油气开采用钛合金石油管材料耐腐蚀性能研究

选取5种油气开发常用钛合金材料(Ti-6Al-4V、Ti-6Al-4V-0.1Ru、Ti-6Al-2Sn-4Zr-6Mo、Ti-3Al-8V-6Cr-4Zr-4Mo和Ti-5.5Al-4.5V-2Zr-1Mo)为研究对象,使用高温高压釜模拟国内典型严酷服役工况环境,研究了不同钛合金材料耐均匀腐蚀、局部腐蚀、点蚀、应力腐蚀开裂(SCC)及缝隙腐蚀的性能,通过使用扫描电镜和能谱分析等手段对腐蚀形貌和腐蚀产物进行了分析,并使用电化学方法对不同合金的耐腐蚀机理进行了研究。结果显示,在所测试工况条件下,所有钛合金材料腐蚀反应均为阳极控制过程,均匀腐蚀速率均低于0.001mm/a,并且对应力腐蚀开裂均有良好的抗力。Ti-6Al-4V和Ti-5.5Al-4.5V-2Zr-1Mo合金出现明显的点蚀和缝隙腐蚀问题。对腐蚀机理研究表明,在工况条件温度下,随着pH值的降低,所有钛合金均发生自腐蚀电位降低,极化电阻减小,腐蚀电流增大,耐腐蚀性能下降,其中Ti-6Al-4V耐腐蚀性能下降的最为明显,研究结果为油气开发工况下钛合金石油管的选材和缝隙腐蚀问题防治提供理论基础。     

TC4钛合金在3.5%NaCl溶液中的应力腐蚀行为

采用楔形张开加载（WOL）试样开展应力腐蚀试验,研究TC4钛合金在3.5%NaCl溶液中的应力腐蚀行为,分析应力腐蚀开裂（SCC）机理。结果表明,腐蚀24 h后,即可在试样表面观察到SCC裂纹。腐蚀30 d和75 d的试样,SCC裂纹长度接近,且都明显大于腐蚀15 d的试样,说明15～30 d内SCC扩展终止。试样的加载应力越大,裂纹长度越长,随着裂纹扩展,应力逐渐松弛,当残余KI值降低到38 MPa·m~(1/2)附近时,SCC扩展终止。SCC扩展是应力和腐蚀耦合作用的过程,在SCC起始阶段,应力主导裂纹快速扩展,断口呈韧窝形貌。SCC中后阶段,断口呈解理形貌和鳞片状花样,鳞片边缘存在钛氧化物,推测是由于应力松弛后的裂纹间歇性驻留和阳极溶解促进的裂纹继续扩展反复交替作用形成的。     

钛合金应力腐蚀开裂过程中氢的作用

本文用金相显微镜和扫描电镜对 Ti-5Al-2.5Sn 合金在近中性3.5%NaCl 水溶液中 SCC 裂纹形核带的微观形貌进行了观察。通过金相显微镜、透射电镜、X 光衍射仪和离子探针等手段对 SCC断口的研究,证明了 SCC 裂纹尖端生成的氢确实进入了钛合金基体,并且裂纹前端最大三向应力区域形成了 fct 型和 bcc 型氢化物沉淀,导致了 SCC 的快速发展。在实验事实的基础上,对 SCC 过程中氢的来源、输运、氢起作用的位置,以及内氢的作用等问题进行了讨论。     

铸造Ti-6Al-4V钛合金疲劳裂纹扩展特性的研究

按照GB6398-1986试验标准,采用紧凑拉伸试样(CT)测定了铸造Ti-6Al-4V钛合金疲劳裂纹扩展速率da/dN,采用扫描电镜(SEM)等现代技术对断口形貌进行观察,分析了不同应力比(R值)条件下的疲劳裂纹扩展特性。结果表明,应力比R对铸造Ti-6Al-4V钛合金的裂纹扩展速率影响较大,应力比R越大,裂纹扩展速率越大。在裂纹预裂区和快速扩展区的断裂机理主要是以微区解理断裂为主,稳态扩展区主要是以疲劳条带扩展机制为主,同时也存在微区解理断裂机制。     

基于全场法的航空Ti-2Al-1.5Mn钛合金疲劳裂纹扩展各向异性研究

准确定量表征航空重要承载结构材料抗疲劳裂纹扩展能力是实施结构件服役寿命评估的基础。本文针对航空用Ti-2Al-1.5Mn钛合金,沿着板材不同取向制备CT试样开展疲劳裂纹扩展速率试验,分别基于全场法及传统方法定量表征了裂纹扩展各阶段应力强度因子幅DK。结果表明：疲劳裂纹扩展速率da/dN-DK关系及裂纹扩展路径显著受到材料取向的影响。相比较于传统表征应力强度因子幅方法,基于全场法一方面能够直接考虑裂尖塑性变形引起裂纹闭合的影响,另一方面能够有效避免因裂纹扩展路径偏折带来的有效裂纹长度测量偏差,从而不能准确获取有效应力强度因子幅的问题,其具有显著优势。基于全场法的疲劳裂纹扩展应力强度因子幅表征具有广泛应用全景。     

氢对Ti-4Al-2V疲劳裂纹扩展速率的影响

采用CT试样对4种含氢量不同的Ti-4Al-2V钛合金的室温疲劳裂纹扩展速率进行了实验测定，并对断裂以后的试样进行了断口观察。实验结果表明：含氢的Ti-4Al-2V材料的稳态裂纹扩展行为符合Paris幂律关系，氢对裂纹稳态扩展区和失稳扩展区的da／dN基本没有影响，但对近门槛扩展行为有明显影响；与自然含氢量的材料相比，高含氢量的材料疲劳裂纹在近门槛扩展区的速率明显较低。     

IncoMAPAl—9052合金在3.5%NaCl溶液中的应力腐蚀行为

采用双悬臂梁试样,实验研究了IncoMAP Al-9052合金在3.5％NaCl溶液中的应力腐蚀开裂(SCC)行为。结果表明该种合金的裂纹扩展机制有别于常规的铝合金。其初期阶段的裂纹扩展过程可划分为三个阶段,在每一阶段的裂纹扩展机制可能是不同的,但其裂纹扩展的主要机制为氢脆。     

置氢Ti-6Al-4V钛合金的热压缩变形行为研究

通过热模拟压缩实验,研究了氢对Ti-6Al-4V钛合金热变形行为的影响。结果表明,置氢可以显著降低Ti-6Al-4V钛合金高温压缩时的流动应力,提高Ti-6Al-4V钛合金的热加工变形速率一个数量级以上,并且明显降低了Ti-6Al-4V钛合金的变形温度。在变形温度760℃~800℃范围内,置氢量为0.4wt%的Ti-6Al-4V钛合金的流动应力最小;在变形温度840℃~920℃范围内,置氢量0.2wt%的Ti-6Al-4V钛合金的流动应力最小。同时,置氢前后Ti-6Al-4V钛合金的变形激活能计算结果表明,置氢量为0.4wt%的Ti-6Al-4V钛合金在α+β两相区的变形激活能为208.3kJ/mol,与未置氢Ti-6Al-4V钛合金相比降低了316kJ/mol。     

温度对钛合金应力腐蚀行为的影响

通过在实验室控制海水温度模拟不同海域和季节海水环境。采用恒位移应力腐蚀实验和慢应变速率拉伸实验(SSRT)考察温度对Ti80钛合金应力腐蚀敏感性的影响规律,结合电化学阻抗谱、Mott-Schottky曲线以及三维视频显微镜和扫描电镜(SEM)分析温度对钛合金的影响机制。结果表明：在常压,5～35℃范围内,随着温度的降低,钛合金样品的应力腐蚀开裂敏感性指数逐渐增大,临界强度因子K1SCC值逐渐减小,应力腐蚀倾向增加。低温海水环境下样品断口局部甚至出现河流花样特征和撕裂岭准解理特征。这是因为低温海水环境中钛合金样品裂纹尖端钝化膜电阻较小、缺陷较多、位错容易堆积从而导致钝化膜局部应力集中,膜致应力增大,与外加应力协同作用下,裂纹成核和扩展加快,导致钝化膜难以修复,应力腐蚀速率加快。     

钛合金与WC-17Co涂层界面结合性能分析

采用超音速火焰喷涂技术在Ti-6Al-4V合金表面制备WC-17Co涂层,从显微形貌、界面氧化行为、裂纹扩展形式等方面系统分析了WC-17Co涂层与Ti-6Al-4V基体界面断裂失效原因,并利用四点弯曲法测量了WC-17Co与Ti-6Al-4V合金的平均断裂能量释放率.结果表明,热喷涂过程使Ti-6Al-4V的表面氧化相含量显著提高.氧化后Ti-6Al-4V的表面显微硬度达到322.4 HV,熔融粒子撞击到Ti-6Al-4V表面很难对基体造成明显的塑性变形,不能形成有效咬合,使得钛合金与WC-17Co涂层的结合性能偏低.     

新型1200 MPa级Ti-35421合金应力腐蚀敏感性的原位电化学研究

以新型1200 MPa级Ti-35421合金(Ti-3Al-5Mo-4Cr-2Zr-1Fe)为研究对象,采用慢应变速率拉伸实验结合原位电化学监测研究了不同应变速率和阴极保护电位对其应力腐蚀开裂行为的影响。结果表明：当应变速率为1.67×10^-5mm·s^-1时Ti-35421合金在3.5%NaCl溶液中应力腐蚀敏感性最高,其塑性损失和应力腐蚀指数分别为27.27%和0.273;裂纹尖端钝化膜层在应力和腐蚀的共同作用下钝化保护弱于溶解,导致了应力腐蚀加剧;当外加阴极保护电位为-600mV时Ti-35421合金在3.5%NaCl溶液中的应力腐蚀敏感性最低,其最佳阴极保护电位范围为-450～-600 mV,降低了阳极共轭反应,从而使其塑性损失和应力腐蚀指数分别降低到1.01%和0.113。     

The effects of gas nitriding on fatigue behavior in titanium and titanium alloys

Fatigue behavior has been studied on gas-nitrided smooth specimens of commercial pure titanium, an alpha/beta Ti-6Al-4V alloy, and a beta Ti-15Mo-5Zr-3Al alloy under rotating bending, and the obtained results were compared with the fatigue behavior of annealed or untreated specimens. It was found that the role of the nitrided layer on fatigue behavior depended on the strength of the materials. Fatigue strength was increased by nitriding in pure titanium, while it was decreased in the Ti-6Al-4V and Ti-15Mo-5Zr-3Al alloys. Based on detailed observations of fatigue crack initiation, growth, and fracture surfaces, the improvement and the reduction in fatigue strength by nitriding in pure titanium and both alloys were primarily attributed to enhanced crack initiation resistance and to premature crack initiation of the nitrided layer, respectively.     

MICROFRACTOGRAPHY OF NEAR-THRESHOLD FATIGUE CRACK GROWTH

The fracture surface micromorphology in the near-threshold FCG region was studied inLD-10 aluminum alloy and Ti-6Al-4V allov.The SEM examinations reveal that the frac-ture surface of both alloys at low crack growth rates(1×10~(-7)-1×10~(-5)mm/cycle)takes ona cyclic facet appearance.The typical morphologies were either sawtoothedfacets or terracedfacets for LD-10 aluminum alloy and isolated island facets for Ti-6Al-4V alloy.The mech-anism of near-threshold fatigue crack growth is explicated on the basis of experimental ob-servations.     

The effects of hydrogen on fatigue crack growth behaviour of Ti-6Al-4V and Ti-4.5Al-3V-2Mo-2Fe alloys

The fatigue crack growth rates (FCGRs) of Ti-6Al-4V and Ti-4.5Al-3V-2Mo-2Fe alloys were determined in gaseous hydrogen, air, and a soft vacuum. In hydrogen and at a stress ratio of 0.1, the deflected crack path associated with the localized brittle fracture of the α-phase could account for the reduced FCGR of Ti-6Al-4V. At a higher stress ratio of 0.5, hydrogen embrittlement enhanced cracking and alleviated the effect of crack deflections in Ti-6Al-4V specimens, resulting in the FCGR in hydrogen similar to that in air. In contrast, the FCGR of Ti-4.5Al-3V-2Mo-2Fe was insensitive to both the environment and stress ratio.     

Effect of Al-5Ti-1B-1Re on the Microstructure and Hot Crack of As-Cast Al-Zn-Mg-Cu Alloy

High crack tendency is easy to occur during preparation of the castings and ingots of Al-Zn-Mg-Cu alloy, and it is most difficult to be solved due to the characteristics for the series alloy. As-cast microstructures and hot cracking tendency of Al-Zn-Mg-Cu alloy with different addition levels of Al-5Ti-1B-1Re were investigated in the paper. Moreover, solidification characteristics of the experimental alloys with different mass fractions of Al-5Ti-1B-1Re were analyzed, and the addition content of Al-5Ti-1B-1Re was optimized. These results indicate that the microstructure of the experimental alloys with Al-5Ti-1B-1Re refiner is fine obviously, the dendrite shape refined by Al-5Ti-1B-1Re becomes more globular, the grain boundary is smoother, and the SDAS is smaller compared with the alloy without Al-5Ti-1B-1Re. When the addition level of the grain refiner is less than 0.2%, the hot cracking tendency for the experimental alloy is reduced. The addition of 0.2% Al-5Ti-1B-1Re is best effective to improve the as-cast microstructures and hot cracking of Al-Zn-Mg-Cu alloy, and the best addition level of Al-5Ti-1B-1Re refiner is 0.2%.     

30CrMnSi钢应力腐蚀裂纹内的电化学行为

<正> 一、前言 应力腐蚀裂纹内的电化学行为与裂纹起裂以及裂纹扩展动力学之间的关系,目前仍然是研究的薄弱环节。其主要原因是由于应力腐蚀裂纹很细而且裂纹内溶液非常少,使得裂纹内尤其是裂纹尖端区域的电化学参数很难测试。本文作者等在前人方法的基础上提出了在液体石蜡保护下测试裂纹内电位、pH值、Cl~-浓度分布的新方法。本工作在该方法的基础上又作了改进,并对30CrMnSi钢应力腐蚀裂纹内的电化学行为进行了研究。     

INTERPHASE STRESS CORROSION CRACKING OF ALLOY Ti－24Al－11Nb IN METHANOL SOLUTION

ＩＮＴＥＲＰＨＡＳＥＳＴＲＥＳＳＣＯＲＲＯＳＩＯＮＣＲＡＣＫＩＮＧＯＦＡＬＬＯＹＴｉ－２４Ａｌ－１１ＮｂＩＮＭＥＴＨＡＮＯＬＳＯＬＵＴＩＯＮ￥ＺＨＡＮＧＹｕｅ;ＣＨＵＷｕｙａｎｇ;ＸＩＡＯＪｉｍｅｉ（ＤｅｐａｒｔｍｅｎｔｏｆＭａｔｅｒｉａｌｓＰｈｙｓ...     

MECHANISM OF SLOW CRACK GROWTH AND STRESS CORROSION CRACKING IN AUSTENITIC STAINLESS STEEL

通过金相跟踪观察、力学测量及断口分析,研究了奥氏体不锈钢氢致开裂和应力腐蚀的机理.结果表明,无论是不稳定型(321)还是稳定型(310)奥氏体不锈钢,电解充氢时先产生塑性变形,当它发展到临界状态时就导致氢致裂纹的形核.但在42%MgCl_2沸腾溶液中应力腐蚀时,裂纹的形核和滞后塑性变形无关.两种(321)輿氏体不锈钢应力腐蚀的门槛值K_(ISCC)远比严重充氢时氢致开裂的门槛值K_(IH)要低.两者的断口形貌也不同,应力腐蚀是解理断口,且和K_I无关.而氢致开裂断口和K_I有关,K_I高是韧窝,K_I低则获得准解理断口.实验表明,氢在奥氏体不锈钢应力腐蚀(沸腾MgCl_2介质)过程中并不起主要作用.