新型医用β钛合金的设计、制备及其固溶时效行为
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摘要
钛合金凭借其优良的生物相容性和力学性能,逐渐取代不锈钢和CoCrMo等传统的生物医用金属材料,已被广泛用作人工关节、脊柱矫形内固定系统、牙科植体等医用内植入材料。而相对于纯钛和传统的α+p型医用钛合金,p型医用钛合金具有更低的弹性模量,更加优异的生物相容性以及耐蚀性能,因此受到越来越多的关注,已成为当前研究的热点。
本文利用第一性原理对Ti-Nb二元合金的能量、电子结构及弹性性质进行了计算,并结合d-电子理论和平均价电子浓度等设计理论与方法,设计了无毒低模量的Ti-25Nb-10Ta-1Zr-0.2Fe(TNTZF, wt.%)新型生物医用p钛合金；采用真空自耗电弧熔炼技术制备了TNTZF合金,利用光学显微镜(OM)、扫描电子显微镜(SEM)、差热分析仪(DSC)、X射线衍射仪(XRD)、透射电镜(TEM)、X射线光电子谱(XPS)等分析手段,对TNTZF合金的时效析出行为、ω相的析出长大动力学、冷变形行为进行了研究,并对合金的拉伸、冲击以及耐蚀性能进行了表征与评价,分析了合金微观结构演变对性能的影响,并对合金的时效析出规律、冷变形机制、断裂及耐蚀机理进行了深入的探讨。主要结论如下：
(1)利用第一性原理方法对Ti-Nb二元合金的能量、β结构稳定性和弹性性质进行了计算。结果表明随着Nb含量的增加：合金的内聚能不断升高,正方剪切常数C'不断增加,β结构稳定性逐渐增强,体模量B不断上升,剪切模量G和弹性模量E则呈现先上升后降低的趋势。当Nb含量>12.5at.%时,Ti-Nb二元合金能够以p结构稳定存在；当Nb含量为12.5～25at.%时,正方剪切常数C'大于并接近于零,此时价电子浓度e/a处于4.125～4.25范围内,合金的弹性模量E最低约为45～46GPa。对Ti-25at.%Nb合金中β相、α"相和ω相的结构稳定性进行了计算,得到p相、α"相和ω相的内聚能分别为5.7046、5.7305和5.726leV·atom-1,说明α"相的结构稳定性最高,p相的结构稳定性相对最低。同时根据第一性原理的计算结果并结合d-电子理论和平均价电子浓度等理论,设计了无毒低模量的Ti-25Nb-10Ta-1Zr-0.2Fe(TNTZF, wt.%)新型生物医用β钛合金。
(2)采用真空自耗电弧熔炼技术制备了TNTZF合金,并对TNTZF合金的时效行为进行了研究。合金经过800℃/lh固溶淬火后主要由过冷p、α"马氏体以及少量淬火ωOath组成,在时效初期,亚稳p与α"发生分解并向α相转变,ω相先与α相竞争长大,最后分解转变成α相,合金最终获得p+α平衡组织。时效早期α相优先在ω/β相界处形核,消耗ω相长大,随着时效时间的延长,α相开始在p晶界处形核,并向晶内生长。α相的形核和长大受溶质原子长程扩散控制,长大速度受扩散速率所控制。合金的时效析出序列与温度的关系如下：较低温度(350℃以下)为：p+α"+ωath→β+ωiso→ωiso+α→β+α；中间温度(400-500℃)为：β+α"+ωath→β+ωiso+α→β+α；较高温度(500℃以上)为：p+α"+ωath→β+α.合金在中间温度(400℃和470℃)时效表现出强烈的时效硬化效应,而在较低(350℃)和较高(500℃)温度下时效表现出较弱的时效硬化效果。
(3)利用DSC和TEM两种手段,对ω相的析出长大动力学行为进行了研究。TNTZF固溶态合金在5-40℃/min的连续升温过程中,随着升温速率的提高,ω相对应的析出峰值温度向高温方向移动；其析出体积分数曲线和析出速率曲线也都表现出向高温方向移动的趋势；利用Kissinger方法计算得到合金在连续升温过程中ω相变激活能为355.1kJ/mol。TNTZF合金在350、400和470℃下等温时效不同时间后,ω相的晶粒生长符合抛物线规律,其生长动力学指数n分别为0.23、0.25和0.26；利用Burke-Turnbull动力学模型,计算得到ω相的晶粒长大激活能为119.7kJ/mol,并建立了ω相的晶粒尺寸D与时效时间t和温度T之间的动力学方程：D4-D04=4.3×1013·t·exp(-119.7/RT)。
(4)合金经900℃/1h固溶后获得等轴β单相组织,抗拉强度为697MPa,弹性模量为75GPa,伸长率为34%。合金在150-450℃温度范围时效,脆性ω相的析出不但引起弹性模量的大幅提高,还导致强度、塑性和韧性急剧下降,尤其是在400和450℃温度下时效后ω相的体积分数超过50%,此时合金的塑性几乎为零,变成完全脆性的材料。合金在550℃下时效,随着时效时间的延长,α相的体积分数不断增加,合金的屈服强度和抗拉强度都呈现出先升高后降低的趋势,两者均在α相体积分数为21.4%(时效1h)时达到最大值,分别为696MPa和876MPa。弹性模量随着α相体积分数的增加呈逐渐增加的趋势,伸长率则先快速降低,在α相体积分数达到13.6%(时效30min)后缓慢下降。
(5)900℃/1h固溶态合金的冲击韧性为58.7J/cm2。在400℃温度下时效5min-72h后,合金的冲击韧性几乎均为零。在550℃下时效5min-72h,合金的冲击韧性随着时效时间的延长而降低,时效24h后基本稳定在18～20J/cm2。固溶态冲击试样的断口特征为韧窝断裂；400℃时效态试样呈完全脆性断裂,断裂模式为沿晶+解理的混合断裂；合金在550℃下时效后的断裂机理均为韧性断裂,断裂机理随着时效时间的延长发生变化,由韧窝断裂逐渐向韧窝+沿晶混合断裂类型转变。
(6)TNTZF合金锻造态和900℃/1h固溶态试样的冲击疲劳寿命均为17600次左右。在400℃下时效5min后,冲击疲劳寿命就降低了～70%,之后随着时效时间的延长,冲击疲劳寿命不断降低,时效72h之后仅为～450次。在550℃下时效后的冲击疲劳寿命也大致呈现逐渐下降的趋势,但是要明显高于400℃下时效的合金试样。在550℃下时效24h后合金的冲击疲劳寿命基本保持在3500～3700次的范围内。固溶态试样的冲击疲劳断裂以穿晶方式进行,裂纹扩展区存在许多的准解理小平面以及疲劳条带和二次裂纹,瞬断区存在大量的韧窝。400℃时效态合金的疲劳断裂机制为解理+沿晶脆性断裂混合模式。550℃下早期时效,合金的疲劳断裂机制较固溶态试样没有发生明显变化,经过72h长时间时效后,瞬断区的断裂模式由韧窝+疲劳条带的混合断裂转变为沿晶韧窝断裂。
(7)与其他热处理状态相比,TNTZF合金经过550℃/30min时效处理之后,获得较好的综合力学性能：屈服强度为615MPa,抗拉强度为804MPa,弹性模量为72GPa,伸长率为9%,冲击韧性为35.8J/cm2,冲击疲劳寿命为13468次,满足生物医用钛合金所需要的高强度、低模量和良好塑韧性的匹配。
(8)TNTZF合金的主导变形机制随着变形量的增加,逐渐从应力诱发α"马氏体相变、位错滑移向孪晶、剪切带以及结构纳米化转变,同时,合金中{111}<110>织构逐渐转向再结晶织构{111}<112>,当变形量达到80%时,{111}<112>成为主导。随着变形量的增加,合金中的位错密度不断升高,晶粒不断被细化,合金的强度和硬度不断提高；弹性模量则随着变形量的增加不断降低,这主要归因于变形过程中应力诱发马氏体相变以及脆性ω相的消失的共同作用。与30%CR和80%CR合金试样相对比,60%CR合金试样具有较高的强度(屈服强度为787MPa,抗拉强度为1213MPa),较低的弹性模量(68GPa)、适中的伸长率(7.8%)以及最高的强模比(17.8×10-3)。
(9)与Ti-6A1-4V ELI合金相比,TNTZF合金在Ringer's溶液中表现出更高的腐蚀电位、更低更稳定的钝化电流密度以及更宽的钝化电位区间,并且合金试样表面没有观察到像Ti-6A1-4V ELI合金那样的点蚀现象,表明TNTZF合金具有更加优异的抗腐蚀性能。这归因于TNTZF合金表面形成了一层主要由TiO2、 Nb2O5、NbO2、Ta2O5和Zr02组成的钝化膜,比Ti-6A1-4V ELI合金的钝化膜(主要成分为TiO2、A12O3、V2O3)更加稳定。冷轧变形之后,TNTZF合金内部产生高密度的位错、应变集中区以及应力诱发α"马氏体相变,加快了合金的腐蚀速率,合金的耐蚀性能下降。TNTZF合金经过时效处理后析出第二相粒子降低了合金的抗腐蚀性能,并且随着时效温度的升高,耐蚀性能不断下降。
Comparing with the conventional stainless steels and cobalt-based alloys, titanium and its alloys exhibit more suitable characteristics for biomedical applications due to their excellent biocompatibility and mechanical property. They are widely used as repair and replacement materials for implants such as artificial hip joints, orthopedics and dentistry, etc. β type titanium alloys generally can be processed lower elastic modulus, superior biocompatibility and better corrosion resistance as compared to those of a and a+P types, which attract more and more attentions and become a hot topic in present research.
The energetic, electronic structure and elastic property of Ti-Nb binary alloys were calculated by the first-principles method. Based on the calculated results and combined with other design theories, such as d-electronic theory and the average valence electron concentration method, a new β titanium alloy with non-toxic and low modulus for biomedical applications------Ti-25Nb-10Ta-1Zr-0.2Fe (TNTZF, wt.%) was designed. TNTZF alloy was prepared by vacuum self consumable arc melting techniques. By means of optical microscope (OM), X-ray diffraction(XRD), scanning calorimetry (DSC), scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS) and tensile tester, impact toughness machine, impact fatigue tester and electrochemical workstation, the ageing precipitation behavior, precipitation and grain growth kinetics of ω phase and cold deformation behavior of TNTZF alloy were studied, and the tensile, impact and corrosion resistant performances were evaluated. The rule of ageing precipitation and the mechanisms of cold deformation, fracture and corrosion resistant were discussed deeply. The main results are summarized as follows.
(1) The energetic, electronic structure and elastic property of Ti-Nb binary alloys were calculated by the first-principle method. With increasing Nb content, the cohesive energy, tetragonal shear constant C',β phase stability and bulk modulus of Ti-Nb alloys increase, shear modulus and elastic modulus increase firstly followed by decreasing. When the Nb content is more than12.5at.%, the alloy achieves the lowest β phase stability. When the Nb content in the range of12.5-25at.%, the value of C' reaches nearly zero from positive, meanwhile the average valence electron concentration e/a lies in the range of4.125-4.25, the alloy achieves the minimum elastic modulus of about45-46GPa. The phase stability of β,α" and co phases in the Ti-25at.%Nb alloy was calculated. The cohesive energies of β,α" and co phases are 5.7046,5.7305and5.7261eV-atom-1showing that among β,α and ω phases, the phase stability of a" phase is the highest and that of β phase the lowest. Based on these calculated results and combined with other design theories, such as d-electronic theory and the average valence electron concentration method, a new β titanium alloy------Ti-25Nb-10Ta-1Zr-0.2Fe (TNTZF, wt.%) for biomedical applications was designed.
(2) TNTZF alloy was prepared by vacuum self consumable arc melting techniques, and the ageing behavior was studied. The results showed that martensite a" and a small amount of athermal ω phase were observed in the β matrix after solution treatment at800℃for1h. At the early stage of aging, metastable β and a" decomposed, ωiso firstly competed to grow with a phase, and then dissolved and transformed into a phase, a stable β+α microstructure was obtained finally, a precipitates nucleated at ω/β interfaces preferentially at the early stage and growed up by consuming co phase. Along with the aging time increase, a started to nucleate from β grain boundary, and growed inside to β grain. The nucleation and growth of a phase were controlled by long-range diffusion of solute atoms, the growth seep was diffusion rate-controlled. The relationship between aging precipitation sequence and aging temperature is as follows:P+a"+ωath→P+ωiso→βP+ωiso+α→β+α at350℃; β+α"+ωath→β+ωiso+α→β+α at400-500℃; β+α"+ωath→β+α above500℃. The alloy showed stronger age-hardening response at intermediate temperatures of400℃and470℃, while exhibited weaker age-hardening response at lower temperature of35O℃and higher temperature of500℃.
(3) By means of DSC and TEM methods, the kinetic behavior of co precipitation and growth was studied. During continuous heating at the speed in the range of5-40"C/min, the peak of co precipitation temperature of solution treated TNTZF alloy shifted to high temperature, the curve of ω precipitation volume fraction and rate shifted to high temperature. The activation energy for co phase transformation during continuous heating was calculated to be355.1kJ/mol by Kissinger method. The grain growth of ωiso obeys an asymptotic law, the grain-growth exponents, n, were computed to be0.23,0.25and0.26for350,400and470℃, respectively. According to Burke-Turnbull model, the activation energy for coiso grain growth,Qg was calculated to be119.7kJ/mol, and a kinetic equation describing the relationship between grain size of co phase and aging time and temperature was constructed as follows:D4-D4=4.3×1013·f·exp(-119.7/RT).
(4) TNTZF alloy after solution treatment at900℃for1h and quenching has a microstructure of typical equiaxed β grains, tensile strength of697MPa, elastic modulus of75GPa and elongation-34%. After aging at the temperature in the range of150-450℃, the elastic modulus of the alloy increased greatly, the strength, plasticity and toughness dropped sharply due to the precipitation of brittle ω phase. The volume fraction of ω precipitate to be above50%after aging at400℃and450℃lea to the plasticity nearly zero, the alloy became completely brittle. When aged at550℃, with increasing aging time, the volume fractions of a phase increased gradually, the yield and tensile strengths increased firstly and achieved the maximum after24h aging of696MPa and876MPa, respectively. The elastic modulus showed a increasing tend with aging time, the elongation first dropped sharply and followed by a slowly decrease after aging for30min.
(5) TNTZF alloy after solution treatment at900℃for1h has the highest impact toughness of58.7J/cm2. After aging at400℃for5min-72h, the impact toughness dropped sharply and nearly zero. When aging at400℃for5min-72h, impact toughness of the alloy decreased gradually with increasing aging time, after24h aging, impact toughness nearly stable approximately18-20J/cm. The fracture analysis shows that a ductile fracture surface morphology with lots of dimples was observed in the solution treated sample. A completely brittle fracture morphology was seen in the alloy aged at400℃with a intergranular and cleavage mixed failure mode. The fracture mechanism for the alloy aged at550℃are ductile type, but it changed form dimple type to dimple and intergranular mixed failure mode along with aging time.
(6) As-forged and ST samples have the impact fatigue life for about17600times. When aging at400℃only for5min, the impact fatigue life decreased by-70%. After that, it fell down furtherly with aging time and to only450times after72h aging. The impact fatigue lifes of the samples aged at550℃are higher than that of400℃, although it also decreased with increasing aging time. It remains about3500to3700times after24h aging. Considerable quasi-cleavage facets and fatigue strips as well as secondary cracks were observed on the crack propagation zone, and equiaxed dimples are observed on the fast fracture surface of ST alloy. The fatigue surface of the alloy aged at400℃showed a brittle fracture morphology with a mixed mode of cleavage and intergranular. The fracture mechanism of the alloy aged at550℃for1h was similar to that of ST alloy. After72h long time aging, the characteristics of fast fracture surface tend to transform from dimples and fatigue strips mixed mode to intergranular dimple type.
(7) Compared with the ST samples and the aged samples which aging treated among150-550℃for different times, the sample aged at550℃for30min showed better comprehensive mechanical properties. Since it with a yield strength of615MPa, a tensile strength of804MPa, elastic modulus of72GPa, elongation of9%, impact toughness of35.8J/cm2, and impact fatigue life about13468times. It can meet matching of high strength, low modulus, appropriate plasticity and toughness for biomedical applications.
(8) The results showed that the dominant deformation mechanisms changed from stress-induced a" martensitic transformation and dislocation tangles to twinning, shear bands and nanostructuring with the increase of cold reduction. Meanwhile, the transition from{111}<110> to{111}<112> orientation took place during CR and a dominant{111}<112> texture was obtained after80%cold deformation. The hardness and strength increased with the increase of cold reduction owing to the effects of the increase of dislocation density and the grain refinement caused by cold deformation. The decrease in Young's modulus after CR was mainly attributed to the stress-induced a" martensitic transformation accompanying with the disappearance of co phase. Compared with30%CR and80%CR samples, the60%CR sample possesses higher strengths (yield strength:787MPa, tensile strength:1213MPa), appropriate plasticity (7.8%) and the highest strength-to-modulus ratio (17.8×10'3).
(9) TNTZF alloy has higher corrosion potential, lower corrosion current density, more stable passive current densities and wider passive region compared with Ti-6A1-4V ELI, which indicates that TNTZF alloy possesses much better corrosion resistance. In addition, pitting corrosion is observed on the surface passive film of Ti-6A1-4V ELI alloy but is not found on that of TNTZF alloy. XPS analysis results reveal that the passive film formed on TNTZF alloy is composed of Nb2O5, NbO2, Ta2O5, ZrO2, TiO and Ti2O3oxides in the matrix of TiO2, it makes the passive film more stable and protective than that of Ti-6A1-4V ELI which consisted of TiO Al2O3、V2O3. The alloy after cold rolling shows inferior corrosion resistance due to its high density of dislocation and strain concentration and stress-induced a" martensitic transformation. Precipitation of ω or a phase in the alloy after aging led to decrease of corrosion resistance compared with the ST alloy.
本文利用第一性原理对Ti-Nb二元合金的能量、电子结构及弹性性质进行了计算,并结合d-电子理论和平均价电子浓度等设计理论与方法,设计了无毒低模量的Ti-25Nb-10Ta-1Zr-0.2Fe(TNTZF, wt.%)新型生物医用p钛合金；采用真空自耗电弧熔炼技术制备了TNTZF合金,利用光学显微镜(OM)、扫描电子显微镜(SEM)、差热分析仪(DSC)、X射线衍射仪(XRD)、透射电镜(TEM)、X射线光电子谱(XPS)等分析手段,对TNTZF合金的时效析出行为、ω相的析出长大动力学、冷变形行为进行了研究,并对合金的拉伸、冲击以及耐蚀性能进行了表征与评价,分析了合金微观结构演变对性能的影响,并对合金的时效析出规律、冷变形机制、断裂及耐蚀机理进行了深入的探讨。主要结论如下：
(1)利用第一性原理方法对Ti-Nb二元合金的能量、β结构稳定性和弹性性质进行了计算。结果表明随着Nb含量的增加：合金的内聚能不断升高,正方剪切常数C'不断增加,β结构稳定性逐渐增强,体模量B不断上升,剪切模量G和弹性模量E则呈现先上升后降低的趋势。当Nb含量>12.5at.%时,Ti-Nb二元合金能够以p结构稳定存在；当Nb含量为12.5～25at.%时,正方剪切常数C'大于并接近于零,此时价电子浓度e/a处于4.125～4.25范围内,合金的弹性模量E最低约为45～46GPa。对Ti-25at.%Nb合金中β相、α"相和ω相的结构稳定性进行了计算,得到p相、α"相和ω相的内聚能分别为5.7046、5.7305和5.726leV·atom-1,说明α"相的结构稳定性最高,p相的结构稳定性相对最低。同时根据第一性原理的计算结果并结合d-电子理论和平均价电子浓度等理论,设计了无毒低模量的Ti-25Nb-10Ta-1Zr-0.2Fe(TNTZF, wt.%)新型生物医用β钛合金。
(2)采用真空自耗电弧熔炼技术制备了TNTZF合金,并对TNTZF合金的时效行为进行了研究。合金经过800℃/lh固溶淬火后主要由过冷p、α"马氏体以及少量淬火ωOath组成,在时效初期,亚稳p与α"发生分解并向α相转变,ω相先与α相竞争长大,最后分解转变成α相,合金最终获得p+α平衡组织。时效早期α相优先在ω/β相界处形核,消耗ω相长大,随着时效时间的延长,α相开始在p晶界处形核,并向晶内生长。α相的形核和长大受溶质原子长程扩散控制,长大速度受扩散速率所控制。合金的时效析出序列与温度的关系如下：较低温度(350℃以下)为：p+α"+ωath→β+ωiso→ωiso+α→β+α；中间温度(400-500℃)为：β+α"+ωath→β+ωiso+α→β+α；较高温度(500℃以上)为：p+α"+ωath→β+α.合金在中间温度(400℃和470℃)时效表现出强烈的时效硬化效应,而在较低(350℃)和较高(500℃)温度下时效表现出较弱的时效硬化效果。
(3)利用DSC和TEM两种手段,对ω相的析出长大动力学行为进行了研究。TNTZF固溶态合金在5-40℃/min的连续升温过程中,随着升温速率的提高,ω相对应的析出峰值温度向高温方向移动；其析出体积分数曲线和析出速率曲线也都表现出向高温方向移动的趋势；利用Kissinger方法计算得到合金在连续升温过程中ω相变激活能为355.1kJ/mol。TNTZF合金在350、400和470℃下等温时效不同时间后,ω相的晶粒生长符合抛物线规律,其生长动力学指数n分别为0.23、0.25和0.26；利用Burke-Turnbull动力学模型,计算得到ω相的晶粒长大激活能为119.7kJ/mol,并建立了ω相的晶粒尺寸D与时效时间t和温度T之间的动力学方程：D4-D04=4.3×1013·t·exp(-119.7/RT)。
(4)合金经900℃/1h固溶后获得等轴β单相组织,抗拉强度为697MPa,弹性模量为75GPa,伸长率为34%。合金在150-450℃温度范围时效,脆性ω相的析出不但引起弹性模量的大幅提高,还导致强度、塑性和韧性急剧下降,尤其是在400和450℃温度下时效后ω相的体积分数超过50%,此时合金的塑性几乎为零,变成完全脆性的材料。合金在550℃下时效,随着时效时间的延长,α相的体积分数不断增加,合金的屈服强度和抗拉强度都呈现出先升高后降低的趋势,两者均在α相体积分数为21.4%(时效1h)时达到最大值,分别为696MPa和876MPa。弹性模量随着α相体积分数的增加呈逐渐增加的趋势,伸长率则先快速降低,在α相体积分数达到13.6%(时效30min)后缓慢下降。
(5)900℃/1h固溶态合金的冲击韧性为58.7J/cm2。在400℃温度下时效5min-72h后,合金的冲击韧性几乎均为零。在550℃下时效5min-72h,合金的冲击韧性随着时效时间的延长而降低,时效24h后基本稳定在18～20J/cm2。固溶态冲击试样的断口特征为韧窝断裂；400℃时效态试样呈完全脆性断裂,断裂模式为沿晶+解理的混合断裂；合金在550℃下时效后的断裂机理均为韧性断裂,断裂机理随着时效时间的延长发生变化,由韧窝断裂逐渐向韧窝+沿晶混合断裂类型转变。
(6)TNTZF合金锻造态和900℃/1h固溶态试样的冲击疲劳寿命均为17600次左右。在400℃下时效5min后,冲击疲劳寿命就降低了～70%,之后随着时效时间的延长,冲击疲劳寿命不断降低,时效72h之后仅为～450次。在550℃下时效后的冲击疲劳寿命也大致呈现逐渐下降的趋势,但是要明显高于400℃下时效的合金试样。在550℃下时效24h后合金的冲击疲劳寿命基本保持在3500～3700次的范围内。固溶态试样的冲击疲劳断裂以穿晶方式进行,裂纹扩展区存在许多的准解理小平面以及疲劳条带和二次裂纹,瞬断区存在大量的韧窝。400℃时效态合金的疲劳断裂机制为解理+沿晶脆性断裂混合模式。550℃下早期时效,合金的疲劳断裂机制较固溶态试样没有发生明显变化,经过72h长时间时效后,瞬断区的断裂模式由韧窝+疲劳条带的混合断裂转变为沿晶韧窝断裂。
(7)与其他热处理状态相比,TNTZF合金经过550℃/30min时效处理之后,获得较好的综合力学性能：屈服强度为615MPa,抗拉强度为804MPa,弹性模量为72GPa,伸长率为9%,冲击韧性为35.8J/cm2,冲击疲劳寿命为13468次,满足生物医用钛合金所需要的高强度、低模量和良好塑韧性的匹配。
(8)TNTZF合金的主导变形机制随着变形量的增加,逐渐从应力诱发α"马氏体相变、位错滑移向孪晶、剪切带以及结构纳米化转变,同时,合金中{111}<110>织构逐渐转向再结晶织构{111}<112>,当变形量达到80%时,{111}<112>成为主导。随着变形量的增加,合金中的位错密度不断升高,晶粒不断被细化,合金的强度和硬度不断提高；弹性模量则随着变形量的增加不断降低,这主要归因于变形过程中应力诱发马氏体相变以及脆性ω相的消失的共同作用。与30%CR和80%CR合金试样相对比,60%CR合金试样具有较高的强度(屈服强度为787MPa,抗拉强度为1213MPa),较低的弹性模量(68GPa)、适中的伸长率(7.8%)以及最高的强模比(17.8×10-3)。
(9)与Ti-6A1-4V ELI合金相比,TNTZF合金在Ringer's溶液中表现出更高的腐蚀电位、更低更稳定的钝化电流密度以及更宽的钝化电位区间,并且合金试样表面没有观察到像Ti-6A1-4V ELI合金那样的点蚀现象,表明TNTZF合金具有更加优异的抗腐蚀性能。这归因于TNTZF合金表面形成了一层主要由TiO2、 Nb2O5、NbO2、Ta2O5和Zr02组成的钝化膜,比Ti-6A1-4V ELI合金的钝化膜(主要成分为TiO2、A12O3、V2O3)更加稳定。冷轧变形之后,TNTZF合金内部产生高密度的位错、应变集中区以及应力诱发α"马氏体相变,加快了合金的腐蚀速率,合金的耐蚀性能下降。TNTZF合金经过时效处理后析出第二相粒子降低了合金的抗腐蚀性能,并且随着时效温度的升高,耐蚀性能不断下降。
Comparing with the conventional stainless steels and cobalt-based alloys, titanium and its alloys exhibit more suitable characteristics for biomedical applications due to their excellent biocompatibility and mechanical property. They are widely used as repair and replacement materials for implants such as artificial hip joints, orthopedics and dentistry, etc. β type titanium alloys generally can be processed lower elastic modulus, superior biocompatibility and better corrosion resistance as compared to those of a and a+P types, which attract more and more attentions and become a hot topic in present research.
The energetic, electronic structure and elastic property of Ti-Nb binary alloys were calculated by the first-principles method. Based on the calculated results and combined with other design theories, such as d-electronic theory and the average valence electron concentration method, a new β titanium alloy with non-toxic and low modulus for biomedical applications------Ti-25Nb-10Ta-1Zr-0.2Fe (TNTZF, wt.%) was designed. TNTZF alloy was prepared by vacuum self consumable arc melting techniques. By means of optical microscope (OM), X-ray diffraction(XRD), scanning calorimetry (DSC), scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS) and tensile tester, impact toughness machine, impact fatigue tester and electrochemical workstation, the ageing precipitation behavior, precipitation and grain growth kinetics of ω phase and cold deformation behavior of TNTZF alloy were studied, and the tensile, impact and corrosion resistant performances were evaluated. The rule of ageing precipitation and the mechanisms of cold deformation, fracture and corrosion resistant were discussed deeply. The main results are summarized as follows.
(1) The energetic, electronic structure and elastic property of Ti-Nb binary alloys were calculated by the first-principle method. With increasing Nb content, the cohesive energy, tetragonal shear constant C',β phase stability and bulk modulus of Ti-Nb alloys increase, shear modulus and elastic modulus increase firstly followed by decreasing. When the Nb content is more than12.5at.%, the alloy achieves the lowest β phase stability. When the Nb content in the range of12.5-25at.%, the value of C' reaches nearly zero from positive, meanwhile the average valence electron concentration e/a lies in the range of4.125-4.25, the alloy achieves the minimum elastic modulus of about45-46GPa. The phase stability of β,α" and co phases in the Ti-25at.%Nb alloy was calculated. The cohesive energies of β,α" and co phases are 5.7046,5.7305and5.7261eV-atom-1showing that among β,α and ω phases, the phase stability of a" phase is the highest and that of β phase the lowest. Based on these calculated results and combined with other design theories, such as d-electronic theory and the average valence electron concentration method, a new β titanium alloy------Ti-25Nb-10Ta-1Zr-0.2Fe (TNTZF, wt.%) for biomedical applications was designed.
(2) TNTZF alloy was prepared by vacuum self consumable arc melting techniques, and the ageing behavior was studied. The results showed that martensite a" and a small amount of athermal ω phase were observed in the β matrix after solution treatment at800℃for1h. At the early stage of aging, metastable β and a" decomposed, ωiso firstly competed to grow with a phase, and then dissolved and transformed into a phase, a stable β+α microstructure was obtained finally, a precipitates nucleated at ω/β interfaces preferentially at the early stage and growed up by consuming co phase. Along with the aging time increase, a started to nucleate from β grain boundary, and growed inside to β grain. The nucleation and growth of a phase were controlled by long-range diffusion of solute atoms, the growth seep was diffusion rate-controlled. The relationship between aging precipitation sequence and aging temperature is as follows:P+a"+ωath→P+ωiso→βP+ωiso+α→β+α at350℃; β+α"+ωath→β+ωiso+α→β+α at400-500℃; β+α"+ωath→β+α above500℃. The alloy showed stronger age-hardening response at intermediate temperatures of400℃and470℃, while exhibited weaker age-hardening response at lower temperature of35O℃and higher temperature of500℃.
(3) By means of DSC and TEM methods, the kinetic behavior of co precipitation and growth was studied. During continuous heating at the speed in the range of5-40"C/min, the peak of co precipitation temperature of solution treated TNTZF alloy shifted to high temperature, the curve of ω precipitation volume fraction and rate shifted to high temperature. The activation energy for co phase transformation during continuous heating was calculated to be355.1kJ/mol by Kissinger method. The grain growth of ωiso obeys an asymptotic law, the grain-growth exponents, n, were computed to be0.23,0.25and0.26for350,400and470℃, respectively. According to Burke-Turnbull model, the activation energy for coiso grain growth,Qg was calculated to be119.7kJ/mol, and a kinetic equation describing the relationship between grain size of co phase and aging time and temperature was constructed as follows:D4-D4=4.3×1013·f·exp(-119.7/RT).
(4) TNTZF alloy after solution treatment at900℃for1h and quenching has a microstructure of typical equiaxed β grains, tensile strength of697MPa, elastic modulus of75GPa and elongation-34%. After aging at the temperature in the range of150-450℃, the elastic modulus of the alloy increased greatly, the strength, plasticity and toughness dropped sharply due to the precipitation of brittle ω phase. The volume fraction of ω precipitate to be above50%after aging at400℃and450℃lea to the plasticity nearly zero, the alloy became completely brittle. When aged at550℃, with increasing aging time, the volume fractions of a phase increased gradually, the yield and tensile strengths increased firstly and achieved the maximum after24h aging of696MPa and876MPa, respectively. The elastic modulus showed a increasing tend with aging time, the elongation first dropped sharply and followed by a slowly decrease after aging for30min.
(5) TNTZF alloy after solution treatment at900℃for1h has the highest impact toughness of58.7J/cm2. After aging at400℃for5min-72h, the impact toughness dropped sharply and nearly zero. When aging at400℃for5min-72h, impact toughness of the alloy decreased gradually with increasing aging time, after24h aging, impact toughness nearly stable approximately18-20J/cm. The fracture analysis shows that a ductile fracture surface morphology with lots of dimples was observed in the solution treated sample. A completely brittle fracture morphology was seen in the alloy aged at400℃with a intergranular and cleavage mixed failure mode. The fracture mechanism for the alloy aged at550℃are ductile type, but it changed form dimple type to dimple and intergranular mixed failure mode along with aging time.
(6) As-forged and ST samples have the impact fatigue life for about17600times. When aging at400℃only for5min, the impact fatigue life decreased by-70%. After that, it fell down furtherly with aging time and to only450times after72h aging. The impact fatigue lifes of the samples aged at550℃are higher than that of400℃, although it also decreased with increasing aging time. It remains about3500to3700times after24h aging. Considerable quasi-cleavage facets and fatigue strips as well as secondary cracks were observed on the crack propagation zone, and equiaxed dimples are observed on the fast fracture surface of ST alloy. The fatigue surface of the alloy aged at400℃showed a brittle fracture morphology with a mixed mode of cleavage and intergranular. The fracture mechanism of the alloy aged at550℃for1h was similar to that of ST alloy. After72h long time aging, the characteristics of fast fracture surface tend to transform from dimples and fatigue strips mixed mode to intergranular dimple type.
(7) Compared with the ST samples and the aged samples which aging treated among150-550℃for different times, the sample aged at550℃for30min showed better comprehensive mechanical properties. Since it with a yield strength of615MPa, a tensile strength of804MPa, elastic modulus of72GPa, elongation of9%, impact toughness of35.8J/cm2, and impact fatigue life about13468times. It can meet matching of high strength, low modulus, appropriate plasticity and toughness for biomedical applications.
(8) The results showed that the dominant deformation mechanisms changed from stress-induced a" martensitic transformation and dislocation tangles to twinning, shear bands and nanostructuring with the increase of cold reduction. Meanwhile, the transition from{111}<110> to{111}<112> orientation took place during CR and a dominant{111}<112> texture was obtained after80%cold deformation. The hardness and strength increased with the increase of cold reduction owing to the effects of the increase of dislocation density and the grain refinement caused by cold deformation. The decrease in Young's modulus after CR was mainly attributed to the stress-induced a" martensitic transformation accompanying with the disappearance of co phase. Compared with30%CR and80%CR samples, the60%CR sample possesses higher strengths (yield strength:787MPa, tensile strength:1213MPa), appropriate plasticity (7.8%) and the highest strength-to-modulus ratio (17.8×10'3).
(9) TNTZF alloy has higher corrosion potential, lower corrosion current density, more stable passive current densities and wider passive region compared with Ti-6A1-4V ELI, which indicates that TNTZF alloy possesses much better corrosion resistance. In addition, pitting corrosion is observed on the surface passive film of Ti-6A1-4V ELI alloy but is not found on that of TNTZF alloy. XPS analysis results reveal that the passive film formed on TNTZF alloy is composed of Nb2O5, NbO2, Ta2O5, ZrO2, TiO and Ti2O3oxides in the matrix of TiO2, it makes the passive film more stable and protective than that of Ti-6A1-4V ELI which consisted of TiO Al2O3、V2O3. The alloy after cold rolling shows inferior corrosion resistance due to its high density of dislocation and strain concentration and stress-induced a" martensitic transformation. Precipitation of ω or a phase in the alloy after aging led to decrease of corrosion resistance compared with the ST alloy.
引文
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