医用镍钛合金表面涂覆技术研究概述

镍钛(NiTi)合金因其优异的形状记忆和超弹性性能,良好的耐腐蚀性和生物相容性,在生物医学领域得到了广泛应用。为了避免直接使用可能出现的生物不相容和细胞毒性,采用表面涂覆技术在合金表面涂覆纳米到微米量级厚度的功能薄膜,使其具有比基体更优良的生物相容性、抗腐蚀性和耐磨性等特殊功能。表面涂覆技术与其它表面改性技术相比,具有约束条件少、技术类型广、材料选择空间大等优势,目前应用最为广泛。对电化学沉积、等离子喷涂、磁控溅射、溶胶凝胶法、浸涂技术制备的涂层微观结构、力学性能和耐腐蚀等性能进行综述,并分析各技术的优缺点。随着涂覆技术的发展及制备涂层性能的进一步提高,NiTi合金在牙齿矫正丝、人工关节骨茎、血管成形环等多种医疗领域中的应用将更加广泛和深入。     

Stress Evolution With Temperature in Titanium‐Rich NiTi Shape Memory Alloy Films

Abstract: The effect of deposition temperature on residual stress evolution with temperature in Ti‐rich NiTi films deposited on silicon substrates was studied. Ti‐rich NiTi films were deposited on 3″ Si (100) substrates by DC magnetron sputtering at three deposition temperatures (300, 350 and 400 °C) with subsequent annealing in vacuum at their respective deposition temperatures for 4 h. The initial value of residual stress was found to be the highest for the film deposited and annealed at 400 °C and the lowest for the film deposited and annealed at 300 °C. All the three films were found to be amorphous in the as‐deposited and annealed conditions. The nature of the stress response with temperature on heating in the first cycle (room temperature to 450 °C) was similar for all three films although the spike in tensile stress, which occurs at ～330 °C, was significantly higher in the film deposited and annealed at 300 °C. All the films were also found to undergo partial crystallisation on heating up to 450 °C and this resulted in decrease in the stress values around 55–60 °C in the cooling cycle. The stress response with temperature in the second thermal cycle (room temperature to 450 °C and back), which is reflective of the intrinsic film behaviour, was found to be similar in all cases and the elastic modulus determined from the stress response was also more or less identical. The three deposition temperatures were also not found to have a significant effect on the transformation characteristics of these films such as transformation start and finish temperatures, recovery stress and hysteresis.     

Fe对NiTi形状记忆合金相变点（Ms）影响的电子结构分析

本文依据固体经验电子理论，建立了ＮｉＴｉ形状记忆合金马氏体晶胞的键络模型，并就合经元素Ｆｅ对其Ｍ点的影响进行了电子结构分析，为揭示该功能材料中成分－性能－结构之间的内在联系做了初步探索，从电子结构的民层次上初步解释了Ｆｅ对ＮｉＴｉ合金相变点（Ｍａ）的作用机制。     

Factors affecting the generation of stress-assisted two-way memory effect in NiTi shape memory alloy

The combined effects of martensite pre-deformation and constrained stress on the generation of stress-assisted two-way memory effect (SATWME) were studied. Particular attention was paid to the generation of internal stress during thermal cycling under constant stress. The result highlights that the maximum SATWME is not determined solely by the maximum internal stress developed. The SATWME strain when subjected to 18% martensite pre-strain coincides, independently of constrained stress applied and internal stress developed. This study also provides experimental evidence that when under 400 MPa constrained stress the maximum SATWME shifts toward higher pre-deformation amplitude and this phenomenon is comparable to the increased cold-work. The results further suggest that the mechanism that associates with the change of M_s temperature plays critical role in determining the SATWME.     

The influence of laser welding parameters on the microstructure and mechanical property of the as-jointed NiTi alloy wires

The Nd:YAG laser welding was used to join the binary NiTi alloy wires with different compositions(Ti-50.0 at.%Ni and Ti-50.9 at.%Ni) which had the same diameter of 1 mm. The wires were welded with different parameters, including impulse width and welding current. The aim was to assess the influence of the laser-welding process on the microstructure and mechanical properties of the welded joint of binary NiTi wires. The optical microscopy (OM) and the metallographic microscopy (MM) were used to analyze the microstructure of the welded joints. The tensile test and the differential scanning calorimetry (DSC) were carried out to examine the ultimate tensile strength and the reverse martensitic transformation temperatures of the welded joints. It was found that the welding current and the impulse width had great influence on the quality of the welded joints, an optimal parameter combination would remove the pores and micro-cracks appeared in the fusion zone, and result in good mechanical properties such as higher fracture strength and elongation. The laser welding had a few effect on the reverse martensitic transformation temperatures of the welded joints.     

Ultrasonic reflection from a stressed interface

In seeking to develop an NDE technique for verifying the serviceability of NiTi couplers for plumbing unions, it was found that the reflection coefficient for a normally incident ultrasonic wave correlated with the stress level at the NiTi-tubing interface. Current theory pertaining to interface reflection is not complete but, even at present status, there is semiquantitative accord between theoretical predictions and normalized data for reflection coefficient versus stress level. These results are at fixed frequency and with comparable surface roughness. Variation of either frequency or surface roughness further affects the reflection coefficient. Current studies are being pursued to define this effect.     

SLM NiTi记忆合金BCC点阵结构的吸能特性研究

通过选区激光熔化（SLM）技术制备了不同体积分数的NiTi记忆合金BCC点阵结构（基于CAD及基于三周期极小曲面TPMS）,分析了失效前的压缩响应,研究了体积分数、单元构型和微观组织对能量吸收的影响。结果表明：NiTi BCC点阵（体积分数5 %~25 %）在压缩至损伤前具有优秀的比能量吸收（0.45~1.89 J/g）,卸载后加热可恢复至92 %以上;体积分数及单元构型对NiTi BCC点阵的压缩响应有重要影响;体积分数小于15 %时,CAD样品具有更长可压缩应变,比能量吸收更好;体积分数大于15 %时,TPMS样品具有更高压缩应力,比能量吸收更好;SLM过程中的阶梯效应导致了点阵支杆的下表面与内部具有不同的材料组织,下表面处熔池条纹更深更宽且晶粒更加粗大;材料异质性导致了相对较差的机械性能,不利于能量吸收;由于受载下应力集中位置及异质比例的不同,该材料异质性对低体积分数的TPMS样品的不利影响更大。     

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。      

Ti-50.8%Ni形状记忆合金R相区力学性能研究

对Ti-50．8％Ni形状记忆合金丝进行了不同预变形量处理和不同温度的时效，研究了合金力学性能和预变形量、时效温度之间的关系。结果表明：时效温度和预变形量对NiTi合金的强度影响很大，经适当的预变形和时效后NiTi合金的屈服强度降低，抗拉强度增大。测试表明10％预变形 500℃时效的合金丝室温组织为R相。