聚苯胺/不锈钢双极板在H2SO4中腐蚀性能的变化规律

目的提高质子交换膜燃料电池(PEMFC)双极板的耐蚀性。方法采用循环伏安法,在316L不锈钢(SS)表面电合成导电聚苯胺(PANI)膜,制备PANI/316L SS复合双极板。用红外光谱确定PANI官能团结构,用扫描电镜观察表面形貌,用X射线光电子能谱研究PANI膜成分和键合状态。用0.2 mol/L H2SO4模拟PEMFC腐蚀环境,采用极化曲线研究PANI/316LSS耐腐蚀性能,采用开路电位(OCP)和电化学阻抗谱(EIS),研究PANI/316L SS在长期浸泡过程中的腐蚀行为的变化规律。结果 PANI膜具有中间氧化态结构,呈现纤维堆积形貌。XPS结果表明,PANI膜中含有C、N、S和O等元素,聚合过程中"对阴离子"SO42-通过"掺杂"进入PANI分子链。涂覆PANI薄膜的316L SS腐蚀电位提高了0.17 V,长期浸泡过程中,OCP介于0.19～0.32 V之间,说明PANI/316L SS的腐蚀倾向降低。浸泡初期,OCP增大对应于膜/基界面处钝化膜的形成;浸泡中期,OCP下降/上升与钝化膜的溶解/修复有关;浸泡后期,OCP持续下降源于钝化膜的溶解。EIS的Nyquist图由高频端容抗弧和低频端扩散尾构成。结论随着浸泡时间延长,PANI膜被氧化,导致"对阴离子"SO_4~(2-)从PANI中发生"脱掺杂",使膜电阻增加,容抗弧半径增大。浸泡82天,PANI/316L SS体系仍具有良好的耐腐蚀性能。     

电位对聚苯胺/不锈钢双极板腐蚀性能的影响

目的 增强双极板在质子交换膜燃料电池(PEMFC)工作条件下的耐腐蚀性能.方法 以1-乙基-3-甲基咪唑硫酸乙酯(EMIES)离子液体作为聚合反应电解质,采用循环伏安法在316L不锈钢(SS)上电聚合聚苯胺(PANI)薄膜制备PANI/316L SS双极板.采用SEM观察表面形貌,采用FTIR分析官能团结构,采用XPS分析元素组成和键合状态.采用恒电位法控制PANI/316L SS电位分别为0.5、0.6、0.7 V(vs.SCE)以模拟PEMFC阴极电位,测量恒电位极化后开路电位、极化曲线和电化学阻抗谱(EIS)的变化.结果 PANI膜均匀平整局部有微裂纹.FTIR显示有苯环、醌环、S=O和—COOH伸缩振动.XPS表明PANI膜含有C、N、O和S等元素.PANI/316L SS极化曲线在钝化区内电流密度波动较大,EIS的Nyquist图由高频容抗弧和低频直线构成,容抗弧半径随着极化电位的升高而增大.结论 PANI为中间氧化态结构,EMIES阴离子(CH3CH2SO4–)和草酸阴离子(HOOC-COO–)在PANI分子链中均有掺杂.在PEMFC阴极工作电位下PANI/316L SS处于阳极极化状态,电位对PANI/316L SS的耐蚀性影响显著,在0.6 V下PANI/316L SS呈现很好的耐蚀性,电位升高至0.7 V时,发生PANI过度氧化,导致"对阴离子"脱掺杂,使PANI/316L SS的导电性和耐蚀性下降.     

阴极气体O2对石墨烯/聚苯胺/不锈钢双极板耐蚀性的影响

目的 提高质子交换膜燃料电池(PEMFC)双极板的耐腐蚀性能。方法 采用循环伏安法(CV)在316L不锈钢(SS)基材上制备还原氧化石墨烯(rGO)/聚苯胺(PANI)层-层复合双极板。用透射电镜(TEM)和扫描电镜(SEM)进行形貌观察,用红外光谱(FTIR)和拉曼光谱(Raman)确定官能团结构,用紫外可见光谱(UV-vis)确定分子共轭状态,用X射线光电子能谱(XPS)确定化学成分和键合状态。在模拟PEMFC阴极工作环境下研究rGO/PANI/316L SS层-层复合双极板的耐腐蚀性能,向体系中通入氧气(O₂),测量开路电位(OCP)、电化学阻抗谱(EIS)和极化曲线评价双极板的抗腐蚀性能。结果 在离子液体1-乙基-3-甲基咪唑硫酸甲酯中,通过电聚合能够获得厚度为53μm的PANI膜层,在pH=4的0.03 mol/L K₂SO₄溶液中还原氧化石墨烯(GO),在PANI上获得厚度为10μm的rGO膜层。PANI呈中间氧化态,sp2杂化的r GO和PANI之间的相互作用使得共轭效应增强。连续致密的rGO覆盖在多孔的P...     

阳极反应气氛氢气对聚苯胺/不锈钢耐蚀性的影响

目的 为了提高双极板在质子交换膜燃料电池(PEMFC)工作环境下的耐蚀性.方法 在1-乙基-3-甲基咪唑磷酸二乙酯盐([EMIM][DEP])离子液体中,在316 L不锈钢(SS)基体上电聚合聚苯胺(PANI)膜.用红外光谱(FTIR)、拉曼光谱(Raman)、X射线光电子能谱(XPS)和扫描电子显微镜(SEM)进行微...     

基体偏压对316L不锈钢表面多层Ti-DLC薄膜摩擦及腐蚀行为的影响

在严苛海洋环境下,传统单一的Ti掺杂类金刚石薄膜（DLC）无法满足减摩耐磨及耐腐蚀性能的要求,仍须进一步探索。为促进DLC薄膜在严苛海洋环境下的应用,采用中频磁控溅射技术在316L不锈钢上制备Ti/TiN/TiCN/Ti-DLC复合薄膜。通过SEM、拉曼光谱、XPS、纳米压痕测试、摩擦磨损试验及电化学测试等方法,重点研究基体偏压对薄膜结构、力学性能、摩擦性能及耐腐蚀性能的影响规律。结果显示：随着基体偏压从-60V到-120V,薄膜中sp3-C/sp2-C比值逐渐增大,薄膜硬度及弹性模量逐渐增大;薄膜结合力呈现先增大后减小的趋势,在-80 V时达到最大24.5 N;在7 N的法向载荷下,薄膜磨损失效时间先增大后减小,偏压为-80 V时磨损寿命最长;316L不锈钢和所有薄膜的阳极极化曲线都表现出明显的钝化现象,在偏压为-120V时,薄膜的维钝电流密度比316L不锈钢低两个数量级,表现出优异的耐蚀性;薄膜电阻Rf和电荷转移电阻Rct逐渐增大,薄膜的耐腐蚀性能逐渐增强。Ti/TiN/TiCN/Ti-DLC复合薄膜的多层结构和元素掺杂相结合的设计有效提高了316L不锈钢的耐腐蚀性能和减摩耐磨性能...     

电化学蚀刻-掺杂316L不锈钢制备PEMFC双极板

目的 研究在0.5 mol/L KNO3和0.1 mol/L HNO3混合溶液中,电极电位对316L不锈钢(316LSS)表层微观形貌、化学组成、耐腐蚀性能和界面接触电阻的影响,以解决316LSS双极板在质子交换膜燃料电池中服役时腐蚀和表面接触电阻较大的问题.方法 借助于电化学交流阻抗、循环伏安、计时电流和动电位极化测试,对316LSS表面发生的电化学反应及改性后性能进行研究.利用电化学工作站、扫描电镜及X射线光电子能谱分析仪,对316LSS的耐腐蚀性能、微观形貌及化合价进行表征,并测量界面接触电阻和反应后溶液中铁铬金属离子浓度进行测量.结果 在0.5 mol/L KNO3+0.1 mol/L HNO3的混合溶液中,316LSS表面发生的反应为不可逆过程,当改性电位为–0.5 V(vs.SCE)时,交流阻抗低频区出现了代表物质吸附的感抗弧,电位负移到–0.6 V(vs.SCE)和–0.7 V(vs.SCE)时,表面发生点腐蚀和晶界腐蚀,膜层的完整性被破坏.最佳电位–0.5 V(vs.SCE)改性后316LSS表面出现凸起结构,表层元素分析发现关键合金元素铬主要以氧化铬和氮化铬形式存在,–0.5 V(vs.SCE)对应的氮化铬占比达54.8％.在140 N/cm2的压力下界面接触电阻与施加电位呈现抛物线关系,最小电阻值为8.7 m?·cm2(–0.5 V(vs.SCE)).改性后的316LSS耐腐蚀性能显著提升,最佳样品的腐蚀电流密度和腐蚀电位分别为0.065μA/cm2和136.738 mV,在模拟燃料电池中运行650 h时,腐蚀电流密度为3.4μA/cm2.结论 电化学改性316LSS的物理化学性能与施加电位大小密切相关.由于316LSS表层钝化膜在电化学反应过程中发生选择性溶解以及原位氮掺杂,促使钝化膜厚度减薄,掺杂氮元素稳定了膜层结构和提高了导电性能,消除了钝化膜对双极板性能的不利影响.最佳改性电位下316LSS表面发生选择性蚀刻形成致密的凸起状氮掺杂膜层,改善了316L不锈钢双极板综合性能.     

原位聚合聚苯胺改性NiFe-LDH复合涂层的防护性能研究

采用水热法结合原位化学氧化法在304不锈钢表面制备了不同种类NiFe-LDH (层状双氢氧化物)/聚苯胺(PANI)复合涂层。利用SEM、EDS能谱分析、XRD、FT-IR和XPS,对不同LDH的表面形貌和结构进行分析。采用极化曲线和电化学阻抗谱研究了涂层对基底的防蚀性能,并对其耐腐蚀机理进行探讨。结果表明,添加Fe(NO₃)₃得到层状结构的LDH,采用PANI改性可进一步优化LDH的表面结构。PANI和LDH之间存在化学键的结合,二者协同作用提升复合涂层的综合性能。在168 h浸泡期间,NiFe-LDH/PANI复合涂层在1 mol/L H2SO4溶液中具有良好的化学稳定性,为304不锈钢提供优良的物理屏蔽和阳极氧化保护作用。     

磁控溅射CrNx薄膜的接触电阻及其耐腐蚀性能

采用磁控溅射工艺,在304不锈钢表面沉积CrNx薄膜。采用扫描电子显微镜(SEM)和场发射扫描电子显微镜(FESEM)观察薄膜形貌,采用能谱仪(EDS)和X射线光电子能谱(XPS)分析薄膜的元素组成和化学价态;测试了其接触电阻及耐腐蚀性能。结果表明:薄膜以柱状晶方式生长,主要由Cr2N和Cr组成;在质子交换膜燃料电池电堆的组装力范围内接触电阻降低明显;在模拟电池环境腐蚀溶液中腐蚀电流降低明显,耐腐蚀性能显著增强。     

Cu的腐蚀与缓蚀的光电化学研究

用光电化学方法研究了Cu在不同浓度NaCl的硼酸-硼砂溶液中的腐蚀以及缓蚀剂聚天冬氨酸(PASP)对Cu的缓蚀作用.Cu在硼酸-硼砂缓冲溶液中,表面的Cu2O膜为P型半导体.当Cu所在的溶液中存在少量NaCl(小于0.5 g/L)时,Cu表面Cu2O膜会受轻微Cl-掺杂但小会改变半导体性质;当溶液中存在较多NaCl(0.5-15 g/L)时,Cu2O膜会受Cl-较严重的侵蚀,Cl-掺杂使Cu2O膜部分转成n型;当溶液中存在大量NaCl(大于15 g/L)时,Cu2O膜完全被Cl-掺杂而转型成n型.缓蚀剂PASP的加入能够对Cu起到缓蚀作用;当NaCl浓度为2 g/L时,PASP与溶液中的Cl-在Cu表面竞争吸附,明显抑制了Cl-对Cu2O膜的掺杂,Cu2O受到了保护仍为P型;在NaCl浓度为30 g/L时,PASP与Cl-竞争吸附只能削弱Cl-对Cu2O膜的掺杂,Cu2O膜仍受Cl-掺杂而转成n型,但n型性质变弱.对Cu2O膜性质的Mott-Schottky测试结果与光电化学结果一致.     

Photoelectrochemical Study of the Corrosion and Inhibition on Copper

用光电化学方法研究了Cu在不同浓度NaCl的硼酸--硼砂溶液中的腐蚀以及缓蚀剂聚天冬氨酸(PASP)对Cu的缓蚀作用. Cu在硼酸--硼砂缓冲溶液中, 表面的Cu2O膜为p型半导体. 当Cu所在的溶液中存在少量NaCl (小于0.5 g/L)时, Cu表面Cu2O膜会受轻微Cl-掺杂但不会改变半导体性质; 当溶液中存在较多NaCl (0.5-15 g/L)时, Cu2O膜会受Cl-较严重的侵蚀, Cl-掺杂使Cu2O膜部分转成n型; 当溶液中存在大量NaCl (大于15 g/L)时, Cu$_{2}$O膜完全被Cl-掺杂而转型成n型. 缓蚀剂PASP的加入能够对Cu起到缓蚀作用：当NaCl浓度为2 g/L时, PASP与溶液中的Cl-在Cu表面竞争吸附, 明显抑制了Cl-对Cu2O膜的掺杂, Cu2O受到了保护仍为p型; 在NaCl浓度为30 g/L时, PASP与Cl-竞争吸附只能削弱Cl-对Cu2O膜的掺杂, Cu2O膜仍受Cl-掺杂而转成n型, 但n型性质变弱. 对Cu2O膜性质的Mott-Schottky测试结果与光电化学结果一致.     

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.     

The Mirror with Patterns of Auspicious Animals and Grapes——Exquisite cast mirror and the technology of surface tin-enrichment by rubbing-in and infiltration of tin-rich powder

<正>Bronze mirrors were used by the Chinese people before the introduction of the glass mirror.Only after it was replaced by the glass mirror did the bronze mirror gradually retreat from people's lives.Different styles of bronze mirrors were made in different historical periods,particularly in the Warring States Period,the Han and Tang Dynasties,which were the three peaks of the development of bronze mirror arts in ancient China.The casting techniques were exquisite.The surface of the bronze mirror was smooth and bright enough to reflect one's image,and there were scarcely any casting defects on the mirror surface.On the back of the bronze mirror,there were rich depictions of Arts and Humanities,and the ornamentations were also