医用多孔NiTi合金微波烧结的初步探讨

以镍粉和氢化钛粉为原料,经混粉、压坯后,在850～1100℃微波烧结10～30min获得多孔NiTi合金。利用阿基米德排水法、OM、SEM、EDS和XRD分别对多孔NiTi合金的孔隙率、表面形貌、成分和相组成进行了系统的分析。结果表明,微波烧结制备的多孔NiTi合金主要由B2型的NiTi相和少量Ni3Ti、Ti2Ni杂质相组成;随着烧结温度的升高,NiTi相增加而杂质相减少;多孔NiTi合金的孔隙率为30%～35.5%,孔径为20～60μm,随着烧结温度的升高,孔隙率在950℃之前变化不大,1000℃时获得最大值,之后逐渐下降;微波烧结的保温时间对合金相组成和孔隙率影响不大。     

尿素含量对Ti-10%Mg多孔材料孔隙结构和抗压性能的影响

以尿素为造孔剂,采用粉末冶金法在630℃真空条件下烧结制备Ti-10%Mg多孔材料,研究了造孔剂含量对其孔隙结构、物相成分、孔隙率及抗压性能的影响。研究表明,造孔剂含量为25%(w)时,烧结体的孔隙大小均匀,主要相为Ti和Mg,造孔剂添加量未对其物相产生明显影响;随着造孔剂含量的增加,烧结体的孔隙率随之增加,抗压强度和弹性模量随之降低;Ti-10%Mg多孔材料的抗压强度和弹性模量分别为16~183MPa和1.87~10.15 GPa,理论上可以作为人体骨骼的替代材料。     

多孔NiTi形状记忆合金的制备及性能

采用球磨后的NiTi合金粉末为原料,添加尿素作为造孔剂,利用粉末烧结法制备多孔NiTi形状记忆合金.研究烧结温度、保温时间和预成型压力等条件对制备的多孔NiTi合金组织结构和力学性能的影响.结果表明:相对于传统的Ni粉和Ti粉近等原子比混合烧结方法,此方法制备的多孔NiTi合金的相组成更加纯净.且随烧结温度升高,多孔N...     

多孔二氧化钛制备及其钙热还原的研究

提出了多孔钛制备的新方法,先采用占位体法制备出具有一定孔结构的二氧化钛,而后通过钙蒸气还原、浸出,获得多孔钛。借助X射线衍射、扫描电镜、X射线能谱仪、压汞仪等检测手段分别考察了造孔剂种类、造孔剂添加量、烧结温度、升温速率等对多孔二氧化钛孔结构的影响;并且通过钙蒸气还原制备出了具有一定孔结构的多孔钛。实验结果表明:添加不同种类造孔剂制备出的多孔二氧化钛的孔隙率大小的顺序为:柠檬酸淀粉石墨;烧结温度区间在800℃~1100℃时,样品的孔隙率呈现先上升后下降的趋势;淀粉为造孔剂时,获得更加均匀的孔分布;将所制备的多孔二氧化钛还原,所得到的多孔钛具有一定孔隙结构,并且随着多孔二氧化钛孔隙率的增大,所得多孔钛表面孔增多,多孔钛结构更加疏松。     

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。     

医用多孔NiTi合金表面微弧氧化改性研究

为解决多孔Ni Ti合金耐蚀性降低和Ni离子释放量增大而引起的使用安全性问题.本文采用微弧氧化技术对医用多孔Ni Ti合金进行表面改性处理,研究结果表明,微弧氧化处理并未改变多孔Ni Ti合金原有的孔隙结构和孔隙率,只在其外表面和孔隙内表面均形成了典型的微弧氧化多孔涂层.该涂层主要由氧化铝相组成,并含有少量的Ti和Ni元素,且外表面涂层的Ti和Ni含量要略低于孔隙内表面涂层.微弧氧化涂层提高了多孔Ni Ti合金的表面接触角,将原有的亲水表面转变成了疏水表面.经微弧处理后,多孔Ni Ti合金的耐蚀性较基体提高了1个数量级以上,Ni离子释放量也较基体降低了1个数量级以上.     

热等静压法制备多孔NiTi形状记忆合金

运用热等静压法(hot isostatic pressing,HIP),制备出多孔的NiTi形状记忆合金.制备出的多孔NiTi合金具有接近球状的孔,孔径在50～200μm,孔的分布均匀且各向同性.本文研究了多孔NiTi形状记忆合金在不同时效条件下的微观结构和马氏体相变行为,发现富Ni的多孔NiTi形状记忆合金的相变机制与富Ni致密NiTi合金相类似,时效后的冷却曲线出现两个峰,表示母相B2→R的转变和R→B19'的转变过程.     

多孔Ti-Nb-Zr合金的孔隙特征与力学性能

合金的多孔化是降低合金弹性模量最有效的方式之一,采用气氛管式炉烧结制备添加不同含量的造孔剂的TiNb24Zr4合金,通过光学显微镜、SEM、XRD、三点弯曲实验以及压缩试验测定合金孔隙率,分析孔隙形貌和试样的力学性能.通过分析,该多孔合金为近β型钛合金,通过控制造孔剂的添加量来控制合金的孔隙度及其孔隙特征,可以根据此关...     

苯甲酸含量对β-SiAlON孔隙率和力学性能的影响

以高纯Si3N4,Al2O3和AlN为原料,Y2O3为烧结助剂,苯甲酸为造孔剂,采用常压烧结方法制备β-SiAlON多孔陶瓷.研究改变苯甲酸的含量,SiAlON陶瓷孔隙率和力学性能的变化趋势问题.结果表明:以苯甲酸为造孔剂在1750℃条件下制备了以β-SiAlON为主相的多孔陶瓷,基体中大量柱状晶交叉分布;气孔形貌多为椭圆形,孔隙率随着苯甲酸含量增加而增加;且陶瓷的抗弯强度及硬度随苯甲酸增加明显降低.     

TiNiHfCu高温形状记忆合金的马氏体相变研究

通过差热扫描分析、X射线衍射和透射电镜等方法研究了Cu的添加对Ti36 Ni49-x Hf15 Cux(x=1,3,5,8)合金马氏体相变行为的影响.研究表明:Cu的加入可稍降低合金的相变温度(约15 ℃),但其Ms仍高于150 ℃,可作为高温形状记忆合金使用;随着Cu含量的升高,合金的B19'马氏体晶格常数a、b和c不发生明显变化,但单斜角β逐渐降低;Ti36 Ni49-x Hf15 Cux(x=1,3,5,8)合金的相组成为B19'单斜马氏体和(Ti,Hf,Cu)2Ni相,马氏体的亚结构为(001)复合孪晶.     

High-porosity NiTi superelastic alloys fabricated by low-pressure sintering using titanium hydride as pore-forming agent

Porous NiTi shape memory alloys (SMAs) were successfully fabricated by low-pressure sintering (LPS), and the pore features have been controlled by adjusting the processing parameters. The porous NiTi SMAs with high porosity (45%) and large pore size (200–350 μm) can be prepared by LPS using TiH_1.5 as pore-forming agent. These alloys exhibit isotropic pore structure with three-dimensional interconnected pores. The porous NiTi SMA produced by LPS exhibits superelasticity and mechanical properties superior to that by conventional sintering.     

Fabrication and characteristics of porous NiTi shape memory alloy synthesized by microwave sintering

Porous nickel titanium (NiTi) shape memory alloy (SMA) was successfully fabricated by microwave sintering method. This method allows formation of porous structures without using any pore-forming agents. Moreover, microwave sintering of NiTi SMA can be successfully performed at a relatively low sintering temperature of 850 °C and a short sintering time of 15 min. The pore characteristics, microstructure, phase transformation and stress-strain behavior of the porous NiTi SMA were investigated. The porous NiTi SMA exhibited porosity ratios from 27% to 48% and pore sizes range from 50 to 200 μm when using different sintering temperatures and holding times. The predominant B2 (NiTi) and B19′ (NiTi) phases were identified in the porous NiTi SMA. A multi-step phase transformation took place on heating and a two-step phase transformation took place on cooling of the porous NiTi SMA. The irrecoverable strains decreased with increasing sintering temperature, but the holding time had little effect on the stress-strain behavior at 60 °C.     

Porous NiTi shape memory alloys produced by SHS: microstructure and biocompatibility in comparison with Ti2Ni and TiNi3

Shape memory alloys based on NiTi have found their main applications in manufacturing of new biomedical devices mainly in surgery tools, stents and orthopedics. Porous NiTi can exhibit an engineering elastic modulus comparable to that of cortical bone (12–17 GPa). This condition, combined with proper pore size, allows good osteointegration. Open cells porous NiTi was produced by self propagating high temperature synthesis (SHS), starting from Ni and Ti mixed powders. The main NiTi phase is formed during SHS together with other Ni–Ti compounds. The biocompatibility of such material was investigated by single culture experiment and ionic release on small specimen. In particular, NiTi and porous NiTi were evaluated together with elemental Ti and Ni reference metals and the two intermetallic TiNi₃, Ti₂Ni phases. This approach permitted to clearly identify the influence of secondary phases in porous NiTi materials and relation with Ni-ion release. The results indicated, apart the well-known high toxicity of Ni, also toxicity of TiNi₃, whilst phases with higher Ti content showed high biocompatibility. A slightly reduced biocompatibility of porous NiTi was ascribed to combined effect of TiNi₃ presence and topography that requires higher effort for the cells to adapt to the surface.     

Surface Effect on Phase Transformation of Single Crystal NiTi Shape Memory Alloys Studied by Molecular Dynamics Simulation

Surface effect on phase transformation of single crystal (SC) NiTi shape memory alloys (SMAs) with various thicknesses and various Ni contents is studied by molecular dynamics simulation. For the SMAs with various thicknesses considering surface effect, the residual strain, the average atomic potential energy, and the four characteristic phase transformation temperatures all increase, and fewer twinned martensite boundaries are left after cooling compared to the sample without considering surface effect. Moreover, with increasing thickness of the sample, the surface effect is gradually weakened, and there is no obvious regularity in phase transformation characteristics. For the SMAs with various Ni contents considering surface effect, segmental martensite phase transformation, phase transformation fluctuation, and wider phase transformation temperature ranges are observed, whereas these phenomena do not occur in the sample without considering surface effect. With the increasing of Ni contents, for both cases of considering surface effect or not, the critical stress of phase transformation, average atomic potential energy, the modulus of detwinned martensite increase, but the phase transformation temperature and modulus of twinned martensite decrease.     

Mg/NiTi复合材料的制备及阻尼性能

采用Mg粉的无压熔渗法制备Mg/NiTi复合材料以提高多孔NiTi合金的强度和阻尼性能。通过OM、SEM、EDS和XRD分析Mg/NiTi复合材料的显微组织结构,采用压缩实验分析其抗压强度、吸能能力,采用热机械分析仪分析其内耗和存储模量。结果表明:经Mg粉无压熔渗后,多孔NiTi合金的孔隙被Mg填充,其孔隙率由原来的50.38%下降至5.6%,且Mg与NiTi合金的界面结合良好。多孔NiTi合金主要由B2奥氏体相和B19'马氏体相及少量Ni₃Ti相和NiTi₂相组成;Mg/NiTi复合材料除增加了熔渗的Mg相外,还新生成了Mg₂Ni相。Mg的渗入未改变多孔NiTi合金相变行为,但提高了相变温度。Mg/NiTi复合材料的抗压强度可达554 MPa,较多孔NiTi合金提高了61%,压缩断裂方式也由多孔NiTi合金的孔壁崩塌断裂转变为Mg/NiTi复合材料的剪切断裂。Mg/NiTi复合材料的吸能较多孔NiTi合金有大幅提高。同时,Mg/NiTi复合材料的内耗值有所增加,而存储模量大幅提高,整体呈现出更佳的阻尼性能。      

Phase transformation and microstructure and mechanical properties of as cast NiTiRe shape memory alloys

Abstract

The microstructure, martensitic transformation and mechanical properties of as cast Ni₅₂Ti_48?xRe_x shape memory alloys (SMAs) were investigated. The microstructure of these alloys consists of B19′ martensite phase as a matrix and B2 austenite in small percentages in addition to some precipitations of NiTi intermetallic compounds. There are two types of NiTi precipitates: the first one is Ti₂Ni, which can be seen in the all microstructures of the three alloys, and the other is Ni₂Ti, which is found only in the microstructure of Ni₅₂Ti_47·7Re_0·3 alloy. According to differential scanning calorimetry measurements, one stage of transformation reaction B2 to B19′ accompanied with forward and backward martensitic transformation was observed. The martensitic peak and the austenitic peak were increased with the addition of rhenium. Both are increased as the number of valence electron per atom increase and the valence electron concentration decrease. Hardness measurements of Ni₅₂Ti_48?xRe_x SMAs are improved by the Re additions.     

表面多孔NiTi-羟基磷灰石/NiTi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了表面多孔NiTi-羟基磷灰石(HA)/NiTi生物复合材料,研究了烧结温度对复合材料宏观形貌、微观结构、表面孔隙特征、力学性能及体外生物活性的影响。结果表明:随着烧结温度从800℃提高到950℃,NiTi-HA/NiTi复合材料由复杂的Ti、Ni、Ti_2Ni、Ni_3Ti、HA混合相逐渐转变为单一的NiTi+HA相,内外层界面形成稳定的冶金结合且表面孔隙率与平均孔径呈缓慢减小趋势;同时抗压强度显著提高而弹性模量变化不明显。与传统NiTi、多孔NiTi及多孔NiTi-HA材料相比,950℃温度下制备的NiTi-HA/NiTi复合材料不仅具有良好的界面结合和表面孔隙特征(孔隙率45.6%、平均孔径393μm)、较高的抗压强度(1 301MPa)、较低的弹性模量(10.2GPa)以及优异的超弹性行为(超弹性恢复应变4%)的最佳匹配,而且还具有良好的体外生物活性。