苛刻工况条件下钛合金管材的腐蚀电化学特性研究

通过室内模拟腐蚀失重试验以及高温高压原位电化学测试分析,研究了TC4钛合金在苛刻腐蚀环境中的电化学特性。结果表明:在模拟含CO_2和H_2S地层水腐蚀环境中,TC4钛合金具有极其优越的抗均匀腐蚀及点蚀性。在180℃时均匀腐蚀速率仅为0.0008 mm/a。TC4钛合金的阳极极化曲线均存在明显钝化区,钝化膜起到良好的保护作用,腐蚀速率仍保持在较低水平;极化电阻随温度的升高而减小,抗腐蚀性有所减弱。但在高达180℃时其钝化膜仍具有良好的热力学稳定性,表现出了较好的抗CO_2和H_2S腐蚀性;钛合金钝化膜的半导体类型为n型,具有阳离子选择性,可排斥Cl~-等侵蚀性离子对钝化膜的侵蚀,有很强的耐蚀性。     

钛合金油管在苛刻井下环境中的抗腐蚀性能研究

通过失重腐蚀试验和应力腐蚀开裂(四点弯曲法)试验,研究了TC4钛合金在地层水和完井液环境中抗均匀腐蚀、局部腐蚀和SCC性能。结果表明:在地层水CO_2腐蚀环境中,TC4钛合金为轻微腐蚀,温度升高,均匀腐蚀速率变化不大,温度达到220℃时,均匀腐蚀速率仅为0.0012 mm/a,且试样表面无局部腐蚀,表明该合金具有良好的抗地层水CO_2均匀腐蚀和局部腐蚀性能;在完井液CO_2腐蚀环境中,TC4钛合金的均匀腐蚀速率高达0.4247 mm/a,该合金发生明显的点蚀和选择性溶解腐蚀;在地层水CO_2腐蚀和完井液CO_2腐蚀环境中SCC试验均未发现裂纹,具有良好的抗SCC性能。     

高pH值完井液中钛合金管材的腐蚀行为研究

基于高温高压腐蚀速率和原位电化学测试,并结合分子动力学模拟和第一性原理计算,探讨了钛合金(TC4)管材在高pH值完井液中的腐蚀行为,以及钝化膜的热力学稳定性。结果表明:TC4钛合金在180℃的高pH值磷酸盐完井液中的腐蚀极为严重,其均匀腐蚀速率高达0.4429mm/a;在高pH值磷酸盐完井液中,TC4钛合金的腐蚀为阳极反应过程控制,随着温度的升高,其腐蚀电位、腐蚀产物膜的膜阻和极化电阻显著降低,腐蚀反应的热力学驱动力增大、动力学阻力降低,腐蚀电流密度显著升高;在碱性溶液中,TiO_2钝化膜的钛氧键发生不同程度断裂,并且随着温度升高、碱性增强,TiO_2与溶液的界面结合能逐渐增大,钝化膜的热力学稳定性明显降低;在碱性焦磷酸钾溶液中,TiO_2钝化膜均可与K_2HPO_4、K_3PO_4反应生成疏松多孔的KTiOPO_4腐蚀产物膜,但TiO_2与K_3PO_4反应的热力学倾向更大。     

防喷器用718合金在CO_2、H_2S/CO_2环境中的腐蚀行为研究

通过腐蚀失重、应力腐蚀开裂(SCC)性能评价实验以及电化学测试研究了镍基合金718在模拟苛刻H2S/CO2环境和CO2环境中的腐蚀行为。结果表明:在模拟高温高压H2S/CO2腐蚀环境中,镍基合金718具有极其优越的抗均匀腐蚀、局部腐蚀和SCC性能;在饱和CO2腐蚀体系中,718合金的阳极极化曲线存在明显的钝化区,加入H2S后,极化电阻减小,钝化膜的保护作用减弱;镍基合金718在饱和CO2溶液体系中均具有较好的钝化和再钝化能力,且在50℃时,其点蚀电位最高,滞后环最小,耐缝隙腐蚀性能良好。     

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。     

微弧氧化钛合金的电化学腐蚀行为

采用微弧氧化技术在TC4钛合金表面制备了多孔陶瓷层,研究了其在Hank′s模拟体液中的电化学腐蚀行为,利用SEM和XRD分析了其表面形貌和物相组成。结果表明,微弧氧化合金的自腐蚀电位升高约0.3V,提高了TC4钛合金在生物体液环境下的化学稳定性。在钛合金植入体电位范围内,微弧氧化处理可明显提高极化电阻,减少腐蚀电流1~2个数量级。随腐蚀时间的延长,TC4钛合金表面钝化膜逐渐发生腐蚀,而微弧氧化膜浸泡初期HA的形核及生长是电极反应中最活跃部分,2周后表面形成均匀的HA薄膜,表现出良好的抗电化学腐蚀性能。     

苛刻腐蚀环境中高耐蚀合金管柱材质的抗腐蚀性能对比分析

通过模拟高温高pH值完井液CO_2腐蚀实验以及电化学测试,研究了高耐蚀合金管柱材质的抗腐蚀性能。结果表明:在高温高pH值CO_2腐蚀环境中,新型17Cr马氏体不锈钢发生了明显的选择性溶解腐蚀,且均匀腐蚀速率较大;2205双相不锈钢具有良好的抗腐蚀性能;TC4钛合金抗腐蚀性能极差,均匀腐蚀速率高达0.4247mm/a,且相比于其他高耐蚀合金,局部腐蚀最为严重。在高温高pH值CO_2腐蚀环境中,2205双相不锈钢的自腐蚀电流密度最小,抗腐蚀性能最好;TC4钛合金的抗腐蚀性能最差。     

H_2S/CO_2腐蚀环境中镍基合金825表面钝化膜的电化学特性

在模拟高温高压H_2S/CO_2气田腐蚀环境中对镍基合金825表面钝化膜进行腐蚀试验,利用电化学方法测量其极化曲线、电化学阻抗谱(EIS)和Mott-Schottky曲线(M-S曲线),研究了温度和H_2S/CO_2分压比对其表面钝化膜电化学特性的影响。结果表明:温度和H_2S/CO_2分压比对镍基合金825表面钝化膜的电化学行为影响规律相同,温度升高或H_2S/CO_2分压比增大时,双电层电容和钝化膜电容均增大,电荷转移电阻和钝化膜电阻减小,载流子浓度增大,说明温度升高和H_2S/CO_2分压比增大时,钝化膜的致密性降低,容易遭到破坏,厚度减薄,对基体的保护性降低。     

模拟海水环境中电化学状态对TC4钛合金腐蚀磨损行为的影响（英文）

采用摩擦失重法、电化学测试以及扫描电子显微镜等技术研究TC4钛合金在模拟海水环境中的腐蚀和腐蚀磨损行为,分析电化学状态对TC4钛合金钝化行为、钝化膜失效机制及腐蚀磨损协同作用的影响。结果表明,摩擦过程中TC4钛合金的开路电位明显负移,而且该合金的腐蚀电流密度相比静态腐蚀时提高了3个数量级。合金的腐蚀磨损失重随着电位的升高明显增大,磨蚀与磨损之间存在明显的协同作用,高电位时的腐蚀速度较大但是摩擦因数较低。电位在OCP和0.9 V之间变化时,纯机械磨损量在总腐蚀磨损量中的比重随着电位的升高逐渐降低,而磨损对腐蚀的促进量和腐蚀对磨损的促进量在总腐蚀磨损量中的比重在高电位时尤其显著。     

温度对X52管线钢C02腐蚀电化学行为影响

利用动电位极化和电化学阻抗谱技术,研究了温度（30℃,50℃,70℃）对X52管线钢在饱和CO2的NaCl溶液中腐蚀过程的影响。由实验结果得出温度升高促进腐蚀反应的阳极过程和阴极过程,使X52管线钢腐蚀速率增大而且温度对阴极过程的促进作用大于阳极,使Ecorr正向移动;同时温度升高增大了腐蚀产物的形成速率,使其在电极表面析出并以膜层的形式存在,但温度的改变并没有改变X52管线钢在此环境下的腐蚀机理。     

改进型镁扩散法制备高临界电流密度MgB2超导体性能研究

本文采用一种改进型镁扩散法成功制备出密度达到1.95g/cm₃的MgB₂超导块材。论文研究了不同的热处理条件对MgB₂块材的超导转变温度(T_c)和临界电流密度(J_c)性能的影响。采用最佳热处理条件制备的MgB₂超导体T_c和J_c分别达到了38.1K和0.53MA/cm₂(10K,自场)。为了改进镁扩散法MgB₂超导体中弱的高场磁通钉扎性能,本文还研究了nano-Pr₆O₁₁和C掺杂对MgB₂超导体的临界电流密度和不可逆场(H_irr)的影响。结果表明C掺杂的MgB₂超导体临界电流密度在10K,6T下达到了10₄A/cm₂,该结果比未掺杂MgB₂超导体在同样条件下性能提高了两个量级,甚至比固态反应法制备的nano-C掺杂MgB₂超导体性能更好。利用该方法制备的nano-Pr₆O₁₁掺杂的MgB₂超导体在10K,2T下也比未掺杂样品J_c提高达9.4倍。根据大量的实验结果和理论分析我们提出基于改进型镁扩散法和化学掺杂,包括纳米粒子和C掺杂,很有可能是一种制备高性能MgB₂超导体非常有效的途径。     

废旧锂离子电池中Li, Fe和V的回收及xLiFePO4-yLi3V2(PO4)3的制备

由于LiFePO_4和Li_3V_2(PO_4)_3材料的特征相近,制备方法类似,提供了一种从废旧LiFePO_4和Li_3V_2(PO_4)_3混合电池中回收Li、Fe和V,再制备xLiFePO_4-yLi_3V_2(PO_4)_3的方法。在空气气氛中600℃热处理1h后,去除粘结剂PVDF使活性物质与集流体分离。调节Li、Fe、V和P摩尔比,球磨、锻烧,配制不同比例的xLiFePO_4-yLi_3V_2(PO_4)_3(x:y=5:1,7:1,9:1)复合电极材料。表征了其形貌、结构和电化学性能,结果表明,回收制备的复合材料将同时具备LiFePO_4和Li_3V_2(PO_4)_3两种材料的电化学性能,能显著改善LiFePO_4的倍率性能。     

Effects of K2O-Li2O doping on surface and catalytic properties of Fe2O3/Cr2O3 system

The effects of K₂O and Li₂O-doping (0.5, 0.75 and 1.5 mol%) of Fe₂O₃/Cr₂O₃ system on its surface and the catalytic properties were investigated. Pure and differently doped solids were calcined in air at 400-600 °C. The formula of the un-doped calcined solid was 0.85Fe₂O₃:0.15Cr₂O₃. The techniques employed were TGA, DTA, XRD, N₂ adsorption at −196 °C and catalytic oxidation of CO oxidation by O₂ at 200-300 °C. The results revealed that DTA curves of pure mixed solids consisted of one endothermic peak and two exothermic peaks. Pure and doped mixed solids calcined at 400 °C are amorphous in nature and turned to α-Fe₂O₃ upon heating at 500 and 600 °C. K₂O and Li₂O doping conducted at 500 or 600 °C modified the degree of crystallinity and crystallite size of all phases present which consisted of a mixture of nanocrystalline α- and γ-Fe₂O₃ together with K₂FeO₄ and LiFe₅O₈ phases. However, the heavily Li₂O-doped sample consisted only of LiFe₅O₈ phase. The specific surface area of the system investigated decreased to an extent proportional to the amount of K₂O and Li₂O added. On the other hand, the catalytic activity was found to increase by increasing the amount of K₂O and Li₂O added. The maximum increase in the catalytic activity, expressed as the reaction rate constant (k) measured at 200 °C, attained 30.8% and 26.5% for K₂O and Li₂O doping, respectively. The doping process did not modify the activation energy of the catalyzed reaction but rather increased the concentration of the active sites without changing their energetic nature.     

Improved capacity and rate capability of Ru-doped and carbon-coated Li4Ti5O12 anode material

Pure Li₄Ti₅O₁₂, modified Li₄Ti₅O₁₂/C, Li₄Ru_0.01Ti_4.99O₁₂ and Li₄Ru_0.01Ti_4.99O₁₂/C were successfully prepared by a modified solid-state method and its electrochemical properties were investigated. From the XRD patterns, the added sugar or doped Ru did not affect the spinel structure. The results of electrochemical properties revealed that Li₄Ru_0.01Ti_4.99O₁₂/C showed 120 and 110 mAh/g at 5 and 10 C rate after 100 charge/discharge cycles. Li₄Ru_0.01Ti_4.99O₁₂/C exhibited the best rate capability and the highest capacity at 5 and 10 C charge/discharge rate owing to the increase of electronic conductivity and the reduction of interface resistance between particles of Li₄Ti₅O₁₂.It is expected that the Li₄Ru_0.01Ti_4.99O₁₂/C will be a promising anode material to be used in high-rate lithium ion battery.     

The high-temperature corrosion behavior of Nb-Al alloys in a H2/H2S/H2O gas mixture

The corrosion behavior of pure Nb and three Nb Al alloys containing 12.5, 25, and 75 at.% Al was studied over the temperature range of 800–1000°C in a H₂/H₂S/H₂O gas mixture. Except for the Nb-12.5Al alloy consisting of a two phase structure of -Nb and Nb₃Al, other alloys studied were single phase. The corrosion kinetics followed the parabolic rate law in all cases, regardless of temperature and alloy composition. The parabolic rate constants increased with increasing temperature, but fluctuated with increasing Al content. The Nb-75Al alloy exhibited the best corrosion resistance among all alloys studied, whose corrosion rates are 1.6–2.2 orders of magnitude lower than those of pure-Nb (depending on temperature). An exclusive NbO₂ layer was formed on pure Nb, while heterophasic scales were observed on Nb-Al alloys whose compositions and amounts strongly depended on Al content and temperature. The scales formed on Nb-12.5Al consisted of mostly NbO₂ and minor amounts of Nb₂O₅, NbS2, and -Al₂O₃, while the scales formed on Nb-25Al consisted of mostly Nb₂O₅ and some -Al₂O₃. The scales formed on Nb-75Al consisted of mostly -Al₂O₃ and Nb₃S₄ atT 900°C, and mostly -Al₂O₃ , Nb₃S₄ and some AlNbO₄ at 1000°C. The formation of -Al₂O₃ and Nb₃S₄ resulted in a significant reduction of the corrosion rates.     

Synthesis of lanthanum carbonate nanoparticles via sonochemical method for preparation of lanthanum hydroxide and lanthanum oxide nanoparticles

Lanthanum carbonate nanoparticles were synthesized from the reaction of lanthanum acetate and Na₂CO₃ under sonication via sonochemical method. Lanthanum hydroxide nanoparticles were prepared by facial hydrothermal processing from the resulted product at 110 °C for 24 h. The role of surfactant, calcination temperature and sonication time were investigated on the morphology and particle size of the products. Products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectrum (XPS), and Fourier transform infrared (FT-IR) spectra. La₂O₃ nanoparticles were obtained by calcinations of the nanoparticles of lanthanum carbonate at 600 °C.     

Preparation and characteristic of spherical Li3V2(PO4)3

Spherical Li₃V₂(PO₄)₃ was synthesized by using N₂H₄ as reducer. The products were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results show that single-phase, spherical and well-dispersed Li₃V₂(PO₄)₃ has been successfully synthesized in our experimental process. Electrochemical behaviors have been characterized by charge/discharge measurements. The initial discharge capacities of Li₃V₂(PO₄)₃ were 123 mAh g⁻¹ in the voltage range of 3.0–4.3 V and 132 mAh g⁻¹ in the voltage range of 3.0–4.8 V.     

Alloyed W–(Co,Ni,Fe)–C phases for reaction sintering of hardmetals

It has been shown that W–Co–C phases could dissolve a substantial amount of metals such as V, Cr and Ta, which are known to positively influence the microstructure of hardmetals with respect to uniform grain size distribution and fine grain size. This offers a tool to circumvent the conventional doping of hardmetals with individual carbides. In the present study we used double- and triple-alloyed κ-W₉Co₃C₄ (i.e. κ-(W,V,Cr)₉Co₃C₄ and κ-(W,V,Cr,Ta)₉Co₃C₄) and applied a variety of sintering experiments to obtain WC–Co, WC–(Ti,Ta,Nb)C–Co and WC–(Ti,Ta,Nb)(C,N)–Co hardmetals. We also prepared κ-W₉Fe₃C₄, alloyed κ-W₉Ni₃C₄, and κ-W₉(Fe/Ni)₃C₄, and used the latter for sintering.     

The high-temperature corrosion behavior of Co-Nb alloys in mixed-gas atmospheres

The corrosion of Co-Nb alloys containing up to 30 wt.% Nb in H₂-H₂S-H₂O gas mixtures was studied over the temperature range of 600–800°C. The gas composition falls in the stability region of cobalt sulfide and Nb₂O₅ in the phase diagrams of the Co-O-S and Nb-O-S systems at all temperatures studied. Duplex scales, consisting of an outer layer of cobalt sulfide and a complex, heterophasic inner layer, were formed at all temperatures studied. In addition to cobalt sulfide and CoNb₃S₆, a small amount of NbO₂ was found in the inner layer. The reason for the formation of NbO₂ over that of Nb₂O₅ in the scale is that the outer sulfide scale lowers the oxygen activity within the scale into the NbO₂-stability region. Two-stage kinetics were observed for all alloys, including an initial irregular stage usually followed by a steady-state parabolic stage. The steady-state parabolic rate constants decreased with increasing amounts of Nb, except for Co-20Nb corroded at 700°C. Nearly identical kinetics were observed for Co-20Nb corroded at 600°C and 700°C. The presence of NbO₂ particles leads only to a limited decrease of the available cross-section area for the outward-diffusing metal ions. The activation energies for all alloys are similar and are in agreement with those obtained in a study of the sulfidation of the same alloys. The primary corrosion mechanism involves an outward Co transport.     

定-转子反应器制备LiFe1-xMxPO4 (M= Mn, Ni)粉体及其性能研究

采用具有高效传质和微观混合性能的定-转子反应器制备了LiFe_1-xMn_xPO₄ (x=0.0, 0.1, 0.2, 0.3)和LiFe_1-xNi_xPO₄ (x=0.00, 0.03, 0.05, 0.07)粉体,分别用作正极材料制成电池后,采用电池测试系统测定了电池的电化学性能随温度的变化规律。结果表明,粉体颗粒呈类球形,尺寸分布均匀,粒径范围为5~10 μm,Mn和Ni的掺杂没有改变粉体的晶体结构。以LiFe_0.8Mn_0.2PO₄和LiFe_0.95Ni_0.05PO₄两种组成的粉体性能最好,在倍率0.1 C下,所得电池的首次充放电比容量在室温和50 _oC时,分别为153.2和155.7 mAh/g,及156.4和160.4 mAh/g;100次充放电循环后电池的容量保持率分别为95.4和96.5%,及93.8和95.0%。借助具有过程强化作用的定-转子反应器制备的Mn和Ni掺杂LiFePO₄正极材料的电性能得到显著提高。原因是定-转子反应器一方面可以制备颗粒尺寸均匀的粉体,另一方面又可使掺杂的Mn和Ni在粉体颗粒中均匀分布,两者同时提高了电池中Li₊的扩散速率,进而提高了锂离子电池的电化学性能和高温电性能。