沉积铁钝化膜的傅立叶变换表面增强拉曼光谱

利用恒电流沉积技术、傅立叶变换表面增强拉曼散射技术现场研究了0 1mol/LNaOH溶液中铁金属电极在不同电位下的表面氧化物的组成。结果表明,在电极预钝化区,表面首先生成的Fe(OH)2可由拉曼谱图中出现的550cm-1表征,证实了以往的研究结果。进入钝化区,表面二价氧化物逐步转化为高价氧化物Fe3O4及α 、δ 和γ FeOOH。在电位回扫的过程中,各氧化产物的还原以及铁表面SERS活性的逐渐消失导致谱峰强度降低。     

P110钢CO2腐蚀产物膜的XPS分析

为了确定CO2腐蚀产物膜的组成及不同层次结构中成分和含量的差异,采用P110钢在高温高压腐蚀静态釜中制备CO2腐蚀产物膜,利用SEM观察了腐蚀产物膜的表面和断面形貌,结合XRD分析结果,通过XPS研究了两层结构膜的化学组成差异。结果表明,腐蚀产物膜断面呈现双层结构;膜层的主要成分是FeCO3,还有少量的CaCO3和铁的氧化物,但内层CaCO3较多且夹杂着Fe3C和单质Fe,外层氧化物稍多;通过内外层Ca^2＋含量差异推断出内层腐蚀膜优先形成。     

Nd2Fe14B的价电子结构分析和磁性计算

应用固体与分子经验电子理论计算了Nd2Fe14B的价电子结构、磁矩和居里温度,计算结果与实验值相符.计算表明:该合金的磁性与3d磁电子数成正比.从Fe(c)晶位到Fe(k2)晶位磁矩增加,其机理源于价电子、哑对电子和3d磁电子之间的转化,有78%的哑对电子和18%的3d共价电子转化成了磁电子.居里温度和磁矩与Fe原子配位数成正比,与加权等同键数Iσ成反比,Nd原子和B原子通过调节原子间键距影响Nd2Fe14B合金的居里温度.     

非晶态RE—TM(RE=Nd,Pr,TM=Fe,Co,Ni)薄膜的磁性和Pr的变价行为

本文通过对非晶态轻稀土Pr,Nd和过渡族金属Fe,Co,Ni薄膜合金的低温磁性研究,分别得到了(Pr,Nd)_x-(Fe,Co,Ni)_1-x合金中Pr,Nd和Fe,Co,Ni金属磁矩随成份x的变化,并且通过对磁矩的研究得到Pr离子的4f电子可能有退局域化的结论。 关键词：     

不同因素影响下Fe(Ⅲ)水解中和法制备FeOOH矿相的光谱分析

羟基氧化铁(FeOOH)作为重金属等污染物的吸附材料倍受关注,但不同因素作用下形成的FeOOH产物矿相、结构性质的差异及其对环境功能的影响,却少有报道。采用X射线衍射仪,红外光谱仪,扫描电子显微镜和激光粒度分析仪,系统考察了Fe(Ⅲ)溶液水解中和形成FeOOH时,不同作用因素如铁盐种类、pH和温度等对产物矿相的影响。结果表明,pH 8条件下,Fe(Ⅲ)溶液水解产物均为二线水铁矿(Fe₅HO₈·4H₂O);随着pH升高,Fe₅HO₈·4H₂O会向α-FeOOH相转化。Cl-和NO-₃离子的存在分别有利于β-FeOOH和α-FeOOH的形成;SO2-₄会阻碍Fe₅HO₈·4H₂O向α-FeOOH相转化;Fe2+存在时,会促进Fe₅HO₈·4H₂O向α-FeOOH相转化。加热陈化,可促进Fe₅HO₈·4H₂O转化为α-FeOOH,且利于良好结晶α-FeOOH的形成。但pH≤5,富含Cl-的Fe(Ⅲ)溶液加热水解利于β-FeOOH的生成。不同因素影响下形成的FeOOH,在矿相、表面基团、颗粒形貌和粒径大小上存在一定的差异。     

冲击波诱导Nd_2Fe_(14)B磁相变的理论计算研究

根据Nd2Fe14B的冲击加载实验,计算了3.3—7.2 GPa压力范围内冲击波阵面上压力与温度的关系.基于分子场理论,引入压力等效场,改进了双亚点阵理论模型,并分析了在不同温度和压力下Nd2Fe14B的磁性转变机理.计算了压力对Nd2Fe14B磁致伸缩系数、磁化率、磁化强度以及居里温度的影响,给出了Nd2Fe14B发生铁磁–顺磁相变的压力和温度判据.计算结果表明:压力使Nd2Fe14B的居里温度逐渐向低温区转移,当压力从0 GPa增加到1.15 GPa时,居里温度从584 K降至292 K;随着压力的增加,Nd2Fe14B的磁化强度不断下降,且临界去磁压力随温度的升高呈下降趋势;在3.3—7.2 GPa压力范围内,Nd2Fe14B发生了铁磁-顺磁相变.     

FeOOH生成条件的研究(Ⅰ)

本文报道了用NaOH,NH₄OH作为沉淀剂在硫酸亚铁溶液中生成FeOOH的条件。用电子显微镜观察了结晶形态;用X射线衍射确定了相组成与相界。NH₄OH及NaOH作沉淀剂所生成的FeOOH在酸性范围内具有相似的相图,而在碱性范围内二者却不同。 关键词：     

钙钛矿型稀土锰氧化合物Nd0.5Sr0.4Pb0.1Mn1-xFexO3中Mn位的Fe替代效应

对Nd0 5Sr0 4Pb0 1 Mn1 -xFexO3系列多晶样品的结构 ,磁和转变特性进行了实验研究 .在x =0 0 0— 0 10的范围内获得了单相样品 ,Fe3+ 的替代并没有引起整个系列的结构变化 ,然而Mn位的掺杂却强烈地抑制了Nd0 5Sr0 4Pb0 1MnO3的铁磁性和金属—绝缘体转变 .在低掺杂情况下 (x≤ 0 0 6)Mn被Fe替代 ,金属—绝缘体转变温度TP 平均下降了 19K ,当x≥ 0 0 8铁磁金属态完全过渡为绝缘态 .这主要归因于Fe3+ 的渗入影响了化合物eg 电子浓度和抑制了双交换作用     

硫原子在镍基合金825(001)面吸附的第一性原理研究

元素硫在镍基合金表面吸附产生严重的电化学腐蚀,为从原子尺度研究硫腐蚀机理,采用第一性原理方法,构建并优化了镍基合金825的晶胞结构模型,计算分析了S原子在镍基合金825耐蚀性较差面(001)晶面的吸附及电子转移情况.结果表明:Ni原子占据顶角, Cr原子和Fe原子对称占据面心是镍基合金825稳定的晶胞结构;原子S在镍基合金825(001)面上最稳定的吸附位为四重穴位,吸附能为-6.51 eV; S吸附前后的态密度(DOS)和二维电荷差分密度图(DCD)对比发现,镍基合金825中Fe与S之间电荷偏移明显,形成离子键,易生成腐蚀产物Fe_xS_y. S的吸附对镍基合金825中Cr原子的电子分布影响不大,且合金中Cr和Ni抑制了合金中Fe与S之间的相互作用,从而提高了合金耐蚀性.     

Fe-C合金膜光纤腐蚀传感器传感规律研究

利用PVD溅射镀以及PVD与电镀复合两种方法在光纤纤芯上制备了不同厚度的Fe-C合金膜,对其进行X-射线衍射分析,所制膜层晶体结构类型与普通碳钢基本一致.通过将镀膜光纤放入不同浓度的HNO3溶液中以及埋入混凝土结构中,进行了腐蚀实验.结果表明:在低浓度的腐蚀溶液中,不同厚度的Fe-C合金膜会从外到内被均匀地腐蚀掉,输出光功率会在腐蚀末期有一个急剧的增大现象;在高浓度的腐蚀溶液中,Fe-C合金膜会在各个局部产生裂纹,膜层被一块一块地腐蚀掉;输出光功率整体趋势增大,但并没有特别急剧的增大现象;混凝土试块中的腐蚀实验中,输出光功率的变化复杂多变,但整体趋势还是一个增大的过程.     

Atmospheric corrosion in the Gulf of México

The corrosion products on steels exposed at two sites in Campeche, México and one site at Kure Beach, USA, have been investigated to determine the extent to which different marine conditions and exposure times control the oxide formation. The corroded coupons were analyzed by Mössbauer, Raman and infrared spectroscopy as well as X‐ray diffraction, in order to completely identify the oxides and map their location in the corrosion coating. The coating compositions were determined by Mössbauer spectroscopy using a new parameter, the relative recoilless fraction (F-value) which gives the atomic fraction of iron in each oxide phase from the Mössbauer sub‐spectral areas. For short exposure times, less than three months, an amorphous oxyhydroxide was detected after which a predominance of lepidocrocite (γ-FeOOH), and akaganeite (β-FeOOH) were observed in the corrosion coatings with the fraction of the later phase increasing at sites with higher atmospheric chloride concentrations. The analysis also showed that small clusters of magnetite (Fe₃O₄), and maghemite (γ(Fe₂O₃), were seen in the micro-Raman spectra but were not always identified by Mössbauer spectroscopy. For longer exposure times, goethite (α-FeOOH), was also identified but little or no β-FeOOH was observed. It was determined by the Raman analysis that the corrosion products generally consisted of inner and outer layers. The protective layer, which acted as a barrier to slow further corrosion, consisted of the α-FeOOH and nano-sized γ-Fe₂O₃ phases and corresponded to the inner layer close to the steel substrate. The outer layer was formed from high γ-FeOOH and low α-FeOOH concentrations.     

Characterization of initial atmospheric corrosion of conventional weathering steels and a mild steel in a tropical atmosphere

The phases and compositions of the corrosion products of a mild steel (A-36) and two weathering steels (A-588 and COR 420) formed after 3 months exposure to the tropical marine atmosphere of Panama were examined using FTIR and Mössbauer spectroscopy. The results show that amorphous or crystallized iron oxyhydroxides goethite α-FeOOH and lepidocrocite γ-FeOOH are early corrosion products. Maghemite γ-Fe₂O₃ and magnetite Fe₃O₄ have also been identified and found to be prominent components for steels exposed to the most aggressive conditions. The formation of akaganeite β-FeOOH was observed when chlorides were occluded within the rust. FTIR showed the presence of hematite α-Fe₂O₃ in one sample.     

Low Temperature CEMS of Corrosion Products by Sulfuric Acid Water

Conversion electron Mössbauer spectroscopy (CEMS) was used to study the corrosion products by sulfuric acid water. The acid water was put on the iron foil and evaporated under the atmosphere of several oxygen ratios in nitrogen-oxygen gas mixture in order to investigate the influence of oxygen contents on the corrosion products. The hyperfine fields of the observed sextets at 15 K suggest that the corrosion products consist of α-FeOOH, γ-FeOOH and γ-Fe₂O₃. The amount of γ-FeOOH becomes larger as the oxygen concentration increases. It is also found that the amount of γ-Fe₂O₃ becomes the largest at 1.4 % of the oxygen concentration.     

Mössbauer and XRD analysis of corrosion products on weathering steel treated by wet-dry cycles using various solutions

Weathering steels (COR-TEN) were corroded by wet-dry cycles using a splay of various solutions in a laboratory. Corrosion products on weathering steel were characterized by X-ray diffractometry and Mössbauer spectrometry at room and low temperatures. Fine α-FeOOH, γ-FeOOH and γ-Fe ₂ O ₃ are fundamentally formed in various atmospheric conditions. β-FeOOH is additionally formed under the existence of chloride ions, but not formed when sulfate ions are coexisting. Spraying a NaF solution prevents the progress of corrosion.     

Conversion electron Mössbauer spectroscopy study of growth and nature of corrosion products on mild steel exposed to different environments

In this study, conversion electron Mössbauer spectroscopy (CEMS) has been utilized for identifying the nature of initial corrosion products formed on the surface of steel under different environments and measurement of relative thickness of corrosion products formed. CEMS studies on mild steel exposed under different environments, viz. mild steel sprayed with (1) distilled water (2) 3% NaCl and (3) mild steel exposed to SO₂ were carried out. The initial stable product of corrosion is found to be γ-FeOOH, which will transform into other oxyhydroxides and oxides, depending on environments. The mechanisms for the corrosion processes occurring under different conditions are also discussed.     

A CEMS Study of the Corrosion of Carbon Steel After Surface Laser Irradiation

The corrosion resistance of laser-irradiated carbon steel surfaces against SO₂-polluted atmospheres has been investigated by means of weight gain measurements and CEMS. The results show that the laser-irradiated samples present a higher corrosion resistance than the non-irradiated steel. The corrosion products are found to be superparamagnetic α-FeOOH and an amorphous Fe³⁺ oxyhydroxide. This revised version was published online in August 2006 with corrections to the Cover Date.     

Kinetics and structural studies of the atmospheric corrosion of carbon steels in Panama

The corrosion of a carbon steel was studied in different atmospheres at sites in the Republic of Panama. The weight loss (corrosion penetration) suffered by the carbon steel is related to time by a bilogarithmic law. Mössbauer spectroscopy indicated the rust was composed of non-stoichiometric magnetite (Fe_3-xO₄), maghemite (γ-Fe₂O₃), goethite (α-FeOOH) of intermediate particle size, lepidocrocite (γ-FeOOH) and superparamagnetic particles. Magnetite formation is related to the alternating dry--wet cycles. Goethite is related to corrosion penetration by a saturation type of behavior, following a Langmuir type of relationship. Goethite in rust protects steel against further atmospheric corrosion.     

Corrosion of weathering steel and iron under wet-dry cycling conditions: Influence of the rise of temperature during the dry period

The effect of a dry-hot period on the SO₂ corrosion of weatherig steel and pure iron under wet-dry cycling was investigated. Corrosion products were identified by Mössbauer spectroscopy and X-ray powder diffraction. The formation of an intermediate corrosion layer of spm α-FeOOH only on weathering steel was the most significant result.     

钢大气腐蚀锈层的激光拉曼光谱研究

本文运用激光拉曼光谱分析方法,对碳钢A3、低合金钢10CrMoAl经青岛大气腐蚀的锈层样品进行了比较测试,由实验结果分析得出锈层主要组成物相为α-Fe2O3,γ-FeOOH,α-FeOOH,δ-FeOOH,激光拉曼光谱分析为大气腐蚀锈层物相的研究提供有力的实验依据。     

Characterization of Iron Oxides Commonly Formed as Corrosion Products on Steel

For fundamental studies of the atmospheric corrosion of steel, it is useful to identify the iron oxide phases present in rust layers. The nine iron oxide phases, iron hydroxide (Fe(OH)₂), iron trihydroxide (Fe(OH)₃), goethite (α-FeOOH), akaganeite (β-FeOOH), lepidocrocite (γ-FeOOH), feroxyhite (δ-FeOOH), hematite (α-Fe₂O₃), maghemite (γ-Fe₂O₃) and magnetite (Fe₃O₄) are among those which have been reported to be present in the corrosion coatings on steel. Each iron oxide phase is uniquely characterized by different hyperfine parameters from M?ssbauer analysis, at temperatures of 300K, 77K and 4K. Many of these oxide phases can also be identified by use of Raman spectroscopy. The relative fraction of each iron oxide can be accurately determined from the M?ssbauer subspectral area and recoil-free fraction of each phase. The different M?ssbauer geometries also provide some depth dependent phase identification for corrosion layers present on the steel substrate. Micro-Raman spectroscopy can be used to uniquely identify each iron oxide phase to a high spatial resolution of about 1 μm. This revised version was published online in August 2006 with corrections to the Cover Date.