铝基水滑石涂层腐蚀行为的电化学噪声特征

采用电化学噪声技术监测了铝基水滑石涂层在3.5%NaCl溶液中的腐蚀行为。通过电化学噪声的时域谱分析、时域统计参数分析、频域分析以及形貌特征分析,对电极的腐蚀过程进行了研究。结果表明,涂层的点蚀发展过程可以分为4个阶段:钝态期,噪声波动较小,各参数比较平稳;亚稳态点蚀核形成期,噪声出现波动,σV、σI、W、k、fc增大,Rn减小;稳态点蚀发展期,电位噪声出现快速下降缓慢上升的典型特征,各参数趋于极值,Li(局部化噪声指数)接近于1;点蚀发展后期,噪声波动减弱,各参数值也趋于减弱。     

静水压力对超纯Fe腐蚀行为的影响

采用失重测试、动电位极化和电化学噪声研究了静水压力对超纯Fe在3.5%NaCl中腐蚀行为的影响。利用离散小波分析方法去除噪声信号的直流漂移,然后进行散粒噪声和随机分析;利用Hilbert-Huang变换对噪声信号进行时频分析;用SEM观察腐蚀试样的表面形貌。失重测试和动电位极化的研究结果表明,增大静水压力提高了超纯Fe在3.5%NaCl中的腐蚀速率。电化学噪声分析结果表明,在整个浸泡期间,增大静水压力促进了点蚀的发展,提高了局部腐蚀的倾向。在浸泡初期,超纯Fe以发生局部腐蚀(如点蚀形核、亚稳态点蚀、点蚀)的模式为主,增大静水压力对点蚀形核过程有一定的抑制作用,降低了点蚀孕育速率,但对亚稳态点蚀和稳态点蚀的发展过程有促进作用,提高了点蚀生长概率;随着浸泡时间的延长,其逐渐转为以均匀腐蚀的模式为主,增大静水压力仍然促进亚稳态点蚀和稳态点蚀的发展,提高点蚀生长概率,但是却相对地抑制了均匀腐蚀过程。     

304不锈钢点蚀行为的电化学噪声研究

本文利用电化学噪声技术检测了304不锈钢在6．0％（质量分数）FeCl3溶液中的点蚀行为。通过电化学噪声的时、频域分析和电化学噪声信号的统计分析以及相应的腐蚀形貌,研究了蚀点的生长过程。结果表明,浸泡初期噪声电阻Rn在较高水平波动,试样处于钝化状态;浸泡4～14h为点蚀诱导期,Rn开始降低,峭度和不对称度增大,出现明显的噪声峰,试样表面业稳态点蚀形核,生成的亚稳态点再钝化,通过扫描电镜观察未发现蚀点;浸泡14～32h为亚稳态点蚀向稳态点蚀过渡期;浸泡22h后,观察到电位噪声突然下降后不再恢复,功率密度（PSD）图低频区出现白噪声水平,亚稳态蚀点发展成为稳态的蚀点,通过扫描电镜观察到小而浅的蚀点;浸泡32～48h后材料处于稳定的点蚀阶段,通过扫描电镜观察到口径较大且较深的蚀点。     

基于Hilbert-Huang变换的电化学噪声解析及其应用

借助Hilbert-Huang变换 (HHT) 研究了Q345B碳钢在模拟混凝土孔隙液中的电化学噪声信号的时频谱,发现相比离散小波变换 (discretewavelet transform,DWT),HHT在噪声信号识别过程中具有更高的时频分辨率和稳定性,能够从本质上提高对电化学噪声中耦合的亚稳态点蚀信号的解析精度。针对Q345B碳钢处于钝化态、亚稳态点蚀萌发和稳态点蚀生长等不同阶段的噪声特点,提出了一套基于HHT边界谱的腐蚀状态量化指数与腐蚀特征识别方法。借助于在线电化学噪声监测装置,HHT算法将可用于诊断工业环境的腐蚀形态和腐蚀发展趋势。     

16Mn钢局部腐蚀中的电化学噪声特征

通过测量16Mn钢在0.1mol/LCI^- 0.5mol/L HCO3^-溶液中的电化学噪声，发现在点蚀诱导期，亚稳态蚀点的形核速率λ不到0.002s^-1，噪声电流峰平均宽约3～5s，而噪声电位峰却平均宽达200s；在点蚀从亚稳态转变为稳态过程中，λ急剧增加，且电流噪声峰宽度也开始增加，但电位峰宽度却开始减小，随着局部腐蚀进入稳定发展期，噪声中出现了大尺度的波动，且噪声电位峰与电流峰宽度基本相等，但λ却有所下降，宏观点蚀的出现导致噪声电阻Rn迅速下降，并在腐蚀进入稳定发展期后逐渐趋于稳定。     

高纯铝在含Cl~-溶液中电化学噪声的小波包子带能量特征

建立了基于小波包分解的电化学噪声子带能量表征方法 ,测试了高纯铝在含Cl-溶液中不同条件下的电化学噪声 ,分析了所测电化学噪声信号的时域特征、PSD特征及小波包分解子带能量特征 .PSD分析显示 :随着浸泡时间的增加 ,当蚀孔开始生长后 ,孔核的生长期缩短 ,消亡期延长 ,而SO2 -4 对孔核的生长期及消亡期没有显著影响 .与PSD方法相比 ,子带能量特征向量可以刻画电化学噪声信号的高频“指纹”特征 ,对腐蚀体系、腐蚀类型及腐蚀状态有较强的敏感性 .通过对第一子带能量变化分析显示 ,SO2 -4 会降低高纯铝在含Cl-溶液中孔核的发生频数 .     

铝稀土涂层在盐雾加速试验中的腐蚀行为

采用扫描电镜,X射线衍射仪和电化学噪声技术研究了高速电弧喷涂铝稀土涂层在铜加速醋酸盐雾试验中的腐蚀行为,分析了涂层腐蚀前后的形貌及成分,通过电化学噪声谱阐释了涂层的点蚀过程。研究表明:铝稀土涂层的钝化膜在腐蚀介质中容易发生点蚀和破碎,腐蚀后涂层中的孔隙和微裂纹增多,腐蚀过程中钝化膜由亚稳态点蚀逐渐转变为稳态点蚀。     

高纯铝在含Cl^－溶液中电化学噪声的小波包子带能量特征

建立了基于小波包分解的电化学噪声子带能量表征方法，测试了高纯铝在含Cl^-溶液中不同条件下的电化学噪声，分析了所测电化学噪声信号的时域特征、PSD特征及小波包分解子带能量特征．PSD分析显示：随着浸泡时间的增加，当蚀孔开始生长后，孔核的生长期缩短，消亡期延长，而SO4^2-对孔核的生长期及消亡期没有显著影响．与PSD方法相比，子带能量特征向量可以刻画电化学噪声信号的高频“指纹”特征，对腐蚀体系、腐蚀类型及腐蚀状态有较强的敏感性．通过对第一子带能量变化分析显示，SO4^2-会降低高纯铝在含Cl^-溶液中孔核的发生频数．     

电化学噪声技术研究X80钢的点蚀过程

采用电化学噪声(Electrochemical Noise,EN)方法研究了X80管线钢在NaHCO3+NaCl溶液中亚稳态与稳态点蚀特征。结果表明:在含Cl-溶液中,当试样处于点蚀亚稳态,电位与电流噪声具有典型的快速下降或上升,缓慢恢复的暂态峰(Transient)特征,噪声电流峰平均宽约5~10s,而噪声电位峰宽为100s。随着腐蚀时间的延长,亚稳态点蚀噪声峰数量增多,亚稳态点蚀程度加剧;当点蚀由亚稳态发展到稳态初期,电流噪声峰恢复时间变长,与电位噪声峰寿命趋于一致;而随着稳态点蚀的发展,电位与电流峰出现的频率显著增加,电位与电流峰具有很好的相位同步性。     

电化学噪声技术在2205钢点蚀行为研究中的应用

采用电化学噪声技术监测2205钢在0.05mol·L-1 HCl+6%FeCl3溶液中的点腐蚀行为。从电化学噪声的时域和频域分析以及腐蚀形貌观察等方面研究了2205钢的点蚀过程。结果表明:根据电化学噪声时域谱中噪声峰的特征,其点蚀形成过程可大致分为4个阶段。电流标准偏差SI、噪声电阻Rn以及电流功率谱密度曲线倾斜部分的斜率KI均能表征点蚀发展的剧烈程度。     

Electrochemical noise analysis of localized corrosion by wavelet transform

Electrochemical noise (EN) was measured during pitting and stress corrosion tests in NaCl solutions for type 403 stainless steel tempered at 390 °C for 2 h. The EN data were analyzed mainly by wavelet transform in terms of the energy contribution of smooth crystal and detail crystals in three frequency regions. In the early stage of the pitting tests, general corrosion occurs, and contribution of smooth crystal to the total energy was greater than that of low frequency detail crystal, but less with the development of meta-stable pitting. A similar trend was observed in the early stage of stress corrosion cracking (SCC) tests. The contribution of low frequency detail crystals to the total energy decreased as stable pits were formed, and it was less than the energy contribution of smooth crystal when crack propagation occurred in the later stage of SCC. In addition, the contribution of energy of high frequency detail crystal is shown to be indicative of the occurrence of plastic deformation. These results demonstrate that the onset of detailed processes in pitting and SCC can be sensitively detected by wavelet analysis in terms of the energy contribution of smooth crystal and low and high frequency detail crystals, but not with that based on the change in position of peak in energy contribution of detail crystals.     

Interpretation of electrochemical noise by wavelet transform and fractal analysis

Electrochemical noise(EN) was measured during pitting and stress corrosion tests in 3.5 % NaCl solutions for type 403 stainless steel tempered at 520 °C and 610 °C. The energy contributions of smooth crystal and detail crystals in three frequency divisions were analyzed after wavelet transform and compared with the change in the Hurst parameter based on the rescaled range analysis. The contribution of smooth crystal to the total energy is greater than that of low-frequency detail crystal in general corrosion and stable pit formation, but it is less in both meta-stable pitting and growth of stable pits. Crack growth rate can be estimated qualitatively by the evaluation of the energy contributions of smooth and detail crystals, and correlation was found between the change in the Hurst parameter and that in the energy contribution of smooth crystal or one of detail crystals in three frequency divisions.     

光电化学响应分析Ni201在中性溶液中形成表面钝化膜的半导体性质

应用光电化学响应法和:Mott-Schottky曲线法,研究了Ni201在500℃空气中生成的氧化膜和在pH值为8.4的中性缓冲溶液中阳极氧化生成钝化膜的半导体性质,分析了Ni201表面钝化膜的结构和组成.Mott-Schottky曲线表明,Ni20l在该中性溶液中生成钝化膜的平带电位约为0.40 V,其在500℃空气中生成的氧化膜的平带电位约为0.15 V,前者的载流子浓度约是后者的34倍.在中性缓冲溶液中生成钝化膜的光电流谱表明,Ni201的结构由内层NiO和外层Ni（OH）₂构成,其带隙宽度分别为2.8和1.6 eV.其中,具有晶体结构的内层NiO的带隙宽度与Ni201在500℃空气中生成的氧化膜的带隙宽度2.4 eV相似.通过光电化学法和Mott-Schottky曲线建立Ni201表面钝化膜的电子能带结构模型,解释了其内层NiO和外层Ni（OH）₂同是p型半导体组成的钝化膜的半导体性质.     

Synthesis,characterization,and thermostability of bis(2,2,6,6-tetramethyl-3,5-heptanedionato)copper(Ⅱ)

Owing to the adaptability to large scale processing,excellent composition control and film uniformity,the metal-organic chemical vapor deposition(MOCVD)technique is a promising process for high-temperature superconductor YBa2Cu3O7-δ(YBCO)preparation.In this technique,the evaporation characteristics and thermostability of adopted precursors in whole process will decide the quality and reproducible results of YBCO film.In the present report,bis(2,2,6,6-tetramethyl-3,5-heptanedionato)copper(Ⅱ)(Cu(TMHD)2)was synthesized by the interaction of copper acetate hydrate with TMHD in methanol solution,and its structure was identified by FTIR,1H NMR,and EI-MS spectroscopy.Subsequently,thermal property and the kinetics of decomposition were systematically investigated by nonisothermal thermogravimetric analysis methods(TGA)at different heating rates in streams of N2,and the average apparent activation energy of evaporation process was evaluated by the Ozawa,Kissinger,and Friedman methods.The possible conversion function was estimated through the Coats-Redfern method to characterize the evaporation patterns and followed a phase boundary reaction mechanism by the contracting area equation with average activation energy of 85.1 kJ·mol-1.     

采用高炉铁液生产大高径比灰铸铁钢锭模

介绍了大高径比钢锭模的铸件结构及技术要求,详细阐述了生产该铸件的铸造工艺:采用横做横浇工艺,封闭式浇注系统,浇口比为ΣF直:ΣF横:ΣF内=1.4:1.2:(1.1~1.0),选用尺寸为φ50 mm的出气冒口;呋喃树脂砂造型,将球铁芯骨固定在芯盒内,砂层厚度为40~50 mm;大高径比钢锭模采用高炉铁液浇注,出铁温度控制在1 400±20℃,在出铁过程中,向流铁槽内加入粒度为3~6 mm的75SiFe及65MnFe,加入量分别为0.3%~0.5%、0.5%~1.0%,铁液最终成分为w(C)4.1%~4.6%、w(Si)0.6%~1.0%、w(Mn)0.7%~1.0%、w(P)≤0.10%、w(S)≤0.03%;浇注前扒渣3~5次,浇注温度控制在1 260~1 300℃,浇注速度2~3 t/min。最终生产的铸件内壁平直度公差为3~5 mm,内壁光滑,抗拉强度也符合技术要求。     

7A60铝合金点蚀行为的电化学噪声和电化学阻抗谱表征

采用电化学阻抗谱（EIS）和电化学噪声（EN）方法研究回归再时效（RRA）热处理状态下7A60铝合金的点蚀行为,通过扫描电子显微镜（SEM）和能谱仪（EDS）观察和分析合金的组织和第二相颗粒成分。结果表明,7A60铝合金在3.5%Na Cl溶液中存在两个腐蚀阶段,并且可以用EIS出现两个电容时间常数的时间和由EN计算出的小波分形维数D的变化来表征。SEM和EDS分析结果表明,在7A60铝合金中,严重的点蚀主要是由阳极相Mg Zn2引起的,其次是Al2MgC u和Mg2Si相,Al7Cu2Fe相对7A60铝合金点蚀行为的影响不大。     

(Y,Gd)2O3:Eu3+纳米粒子制备过程中的合成动力学

采用反向滴定共沉淀法制备出（Y,Gd）₂O₃:Eu³⁺前躯体,再在不同温度下煅烧,获得（Y,Gd）₂O₃:Eu³⁺纳米粒子,用XRD和SEM对样品物相组成及形貌进行了表征;用TG-DTA获得了佯品在不同升温速率下的热分解曲线.结果表明,前躯体在煅烧过程中的物相变化分为3个阶段,用Doyle-Ozawa法和Kissinger法分别计算出各个反应阶段的表观活化能,其平均值分别为191.54,557.05和236.58 kJ·mol^-1并建立了动力学方程;（Y,Gd）₂O₃:Eu³⁺晶粒生长活化能是35.58 kJ.mol^-1,纳米粒子形核过程中的晶粒长大由晶界扩散控制.     

Spectroscopic properties of Yb: LuLiF4 crystal grown by the Czochralski method for laser applications and evaluation of quenching processes: a comparison with Yb: YLiF4

Spectroscopic properties of Yb³⁺ ion in LuLiF₄ (LLF) laser host are presented here for the first time. Czochralski technique was used to grow undoped and Yb³⁺-doped LLF single crystals under CF₄ atmosphere. Detailed analysis of Yb³⁺-doped LLF spectroscopy were made to contribute to the determination of energy levels in this host and a comparison with the isomorphic YLiF₄ (YLF) laser host is done. We are dealing with temperature and concentration dependences of both π and σ polarizations of the infrared (IR) absorption and emission spectra. Raman spectra were also used to give an attempt for the interpretation of electronic and vibronic levels. Concentration dependence of fluorescence lifetimes allows the measurement of the high radiative lifetime in the range of 2–3 ms and shows a strong self-trapping process. Self-quenching was not seen by the reduction of the decay times but observed by non-radiative up-conversion energy transfer due to the presence of Er³⁺ and Tm³⁺ ions as unexpected impurities. Contrary to oxide crystals this process still remains lower than the self-trapping process. Yb³⁺ pairing and clustering were investigated as well. Evaluation of the laser potentiality of this host by the evaluation of figure-of-merit developed by our group is presented.     

Surface modification of die casting mold steel by a composite technique of hot-dipping and plasma electrolytic oxidation

The hot dipping process of pure aluminum on H13 steel substrates followed by plasma electrolytic oxidation（PEO） was studied to form alumina ceramic coatings for protective purpose.H13 steel bars were first dipped in pure aluminum melts,and then,a reactive iron-aluminum intermetallic layer grew at the interface between the melt and the steel substrate.The reactive layer was mainly composed of intermetallic Fe-Al（Fe₂Al₅）;the thickness of aluminum layer and Fe-Al intermetallic layer were mainly influenced by dipping time（1.5～12.0 min） and dipping temperature（710～760 ℃）.After PEO process,uniform Al₂O₃ ceramic coatings were deposited on the surface of aluminized steel.The element distribution,phase composition and morphology of the aluminized layer,and the ceramic coatings were characterized by SEM/EDS and XRD.The distribution of hardness across the composite coating is demonstrated,and the maximum value reaches 1864 HV.The thermal shock resistance of the coated sample is also well improved.     

电弧喷涂制备Fe65Cr20Mo7B3.5SiMn1.5W3涂层

在Q235低碳钢板上利用电弧喷涂工艺进行喷涂,以制得Fe65Cr20Mo7B3.5SiMn1.5W3涂层。喷涂材料为自行配制的丝材,按照35%的填充率将配好的粉填充到U型不锈钢外皮中,经过多道拉拔、挤压工艺制成Φ2mm的粉芯丝材。采用X射线衍射仪、扫描电镜、能谱分析仪、透射电镜对涂层的物相和组织形貌及成分进行了表征;采用差示扫描量热仪、显微硬度仪等设备对涂层的热稳定性及显微硬度进行了检测和分析。试验结果表明:涂层组织形貌呈典型的层状组织结构,由变形良好的带状粒子相互搭接堆积而成。涂层含有50.63%的非晶相,同时含有纳米级的晶相。涂层组织均匀、结构致密、孔隙率低,并且涂层硬度高达1040.5HV0.3,属硬质涂层,具有良好的热稳定性。