NiCr涂层结构对Nb-1Zr合金抗氧化性能的影响

为提高Nb-1Zr合金基体在600℃大气环境下的抗氧化性能,采用等离子增强电弧离子镀技术在Nb-1Zr合金表面低于300℃下实现不同复合结构的NiCr涂层。利用恒温氧化表征了涂层在600℃、500 h大气环境下的抗氧化性能,揭示了不同复合结构涂层失效以及抗氧化机理。结果表明,单一NiCr涂层中存在的大量"微孔"结构缺陷相互连通构成了氧元素进入基体的扩散通道,界面处基体首先发生氧化,生成以Nb_2O_5为主的粉末状氧化产物。随着氧化时间的延长,氧化产物逐渐增多,体积逐渐膨胀,造成表面鼓泡直至破裂失效。采用NiCr多层复合结构能够显著降低涂层中形成"贯穿孔"的几率,但并未改变涂层的失效方式。而基体与NiCr层之间引入Cr过渡层,能够在界面处与扩散进入的氧首先反应生成致密的Cr_2O_3层,阻碍氧向基体的进一步扩散,且随着氧化时间的延长,涂层中的Cr向表面的扩散使得其表面相应形成一层致密的Cr_2O_3层,双层致密氧化膜的形成确保了基体抗氧化性能的提高。结果显示,Cr/NiCr多层复合结构涂层能够使Nb-1Zr合金在600℃大气环境下的抗氧化时间延长至500 h,氧化增重率仅有0.08g·(m~2·h)~(-1)。     

涂层厚度对Cr涂层锆合金包壳高温蒸汽氧化动力学及微观机制的影响

目的 研究涂层厚度对Cr涂层锆包壳高温蒸汽氧化行为的影响规律及其微观机制,为耐事故锆包壳表面涂层优化设计提供理论依据。方法 以锆合金包壳为基体材料,采用磁控溅射工艺制备纯金属Cr涂层,目标厚度设计值为10、15、20 μm 3类。采用高温蒸汽氧化设备开展试验,氧化温度为1 200 ℃,等温氧化时间为500~3 000 s,系统研究模拟反应堆失水事故(LOCA)工况下涂层厚度对该材料体系高温蒸汽氧化行为及氧化动力学的影响。试验后,通过X射线衍射仪、场发射扫描电子显微镜及能谱仪等表征各样品氧化膜微结构特征、氧化层厚度、元素分布及物相组成等,基于氧化膜层厚度构建Cr涂层氧化动力学模型,同步探讨涂层原始厚度对其高温蒸汽氧化-失效微观机理的影响。结果 涂层厚度为10 μm时,其对锆合金基体保护作用有限,等温氧化2 000 s时其表面Cr2O3氧化膜和残余Cr涂层已完全丧失保护功能,锆合金基体被连续氧化。涂层厚度为15 μm时,第一阶段,生成保护性能较好的Cr2O3氧化膜,Cr涂层的氧化行为满足抛物线规律;第二阶段,Cr涂层的氧化行为发生转变,氧化膜及其残余涂层保护性能衰退,但锆合金基体始终未被氧化。涂层厚度为20 μm时,Cr涂层的氧化行为满足抛物线规律,但氧化行为未发生转变,表面氧化膜及残余Cr涂层保护性能较好。结论 Cr涂层厚度增加可在一定程度上提升其抗高温蒸汽氧化性能,进而提高反应堆事故工况下燃料包壳抵御事故的能力,从而在一定程度上延长不干预时间。     

电弧离子镀制备耐事故包壳材料厚Cr涂层及高温抗氧化性能

目的在Zr-4包壳材料表面制备具有耐事故高温性能的抗氧化厚Cr涂层,保护Zr基体,以防止与高温水蒸汽反应。方法采用自主研发的φ155 mm大弧源电弧离子镀技术在Zr-4合金表面制备约20μm的Cr涂层,通过X射线衍射仪(XRD)分析氧化前后的物相变化,通过扫描电子显微镜(SEM)和电子探针(EPMA)研究厚Cr涂层在不同温度下产生的多种缺陷,探究厚Cr涂层对Zr基体的防护机制。结果当涂层沉积速率3μm/h,制备的Cr涂层均匀致密,结合力优异,具有柱状晶结构,可经受至少15.8%的形变量,其抗塑性形变能力优异。沉积Cr层样品经过1000、1100、1200℃氧化,保温1h后快速冷却至室温,厚Cr涂层分化为Cr Ox层、Cr_2O_3层、残余Cr层和Cr-Zr扩散层。经受苛刻条件(1200℃/3600 s)测试,除保持连续性的氧化层外,在基体上仍残余良好结合的6.8μm Cr层。氧化层两次开裂阻止基体被进一步破坏。Cr-Zr扩散层是由Zr元素向Cr涂层方向渗透生长的。1200℃时,在基体近表面处产生的大尺寸隆起,是由于在近表面处韧性β-Zr(O)相转变为脆性α-Zr相,以及Cr偏聚贫Sn造成的。残余Cr层的柱状晶结构会形成Zr-O扩散通道,对涂层最后失效将起关键作用。结论 Zr合金包壳材料镀覆20μm的Cr涂层具有充分的耐事故能力,在严苛的事故条件测试下,各缺陷均未能使Zr-4合金基体暴露,涂层能够形成有效壁垒,防止锆合金基体暴露造成核事故,阻止基体进一步被破坏。     

锆合金表面Mo/Al/Cr复合涂层的抗高温水蒸气氧化性能

锆合金是重要的核燃料包壳材料,在包壳表面沉积抗高温水蒸气氧化涂层是在失水事故中避免核泄漏的有效途径,然而涂层在高温氧化过程中存在氧化产物不稳定及界面扩散问题。用磁控溅射的方法在Zr-4合金表面沉积Mo/Al/Cr复合涂层,拟利用Al层生成氧化铝提升抗氧化温度上限,利用Mo层阻挡Al与Zr-4基体的扩散。用SEM表征涂层的表面及横截面形貌,利用XRD分析涂层物相结构,用纳米压痕的方法评价涂层的力学性能,用管式炉连接水蒸气发生器来评价涂层的抗高温水蒸气氧化性能。结果表明：在锆合金表面制备的Mo/Al/Cr复合涂层与基体结合良好,结构完整,界面清晰,硬度高于Zr-4合金基体。在高温水蒸气氧化试验中,复合涂层中的Al会发生熔融,导致涂层结构的破坏而不能生成连续致密氧化铝膜。在Cr层、Al层失效的情况下,Mo层可以有效阻挡Al及O元素向基体内部扩散。探讨了Al作为抗氧化层及Mo作为扩散阻挡层的可行性,试验结果可为核燃料包壳涂层的设计选材提供借鉴和支撑。     

磁控溅射沉积CrAlN涂层抗高温氧化性能研究

采用非平衡磁控溅射技术在M2工具钢表面沉积Cr Al N涂层,利用SEM、EDS、XRD、纳米压痕仪研究了Cr Al N涂层不同温度氧化后的表面和截面形貌、成分、相结构、硬度和弹性模量。结果表明,Cr Al N涂层在高温环境下氧化生成的Al_2O_3和Cr_2O_3致密氧化层可以有效阻止氧进一步向内扩散,涂层在900℃氧化2 h后的氧化层深度仅0.2μm。Cr Al N涂层900℃氧化后仍基本保持氧化前的力学性能。     

微晶化对Ni20Cr合金热生长氧化膜应力的影响

利用氧化膜应力原位测量装置对Ni20Cr微晶涂层/合金体系在1000℃空气中氧化过程中发生的弯曲挠度变化进行测量.结果表明,微晶涂层1000℃氧化所形成的Cr_2O_3氧化膜中存在压应力,应力绝对值高于相同厚度的合金表面的热生长氧化膜,其原因在于涂层/Cr_2O_3界面结合好,应力释放较小.降温冷却过程中,通过微晶涂层...     

Cr涂层锆合金包壳高温蒸汽氧化动力学及微观机理研究

Cr涂层锆合金包壳具备抗高温蒸汽氧化性能优异、耐腐蚀和耐磨蚀性能良好、工程应用难度较小等特点,成为最具前景的近期型事故容错燃料候选材料之一。本工作以Zr-1Nb合金管为基体材料,采用磁控溅射工艺制备均匀致密Cr涂层,涂层厚度范围12～15μm。通过同步综合热分析仪开展双面高温蒸汽氧化试验,氧化温度为1000、1100和1200℃,氧化时间为300～5000s,系统研究反应堆事故工况下Cr涂层锆合金包壳高温蒸汽氧化行为。采用扫描电子显微镜、能谱仪和X射线衍射仪表征高温氧化产物膜微观形貌特征、氧化层厚度、元素分布以及物相组成等,建立Cr涂层氧化动力学模型,探讨高温氧化机理。研究表明,高温蒸汽环境中,Cr涂层锆合金包壳外壁形成致密Cr2O3层,有效阻止O元素扩散至Zr合金基体,从而提升复合包壳的耐高温性能。其次,Cr涂层高温蒸汽氧化动力学曲线遵循抛物线规律,氧化速率常数比锆合金低大约2个数量级,显著提升锆合金包壳抗高温蒸汽氧化性能。     

热处理对S30432喷丸不锈钢抗高温水蒸汽氧化性能的影响

将S30432钢喷丸样品进行不同温度热处理,研究样品620℃下在90%H_2O+10%Ar气氛中的氧化行为。采用光学显微镜(OM)观察喷丸形变层组织形貌;通过测量不同时间氧化膜厚度,获得氧化动力学曲线;利用X射线衍射仪(XRD)、扫描电镜(SEM)及能谱仪(EDS)等对氧化产物成分、形貌及结构进行分析。结果表明:热处理过程中S30432钢喷丸样品形变层组织形貌无明显变化;氧化过程中,样品喷丸形变层内晶粒发生再结晶长大;氧化2000 h后,样品喷丸形变层内晶粒尺寸及碎化晶层厚度基本相同。不同温度热处理的S30432钢喷丸样品在高温水蒸汽中均生成由Cr_2O_3、(Fe,Cr)_2O_3、FeCr_2O_4以及少量Fe_3O_4和Fe_2O_3组成的富Cr氧化物薄膜。730～800℃热处理对S30432喷丸不锈钢抗高温水蒸汽氧化性能无明显影响。     

Cr_3C_2-NiCr涂层的高温抗氧化和耐热腐蚀性能

采用大气等离子喷涂技术制备Cr_3C_2-NiCr复合涂层,并对制备的Cr_3C_2-Ni Cr涂层试样进行800℃×100 h氧化和熔盐(Na_2SO_4+25wt%NaCl)热腐蚀试验。利用X射线衍射仪(XRD)和带能谱的扫描电镜(SEM/EDX)分析氧化、腐蚀涂层表面和截面的成分及结构变化,探讨其高温氧化、腐蚀机理。结果表明:等离子喷涂Cr_3C_2-Ni Cr涂层具有层状组织结构,喷涂过程中无明显相分解或氧化。高温氧化后的Cr_3C_2-NiCr涂层表面及层片界面形成了连续、致密的Cr_2O_3保护膜,涂层表现出优异的抗高温氧化性能。在热腐蚀过程中,腐蚀盐破坏了涂层表面及层片界面形成的氧化膜,腐蚀性元素沿着涂层中的孔洞及层片界面扩散到涂层内部,涂层发生"活化氧化",耐腐蚀性较差。     

锆合金表面CrAl基耐高温涂层及氧化行为研究

目的了解锆合金和涂层的高温氧化行为,通过表面涂层提升锆合金的耐高温氧化性能。方法采用多弧离子镀技术在锆合金基体上制备了CrAlN、CrTiAlN涂层,模拟反应堆失水(LOCA)事故时的高温氧化行为,在360～1160℃下进行1 h氧化测试,对原始锆合金和带涂层样品的氧化增重行为进行了研究。通过X射线衍射和扫描电子显微镜对氧化前后样品的物相结构和形貌进行系统表征分析。结果锆合金在760℃及以下形成深色的混合型锆氧化膜,在860℃以上呈现龟裂和局部剥落。两种涂层氧化时,通过形成致密的Cr_2O_3和Al_2O_3混合氧化层,显著降低了氧化增重。CrAlN涂层在760℃时具有较好的抗氧化性,1060℃时开裂而失去保护作用。CrTiAlN涂层在860℃时能保护基体不受氧化,1060℃时局部开裂,基体开始出现氧化层。结论利用多弧离子镀技术制备的锆合金表面CrAlN和CrTiAlN涂层,在模拟反应堆LOCA事故下具有良好的耐高温氧化性,显示出这两种涂层有潜力发展成为核用事故容错燃料(ATF)包壳涂层。     

Effects of Post-weld Heat Treatment on Microstructure,Mechanical Properties and the Role of Weld Reinforcement in 2219 Aluminum Alloy TIG-Welded Joints

In as-welded state, each region of 2219 aluminum alloy TIG-welded joint shows diff erent microstructure and microhardness due to the diff erent welding heat cycles and the resulting evolution of second phases. After the post-weld heat treatment, both the amount and the size of the eutectic structure or θ phases decreased. Correspondingly, both the Cu content in α-Al matrix and the microhardness increased to a similar level in each region of the joint, and the tensile strength of the entire joint was greatly improved. Post-weld heat treatment played the role of solid solution strengthening and aging strengthening. After the post-weld heat treatment, the weld performance became similar to other regions, but weld reinforcements lost their reinforcing eff ect on the weld and their existence was more of an adverse eff ect. The joint without weld reinforcements after the post-weld heat treatment had the optimal tensile properties, and the specimens randomly crack in the weld zone.     

The First Phase of the SRIF Industrialized Base in ＂West Area＂ Has Been Put into Operation

After nearly two years＇ tense construction, the first phase of industrialized base of Shenyang Research Institute of Foundry （SRIF）, located at the Tiexi Casting and Forging Industrial Park in the west of Tiexi District, has now been completed and formally put into operation.     

Thermodynamics Study on the Decomposition of Chromite with KOH

Institute of Process Engineering, Chinese Academy of Sciences, China, has proposed a method for oxidative leaching of chromite with potassium hydroxide. Understanding the mechanism of chromite decomposition, especially in the potassium hydroxide fusion, is important for the optimization of the operating parameters of the oxidative leaching process. A traditional thermodynamic method is proposed and the thermal decomposition and the reaction decomposition during the oxidative leaching of chromite with KOH and oxygen is discussed, which suggests that chromite is mainly destroyed by reactions with KOH and oxygen. Meanwhile, equilibrium of the main reactions of the above process was calculated at different temperatures and oxygen partial pressures. The stable zones of productions, namely, K2CrO4 and Fe2O3, increase with the decrease of temperature, which indicates that higher temperature is not beneficial to thermodynamic reactions. In addition, a comparison of the general alkali methods is carried out, and it is concluded that the KOH leaching process is thermodynamically superior to the conventional chromate production process.     

Influence of Heat Treatment on Damping Behaviour of the Magnesium Wrought Alloy AZ61

The effect of isochronal heat treatments for 1h on variation of damping, hardness and microstructural change of the magnesium wrought alloy AZ61 was investigated. Damping and hardness behaviour could be attributed to the evolution of precipitation process. The influence of precipitation on damping behaviour was explained in the framework of the dislocation string model of Granato and Lücke.     

Effect of Rare Earth Doping on Impedance,Modulus and Conductivity Properties of Multiferroic Composites:0.5(BiLa_xFe_(1-x)O_3)–0.5(PbTiO_3)

The Lanthanum-doped bismuth ferrite–lead titanate compositions of 0.5(Bi LaxFe1-xO3)–0.5(Pb Ti O3)(x = 0.05,0.10,0.15,0.20)(BLxF1-x-PT) were prepared by mixed oxide method.Structural characterization was performed by X-ray diffraction and shows a tetragonal structure at room temperature.The lattice parameter c/a ratio decreases with increasing of La(x = 0.05–0.20) concentration of the composites.The effect of charge carrier/ion hopping mechanism,conductivity,relaxation process and impedance parameters was studied using an impedance analyzer in a wide frequency range(102–106Hz) at different temperatures.The nature of Nyquist plot confirms the presence of bulk effects only,and non-Debye type of relaxation processes occurs in the composites.The electrical modulus exhibits an important role of the hopping mechanism in the electrical transport process of the materials.The ac conductivity and dc conductivity of the materials were studied,and the activation energy found to be 0.81,0.77,0.76 and 0.74 e V for all compositions of x = 0.05–0.20 at different temperatures(200–300 °C).     

Quantitative Analysis of the Crystallographic Orientation Relationship Between the Martensite and Austenite in Quenching–Partitioning–Tempering Steels

The orientation relationships(ORs)between the martensite and the retained austenite in low-and medium-carbon steels after quenching–partitioning–tempering process were studied in this work.The ORs in the studied steels are identified by selected-area electron diffraction(SAED)as either K–S or N–W ORs.Meanwhile,the ORs were also studied based on numerical fitting of electron backscatter diffraction data method suggested by Miyamoto.The simulated K–S and N–W ORs in the low-index directions generally do not well coincide with the experimental pole figure,which may be attributed to both the orientation spread from the ideal variant orientations and high symmetry of the low-index directions.However,the simulated results coincide well with experimental pole figures in the high-index directions{123}_(bcc).A modified method with simplicity based on Miyamoto’s work was proposed.The results indicate that the ORs determined by modified method are similar to those determined by Miyamoto’method,that is,the OR is near K–S OR for the low-carbon Q–P–T steel,and with the increase of carbon content,the OR is closer to N–W OR in medium-carbon Q–P–T steel.     

Using Finite Element and Contour Method to Evaluate Residual Stress in Thick Ti-6Al-4V Alloy Welded by Electron Beam Welding

This work was to reveal the residual stress profile in electron beam welded Ti-6Al-4V alloy plates(50 mm thick) by using finite element and contour measurement methods.A three-dimensional finite element model of 50-mmthick titanium component was proposed,in which a column–cone combined heat source model was used to simulate the temperature field and a thermo-elastic–plastic model to analyze residual stress in a weld joint based on ABAQUS software.Considering the uncertainty of welding simulation,the computation was calibrated by experimental data of contour measurement method.Both test and simulated results show that residual stresses on the surface and inside the weld zone are significantly different and present a narrow and large gradient feature in the weld joint.The peak tensile stress exceeds the yield strength of base materials inside weld,which are distinctly different from residual stress of the thin Ti-6Al-4V alloy plates presented in references before.     

Microstructures and Tensile Properties of Ultrafine-Grained Ni–(1–3.5) wt% SiC_(NP) Composites Prepared by a Powder Metallurgy Route

Silicon carbide nanoparticle-reinforced nickel-based composites(Ni–Si CNP),with a Si CNPcontent ranged from1 to 3.5 wt%,were prepared using mechanical alloying and spark plasma sintering.In addition,unreinforced pure nickel samples were also prepared for comparative purposes.To characterize the microstructural properties of both the unreinforced pure nickel and the Ni–Si CNPcomposites transmission electron microscopy(TEM) was used,while their mechanical behavior was investigated using the Vickers pyramid method for hardness measurements and a universal tensile testing machine for tensile tests.TEM results showed an array of dislocation lines decorated in the sintered pure nickel sample,whereas,for the Ni–Si CNPcomposites,the presence of nano-dispersed Si CNPand twinning crystals was observed.These homogeneously distributed Si CNPwere found located either within the matrix,between twins or on grain boundaries.For the Ni–Si CNPcomposites,coerced coarsening of the Si CNPassembly occurred with increasing Si CNPcontent.Furthermore,the grain sizes of the Ni–Si CNPcomposites were much finer than that of the unreinforced pure nickel,which was considered to be due to the composite ball milling process.In all cases,the Ni–Si CNPcomposites showed higher strengths and hardness values than the unreinforced pure nickel,likely due to a combination of dispersion strengthening(Orowan effects) and particle strengthening(Hall–Petch effects).For the Ni–Si CNPcomposites,the strength increased initially and then decreased as a function of Si CNPcontent,whereas their elongation percentages decreased linearly.Compared to all materials tested,the Ni–Si CNPcomposite containing 1.5% Si C was found more superior considering both their strength and plastic properties.     

Directional Growth of Tin Crystals Controlled by Combined Solute Concentration Gradient Field and Static Magnetic Field

A new method was introduced to achieve directional growth of Sn crystals. Microstructures in liquid(Pb)/liquid(Sn) diffusion couples were investigated under various static magnetic fields. Results show that the β-Sn crystals mainly reveal an irregular dendritic morphology without or with a relatively low static magnetic field(B0.3 T). When the magnetic field is increased to 0.5 T, the β-Sn dendrites close to the final stage of growth begin to show some directional character. With a further increase in the magnetic field to a higher level(0.8–5 T), the β-Sn dendrites have an enhanced directional growth character, but the dendrites show a certain deflection. As the magnetic field is increased to 12 T, the directional growth of the β-Sn dendrites in the center of the couple is severely destroyed. The mechanism of the directional growth of the β-Sn crystals and the deflection of the β-Sn crystals with the application of static magnetic field was tentatively discussed.     

电化学噪声数据处理方法概述

综述了常见的电化学噪声数据处理方法,介绍了直流趋势剔除、统计分析、快速傅立叶变换(FFT)法计算功率谱密度(PSD)以及小波变换处理电化学噪声信号的基本过程,并阐释了各种数学处理及所得参数的物理意义。