloy developed for biomedical application. This alloy has low modulus and high strength, which indicates that it can be used for medical purposes such as surgical implants.To evaluate the biocompatibility and effects of the surface morphology of Ti-39Nb-13Ta-4.6Zr on the cellular behaviour, the adhesion and proliferation of rat gingival fibroblasts were studied with substrates having different surface roughness and the results were also compared with commercial pure titanium and Ti-6Al-4V. The results indicate that fibroblast shows similar adhesion and proliferation on the smooth surfaces of commercial pure titanium (Cp Ti), Ti-39Nb-13Ta-4.6Zr, and Ti-6Al-4V, suggesting that Ti-39Nb-13Ta-4.6Zr has similar biocompatibility to Cp Ti and Ti-6Al-4V. The fibroblast adhesion and spreading was lower on rough surfaces of Cp Ti, Ti-39Nb-13Ta-4.6Zr and Ti-6Al-4V than on smooth ones. Surface roughness appeared to be a dominant factor that determines the fibroblast adhesion and proliferation.     

Influence of hydroxyapatite on the corrosion resistance of the Ti-13Nb-13Zr alloy

Electrochemical analyses on the biocompatible alloy Ti-13Nb-13Zr wt% in an electrolyte simulating physiological medium (PBS solution) are reported. Hydroxyapatite (HA) films were obtained on the alloy by electrodeposition at constant cathodic current. Samples of the alloy covered with an anodic-oxide film or an anodic-oxide/HA film were analyzed by open circuit potential and electrochemical impedance spectroscopy measurements during 180 days in the PBS electrolyte. Analyses of the open-circuit potential (E _oc) values indicated that the oxide/HA film presents better protection characteristics than the oxide only. This behavior was corroborated by the higher film resistances obtained from impedance data, indicating that, besides improving the alloy osteointegration, the hydroxyapatite film may also increase the corrosion protection of the biomaterial.     

A novel biomedical titanium alloy with high antibacterial property and low elastic modulus

β-type titanium alloys have attracted much attention as implant materials because of their low elastic modulus and high strength,which is closer to human bones and can avoid the problem of stress fielding and extend the lifetime of prosthetics.However,other issues,such as the infection or inflammation postimplantation,still trouble the titanium alloy's clinical application.In this paper,we developed a novel near β-titanium alloy (Ti-13Nb-13Zr-13Ag,TNZA) with low elastic modulus and strong antibacterial ability by the addition of Ag element followed by proper microstructure controlling,which could reduce the stress shielding and bacterial infections simultaneously.The microstructure,mechanical properties,corrosion resistance,antibacterial properties and cell toxicity were studied using SEM,electrochemical testing,mechanical test and cell tests.The results have demonstrated that TNZA alloy exhibited an elastic modulus of 75-87 GPa and a strong antibacterial ability (up to 98 ％ reduction) and good biocompatibility.Moreover,it was also shown that this alloy's corrosion resistance was better than that of Ti-13Nb-13Zr.All the results suggested that Ti-13Nb-13Zr-13Ag might be a competitive biomedical titanium alloy.     

基于α'组织设计适于激光立体成形的新型高塑性Ti-4.13Al-9.36V合金

为了提高Ti-6Al-4V合金的加工硬化率和塑性,基于其团簇成分式12[Al-Ti₁₂](AlTi₂)+5[Al-Ti₁₄](V₂Ti)设计成分式为4[Al-Ti₁₂](AlTi₂)+12[Al-Ti₁₄](V₂Ti)的(Ti-4.13Al-9.36V, %)合金,采用激光立体成形工艺制备Ti-4.13Al-9.36V和Ti-6.05Al-3.94V(对比合金),研究了沉积态和固溶温度对其显微组织和力学性能的影响。结果表明,沉积态Ti-4.13Al-9.36V和Ti-6.05Al-3.94V合金的显微组织均由基体外延生长的初生β柱状晶和晶内细小的网篮α板条组成。Ti-6.05Al-3.94V合金的初生β柱状晶的宽度约为770 μm,α板条的宽度约为0.71 μm;而Ti-4.13Al-9.36V合金的初生β柱状晶的宽度显著减小到606 μm,α板条的宽度约为0.48 μm。经920℃固溶-淬火处理后Ti-6.05Al-3.94V样品的显微组织为α'+α相,其室温拉伸屈服强度约为893 MPa,抗拉强度约为1071 MPa,延伸率约为3%。经750℃固溶-淬火处理后Ti-4.13Al-9.36V样品的显微组织为α'+α相,与α'马氏体相比,应力诱发的α'马氏体能显著地提高合金的加工硬化能力,其室温拉伸屈服强度约为383 MPa,抗拉强度约为 989 MPa,延伸率达到了17%。这表明,根据团簇理论模型调控α'+α的显微组织能有效提高激光立体成形Ti合金的加工硬化能力和塑性。     

Fatigue behaviour of in situ TiB reinforced β-titanium alloy composite

In the present study, the effect of in situ TiB reinforcements on the fatigue behaviour of β-type Ti-35Nb-5.7Ta-7.2Zr (TNTZ) alloy has been investigated. It has been found that TiB reinforcements have no substantial influence on the yield strength and the fatigue strength of TNTZ alloy. Moreover, the presence of ω precipitates in the β matrix shows higher fatigue limit than the presence of α precipitates.     

Hydroxyapatite coating on the Ti-35Nb-xZr alloy by electron beam-physical vapor deposition

The aim of this study was to investigate the hydroxyapatite coating on the Ti-35Nb-xZr alloy by electron beam-physical vapor deposition. The Ti-35Nb-xZr ternary alloys contained from 3 wt.% to 10 wt.% Zr content were manufactured by arc melting furnace. Hydroxyapatite (HA) coatings were prepared by electron-beam physical vapor deposition (EB-PVD) method, and crystallization treatment was performed in Ar atmosphere at 300 and 500 °C for 1 h. The coated surface morphology of Ti-35Nb-xZr alloy was examined by FE-SEM, EDX and XRD, respectively. In order to evaluate the corrosion behavior, the tests were performed by potentiodynamic, cyclic polarization and AC impedance test. All the electrochemical data were obtained using a potentiostat. The Ti-35Nb-xZr alloys exhibited equiaxed structure with β phase, the peak of β phase increased with Zr contents. The hardness and elastic modulus of Ti-35Nb-xZr alloys decreased as Zr content increased. The HA coated layer was approximately 150 nm and Ca/P ratio of HA coated surface after heat treatment at 500 °C was around 1.67. The HA thin film consisted of small droplets with spherical shape by crystallization. From the anodic polarization curves, HA coated and heat treated Ti-35Nb-10Zr alloy showed higher corrosion potential than other samples. HA coated film on the Ti-35Nb-10Zr alloy can be shown high polarization resistance by crystallization.