温度对718镍基合金在高酸性环境下耐腐蚀性能的影响

718镍基合金是高酸性油气井中常用的金属材料,但目前对其腐蚀机理和影响因素的研究较少。利用高温高压反应釜进行腐蚀模拟,采用失重法、扫描电镜(SEM)等手段研究了温度对718镍基合金在高含H_2S/CO_2环境下腐蚀行为的影响。结果表明:在CO_2分压3.5 MPa、H_2S分压3.5 MPa、Cl~-含量150 000 mg/L的模拟环境下,718镍基合金在150,175,205℃下均呈现全面腐蚀,未出现点蚀和局部腐蚀。但随温度升高,镍基合金718的均匀腐蚀速率逐渐增加,材料表面钝化膜出现硫化,并逐渐向腐蚀产物膜转变,质地由致密变得疏松。     

元素S对镍基合金718在含H2S和CO2盐溶液中腐蚀行为的影响

目前就元素S对高酸性油气井中常用的金属材料镍基合金718腐蚀行为影响的研究较少。在模拟高温、高含H2S/CO2和高Cl-浓度的腐蚀环境中,通过高温高压腐蚀模拟试验,结合失重测量、扫描电子显微镜(SEM)和X射线能谱分析(EDS)等技术手段研究了元素S对镍基合金718腐蚀行为的影响。试验表明:在205℃,CO2分压3.5 MPa、H2S分压3.5 MPa、Cl-浓度200 g/L环境下,1 g/L元素S的加入加剧了镍基合金718的腐蚀,增加了应力腐蚀开裂的敏感性。点蚀主要源于Cl-参与的歧化反应,而均匀腐蚀是高温下的单质S直接或间接与金属发生反应导致的。开裂的成因是单质S的加入加速了点蚀坑的形成和发展,导致多个点蚀坑连通构成长条状的腐蚀坑,最终形成裂纹导致开裂。     

高温高酸性环境下镍基合金718与异种金属偶接的电偶腐蚀行为

高温/高压高酸性腐蚀环境中镍基合金718常作为可靠的材料使用,但不可避免会与其他金属偶接使用,易产生电偶腐蚀。模拟150℃,H_2S分压1.0 MPa,CO2分压1.5 MPa,Cl~-浓度200 000 mg/L的高温高酸性腐蚀环境,采用高温高压电化学测试技术和浸泡腐蚀模拟试验,研究了镍基合金718分别与低合金钢35Cr Mo、C110和不锈钢13Cr偶接后的电偶腐蚀行为。结果表明:在模拟高温高酸性环境下,3种金属分别与718合金偶接后,均发生了一定程度的电偶腐蚀,其中C110电偶腐蚀速率最大,而不锈钢13Cr的电偶腐蚀速率最小。电偶腐蚀的驱动力是2种金属的自腐蚀电位差,异种金属偶接后的电偶效应与两偶接材料的电位差成正比,而阳极材料自身的极化特性决定了其与耐蚀合金偶接后的电偶腐蚀程度。     

镍基合金825在模拟油气井含CO_2环境中的耐蚀性研究

针对深层油气井开采过程中的CO_2腐蚀问题,采用高温高压釜模拟腐蚀试验和动电位极化曲线、电化学阻抗谱(EIS)等测试手段研究了镍基合金825在苛刻CO_2环境中的腐蚀行为。试验结果表明:镍基合金825在210℃、CO_2分压4.4 MPa的腐蚀环境中,腐蚀速率为0.015 7 mm/a,均匀腐蚀很轻微,表现出良好的抗均匀腐蚀性能;镍基合金825的阳极极化曲线呈现出明显的钝化区,且在120℃、CO_2分压为3.5 MPa条件下存在二次钝化现象;随着温度升高,CO_2分压增大,自腐蚀电位负移,腐蚀驱动力变大; EIS表明电化学阻抗谱有明显的容抗弧特征,电荷转移电阻呈减小的趋势,而钝化膜电容呈减少趋势,电化学腐蚀动力学阻滞性能减弱,降低了镍基合金825在模拟工况中的耐蚀性。     

镍基合金825在元素硫环境中的局部腐蚀特征

通过模拟普光气田元素硫沉积环境,调节腐蚀体系的温度,研究了固溶强化镍基合金825的腐蚀特征,并利用扫描电子显微镜(SEM)、能谱仪(EDS)等技术手段研究了镍基合金825发生点蚀后腐蚀产物的形貌和成分。结果表明,一定温度下元素硫(S8)与酸性NaCl溶液共同作用使镍基合金825产生明显的以点蚀为主的局部腐蚀。腐蚀产物层存在开裂现象,其腐蚀产物主要由Cr、Ni、S、O等元素组成。镍基合金825在高于元素硫熔点的温度及Cl-存在条件下易发生局部腐蚀。     

L360钢在含H_2S/CO_2溶液中的腐蚀失效形式研究

在模拟NY气田含H2S/CO2地面集输工况环境中,采用高温高压釜进行了L360钢的腐蚀实验,结果表明,均匀腐蚀速率略高于NACE标准0.076mm/a,但应力腐蚀敏感性很低,应力诱导点蚀是L360钢腐蚀的主要破坏形式。应力使金属表面能增大,腐蚀产物膜变得疏松,促进了局部腐蚀的发展。     

管线钢在湿气介质中的H_2S/CO_2腐蚀行为研究

利用高温高压反应釜模拟高含硫气田H2S/CO2共存环境,在流动湿H2S/CO2介质中进行腐蚀实验,辅以SEM,EDS和XRD,探讨了湿气介质中高H2S分压对API-X52和API-X60管线钢H2S/CO2腐蚀行为的影响。两种钢在湿气介质中的腐蚀速率均随H2S分压的升高而增加,X60腐蚀速率略高于X52,随着H2S分压由0.15MPa增至2.0MPa,腐蚀形态由全面腐蚀趋向局部腐蚀,腐蚀过程由H2S控制,腐蚀产物以四方晶系的FeS1-x(Mackinawite)为主。X60钢表面出现氢鼓泡,内部发生氢致开裂。     

模拟下古气藏工况下抗硫油管钢的CO_2/H_2S腐蚀行为

为了更好地理解抗硫油管钢在含硫气田中的腐蚀行为和机理,利用高温高压反应釜装置,结合SEM和XRD分析方法,对N80S和P110S抗硫油钢管在模拟下古气藏环境中CO_2,H_2S共存时的腐蚀行为进行了研究,计算了不同CO_2和H_2S分压比时的腐蚀速率,分析了腐蚀产物特征和成分,探讨了其腐蚀机理。结果表明:2种抗硫油管钢随H_2S含量的增大,腐蚀速率先增大后减小;H_2S微量时抗硫油管钢表面形成了Fe CO3和Fe S等腐蚀物,未见明显的腐蚀坑,随H_2S含量的增大,表面的腐蚀产物为铁的硫化物且存在明显的局部腐蚀。     

基于点蚀的316L不锈钢在酸性气田环境中的适应性评价

国内外酸性气田的开发使腐蚀环境越来越苛刻,为满足气液混输的工艺要求,发展了耐蚀合金/碳钢的双金属复合管技术。316L不锈钢被广泛用于双金属管的内衬,在含H_2S和CO_2环境中腐蚀速率很低,然而在高含Cl-的溶液中,316L不锈钢容易出现点蚀而诱发集输管线失效,为此,就316L不锈钢在酸性气田集输环境中的点蚀进行评述。讨论了影响316L不锈钢点蚀的材质因素,Mn和Fe的硫化物及Mg、Al、Ca的氧化物等两种夹杂物均能促进钝化膜的溶解而引起点蚀;分析了316L不锈钢点蚀的H_2S、CO_2、温度、Cl-浓度和pH值等环境的适应性条件,发现H_2S环境比CO_2环境更容易发生点蚀,H_2S和CO_2对点蚀发生存在协同机制,温度升高、Cl-浓度增加和酸性介质均会增加316L不锈钢点蚀的敏感性。为进一步优化选材原则,需重点加强环境因素的协同机制、环境适应性的边界条件、点蚀发展的动力学以及新的标准研究。     

不同腐蚀环境下压力容器材质耐蚀性评价

结合塔河油田实际情况,通过对压力容器拟选用的5种材料20、20G、Q345、A333、Q245分别进行CO_2+H_2S共同控制环境、H_2S主控腐蚀环境和CO_2主控腐蚀环境3个环境下的腐蚀失重试验,并对经过试验的挂片进行扫描电镜(SEM)观察和能谱(EDS)分析。结果显示:选取的5种材质的挂片在CO_2+H_2S共同控制环境和H_2S主控腐蚀环境的腐蚀速率均小于0.1 mm/a,且比CO_2主控腐蚀环境条件下的腐蚀速率小;在H_2S+CO_2共同控制的腐蚀环境中,5种材质腐蚀速率大小依次为Q345>20>Q245>A333>20G;在H_2S腐蚀为主的环境中,5种材质腐蚀速率大小依次为20>20G>Q245>Q345>A333;在CO_2腐蚀为主的环境中,5种材质腐蚀速率大小依次为Q345>A333>20G>20>Q245。根据试验结果,不同腐蚀环境下5种材料的防腐蚀性能均不同,结合现场实际工况,对压力容器材质进行相应的选材。     

Preparation of ZrO2-CeO2 and HfO2-CeO2 nanopowders

We prepared weakly agglomerated powders of ZrO₂-CeO₂ and HfO₂-CeO₂ solid solutions 5–8 nm in particle size, consisting of monoclinic and tetragonal phases. After heat treatment at 1200°C, the crystallite size was 30 and 14 nm, respectively. We also examined the effect of precipitate freeze drying on the crystallization of hafnia-based solid solutions containing up to 20 mol % CeO₂.     

Comparison of the Electronic Structures of La2CuO4, Sr2CuO2Cl2, and Sr2CuO2F2

First-principles cluster calculations are reported of the local electronic structure of the three compounds: La₂CuO₄, Sr₂CuO₂Cl₂, and Sr₂CuO₂F₂. The copper ${\text{3d}}_{x^2 - y^2 } $ and the planar oxygen 2p _σ atomic orbitals exhibit a similar degree of covalency. The out-of-plane orbitals, however, are quite different with the ${\text{3}}d_{3z^2 - r^2 } $ atomic orbital lowered significantly in energy for chlorine and fluorine apical positions.     

Thermoelectric power of single-phase samples of Tl2CaBa2Cu2O y and Ba2CaSr2Cu2O y

Single-phase 2122 samples of thallium and bismuth superconductors were made by the precursor matrix method. The thermopower of these samples was measured in the temperature range 250 K-T _c . The thermopower was positive and decreased linearly with increasing temperature aboveT _c (onset). The exponential enhancement of thermopower seen in the undoped and doped YBCO was not observed in these samples. The linear variation of thermopower can be explained on the basis of either a two-band model or a narrow band model.     

VLE data for CO2-CF2Cl2, N2-CO2, N2-CF2Cl2 and N2-CO2-CF2Cl

Knowledge about vapour-liquid (VLE) is required as a basis of reliable calculations for separation processes. Correlations available for the prediction of T, p, x, y data are less accurate for mixtures at high pressures and mixtures containing supercritical components. The results of VLE experiments are reported and compared with data calculated with equations of state.     

Structure of Na2O·2TiO2 glass

X-ray radial distribution analysis and Raman spectroscopic measurement were carried out on Na₂O-2TiO₂ glass prepared by twin-roller quenching method. It is found that four-coordinated Ti⁴⁺ ions may be predominant over six-coordinated ones in the present glass. It is also found that the fraction of six-coordinated Ti⁴⁺ ions is larger in the present glass than in K₂O·2TiO₂ and Cs₂O·2TiO₂ glasses. Poorer glass-forming ability of the Na₂O-TiO₂ system compared with the K₂O-TiO₂ and Cs₂O-TiO₂ systems is ascribed to a larger fraction of TiO₆ octahedron for the former system.     

SiO2—TiO2—ZrO2系涂层的制备及其特性

用溶胶－凝胶法（sol-gel method）在不锈钢表面制备了SiO2-TiO2-ZrO2系无机氧化膜（STZ）。用DTA／TG、IR、XRD和SEM等手段研究了涂层制备时由凝胶向玻璃态的转变以及涂层薄膜的显微结构特点，考察了涂层对基体的保护效果。试验结果表明，在溶胶至凝胶最终转变为无机氧化物的过程中形成了无机网络，Si^4 和Zr^4 充当了网络骨架的形成离子。涂层为无定型玻璃态，其间混有石英、锐钛矿或金红石等微晶。     

Elastic and Electronic Properties of Superconducting CaPd 2 As 2 and SrPd 2 As 2 vs. Non-superconducting BaPd 2 As 2

The first-principles calculations were performed to predict the elastic and electronic properties of the superconducting ThCr₂Si₂-type phases CaPd₂As₂ and SrPd₂As₂ in comparison with the non-superconducting CeMg₂Si₂-type phase BaPd₂As₂. Besides, the same properties were compared for CeMg₂Si₂- and ThCr₂Si₂-type polymorphs of BaPd₂As₂. We found that all these phases are mechanically stable and belong to soft materials with low hardness. The near-Fermi region is formed by the valence states of the blocks [Pd₂As₂] with decisive contributions of Pd 4d states. The values of N(E _F) increase in the sequence: CaPd₂As₂ < SrPd₂As₂ < BaPd₂As₂, i.e. in the reverse sequence relative to the transition temperatures T _C. Thus, the change in T _C cannot be explained by the electronic factor, i.e. by the simple correlation T _C～N(E _F). Most likely the decrease in T _C in the sequence CaPd₂As₂ → SrPd₂As₂ and the absence of a superconducting transition in BaPd₂As₂ are related to the structural factors and the peculiarities of the electron–phonon coupling mechanism.     

Investigation of Instability of Lattice of Bi_2Sr_2CaCu_2O_x

Bi2Sr2CaCu2Ox superconductor was studied by differential scanning calorimetry (DSC) and thermogravimetry (TG) in different atmospheres. It is discovered that there is a thermal anomaly in the DSC curve, associated with a weight loss in the TG curve before the melting of the sample. Careful thermal analysis and high temperature X-ray diffraction reveal that the thermal anomaly and the weight loss show an instability of the crystalline Iattice. By annealing the sample in oxygen and argon, respectively and then by TC measurement and thermal analysis, the coincidence of transition temperature with the instability is found. The coincidence is further confirmed by Y-doped 2212 phase.     

Thermal conductivity of the system N2O4 ⇄ 2NO2 ⇄ 2NO + O2

Experimental data on the thermal conductivity of dissociating nitrogen tetroxide have been obtained by the hot-wire method in the temperature range from 290 to 870° K at pressures up to 10⁵ N/m².