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。     

The fluorescence and thermoluminescence characteristics of α-Al2O3:C ceramics

This paper reports that polycrystalline α-Al₂O₃:C ceramics are fabricated by conventional ceramics process. The excitation, emission spectra, thermoluminescence (TL) and optical stimulated luminescence (OSL) of α-Al₂O₃:C polycrystalline ceramics are investigated. There exists 410nm maximum emission peak which is caused by recombination of an electron with F⁺ centre to produce an excited F centre. The samples show three clear TL glow peaks at 405, 493 and 610K. The attenuation constant of exponentially decaying fast component (τ₁) and slow component(τ₂) of OSL curve are 8.43s and 41.73s, respectively. Those fluorescence and thermoluminescence characteristics are similar with α-Al₂O₃:C crystal.     

氧化铁还原率及金属化率的测量新方法

用H₂及CO还原氧化铁过程中,使用了X-ray粉末衍射和化学分析方法确定了氧化铁及金属铁的定量分析关系。铁素体(α_Fe)、奥氏体(γ_Fe)、碳化铁(Fe₃C)、磁铁矿(Fe₃O₄)、赤铁矿(Fe₂O₃)与浮氏体(Fe_0.947O)的摩尔强度定量关系的系数分别为0.56,0.56,0.52,0.87和2.57。通过这些系数,可以计算出氧化铁的金属化率和还原率。     

三种具有Keggin结构的硅钨氧簇化合物的光谱研究

合成了三种具有Keggin结构的硅钨氧簇化合物：K₃H[SiWⅥ₁₂O₄₀]·3H₂O(Ⅰ),(H₃O)₄[H₃SiWⅥ₉WⅤ₃O₄₀]·2H₂O(Ⅱ)和[(CH₃)₄N]₄[SiWⅥ₁₂O₄₀]·4.5 H₂O(Ⅲ),用FTIR,NIR FT-Raman,UV-Vis和荧光光谱等研究手段进行了光谱研究,探讨其结构与性能的关系。在这些化合物中, 阴离子相同或类似,具有孤立的[SiW₁₂O₄₀]簇骼基元,通过静电作用和弱的氢键与阳离子及水相连。它们的FTIR和NIR FT-Raman光谱研究表明：硅钨酸盐的特征振动频率与其结构相关,由于化合物Ⅱ中的部分W6+已被还原成W5+,使ν_as(WO_d)振动频率降低,且簇阴离子电荷大小也明显地对ν_as(W—O_c—W),ν_as(Si—O_a),δ(O_a—Si—O_a)等产生影响;化合物Ⅰ和Ⅱ的UV-Vis光谱显示,在200和250 nm左右有紫外吸收谱带;化合物Ⅰ的稳态荧光光谱观察到分别以220,350和440 nm激发时,相应在350,440和520及675 nm左右产生一个或两个发射峰。     

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。     

X射线荧光光谱法快速分析盐湖粘土矿物元素含量

以低压聚乙烯粉镶边垫底粉末压片法制样,用X射线荧光光谱法测定盐湖粘土矿物中主次组分含量的定量分析曲线,测量了粘土矿物中As, Mn, Co, Cu, Cr, Dy, Ga, Mo, P, Pb, Rb, S, Sr, Ba, Cs, Ta, Th, Ti, U, V, Y, Zn, Zr, MgO, K₂O, Na₂O , CaO, Fe₂O₃, Al₂O₃, SiO₂含量。研究了各元素的谱线干扰特别是谱线的间接干扰,同时提出了元素周期表中各周期元素相互之间干扰的判别方法; 使用α经验系数法及康普顿内标法校正基体效应,经对国家标准物及实际样品进行分析,测量值与标准值结果吻合。方法的检出限和准确度均满足分析要求,除了Mo,Cs,Ta ３个元素RSD较高,其他元素RSD 为0.01%～5.45%。     

多酸有机亚胺衍生物的紫外-可见光谱及其取代基效应

以(Bu₄N)₄[α-Mo₈O₂₆]和各种取代苯胺及其盐酸盐为原料, 在碳二环己基亚胺(DCC)存在下, 经脱水反应,合成了多种六钼酸根有机亚胺衍生物, 并用元素分析,1H-NMR,IR和UV-Vis光谱等进行表征,重点研究了六钼酸根有机亚胺衍生物在乙腈溶液中的紫外光谱。研究结果表明,该类化合物具有典型的分子内电子转移的紫外-可见光谱特征,其特征峰位移Δλ_max与苯胺的苯环取代基的共轭效应指数(σ_R)之间存在良好的线性关系。     

卤代苯甲酰基二茂铁的紫外光谱研究

研究了全系列的邻、间、对-卤代苯甲酰基二茂铁的紫外光谱,发现化合物紫外光谱K带及R带 λ_max值呈现如下规律：卤素相同而取代位置不同时,K带和R带λ_max值均为λ_max(m-X)＞λ_max(p-X)＞λ_max(o-X); 卤素不同而取代位置相同时,K带λ_max值顺序为λ_max(Cl)＞λ_max(Br)＞λ_max(I)＞λ_max(F),而R带λ_max值顺序为λ_max(I)＞λ_max(Br)＞λ_max(Cl)＞λ_max(F), 邻位为Br,I时出现例外。     

两种含铋的杂多化合物的光谱研究

在水热条件下合成了两个含铋的杂多化合物：Co₅[Bi₂Co₂W₂₀O₇₀(H2O)₆]·44H₂O(Ⅰ)和Na₃H₂[Ce₃(H₂O)₁₈Bi₂W₂₂O₇₆]·23H₂O(Ⅱ),通过用FTIR, NIR FT-Raman和UV-Vis DRS光谱研究了它们的结构和性能的关系。ν_as(MO_d)和ν_s(M—Ob—M)的特征振动频率和材料的结构相关。ν_as(M—O_b—M)振动频率可说明当W原子被Co原子取代时氧化活性增强。在化合物Ⅰ和Ⅱ的UV-Vis DRS谱中,分别存在254,319和220,310 nm的(O_d→W),(O_b, c→W)的荷移跃迁特征峰,化合物Ⅰ还在529 nm处出现宽而弱的Co2+的d-d跃迁吸收谱带。最后,文章还对化合物Ⅰ进行了量子化学计算,用于说明其结构特征。     

金色海水养殖珍珠异常的UV-Vis反射与FTIR光谱特征

采用紫外-可见(UV-Vis)反射光谱对天然与改色处理的金色海水养殖珍珠进行了谱图对比性研究,并进一步探究了上述天然与经改色处理金珠中外层的珍珠层及内核中文石型碳酸钙的ν₃,ν₁,ν₂和ν₄特征吸收峰位的频率改变特征。 结果表明：(1)基于金珠样品的UV-Vis反射谱图的测试,天然金珠样品由于表面微结构的差异,同一颗天然金珠的UV-Vis反射光谱存在一定的差异性。 同时,依据改色处理金珠的UV-Vis反射谱图的吸收峰的峰位及其谱图特征,首次将目前较常见的改色处理金珠归纳为四类。 (2)天然的或者经改色处理的金珠的外层珍珠层中的文石ν₂振动频率相对内核中文石的ν₂振动频率而言,前者出现明显的蓝移特征。 但两者中文石的ν₃, ν₁, ν₄振动频率则表现出一致性, 且与合成文石的相关谱带频率一致。 此外,天然与改色处理的金珠珍珠层中文石的红外特征吸收峰峰位一致,结果表明改色处理工艺对珍珠层中文石的晶体结构无直接影响。     

大气腐蚀研究中钢锈层的光谱分析

运用现任中光谱分析的方法,对青岛、成都两地的大气腐蚀锈层样品,进行了比较测试,得出锈层中各元素的含量、主要组成物相及各相对含量随腐蚀环境、时间的变化情况。     

Influence of Cu and Ni on the morphology and composition of the rust layer of steels exposed to industrial environment

Four samples of steels with alloying elements were exposed to an industrial environment during 1,955 days, aiming to elucidate the effect of the alloying elements Cu and Ni on the resistance of weathering steels to corrosion processes. The samples were characterized with optical microscopy, scanning electron microscopy (SEM), powder X-ray diffraction (XRD), saturation magnetization measurements and with energy dispersive (EDS), infrared, Mössbauer and Raman spectroscopies. All the steels originated orange and dark corrosion layers; their thicknesses were determined from the SEM images. EDS data of such rust layers showed that the alloying element content decreases from the steel core towards the outer part of the rust layer. Moreover, in the dark rust layer some light-gray regions were identified in the W and Cu-alloy steel, where relatively higher Cr and Cu contents were found. XRD patterns, infrared, Raman and Mössbauer spectra (298, 110 and 4 K) indicated that the corrosion products are qualitatively the same, containing lepidocrocite (γFeOOH; hereinafter, it may be referred to as simply L), goethite (αFeOOH; G), feroxyhite (δ′FeOOH; F), hematite (αFe₂O₃; H) and magnetite (Fe₃O₄; M) in all samples; this composition does not depend upon the steel type, but their relative concentrations is related to the alloying element. Mössbauer data reveal the presence of (super)paramagnetic iron oxides in the corrosion products. Saturation magnetization measurements suggest that feroxyhite may be an occurring ferrimagnetic phase in the rust layer.     

Recent Research and Development in Solving Atmospheric Corrosion Problems of Steel Industries in Japan

A rust layer, so called protective rust layer, on a weathering low-alloy steel has strong protective ability for atmospheric corrosion of the steel. We have recently found through a large number of spectroscopic studies including Mössbauer spectroscopy that the protective rust layer forms after long-term phase transformation. The phase and structure of the rust definitely control the protective ability of the rust layer. From this recent knowledge, some new technologies have been developed. One is the surface-treatment technique that provides a possibility for obtaining the protective rust layer in a relatively short period even in the severe environments such as in marine and chloride (de-icing salts) containing environments. Others are based on selection of effective alloying elements for steel materials. These are particularly important for application in areas where protective rust layer formation may be hindered or prevented. In this paper, we mention recent progress in research and development on rusting protection by rust for atmospheric corrosion of steels in Japan.     

Fe–Mn–Al–C Alloys: a Study of Their Corrosion Behaviour in SO2 Environments

The corrosion reaction of four Fe–Mn–Al alloys exposed to a cycling, dry–humid, SO₂ (0.001% by volume) polluted atmosphere was studied. ICEMS, XPS, AES-SAM and transmission Mössbauer spectroscopy at different temperatures were employed to characterize the corrosion products. The analytical results indicate that (i) ferrihydrite is the main component of the rust; (ii) there is an abundant presence of Mn²⁺ and SO₃ ^2–/SO₄ ^2– on the top of the corrosion layer, the concentration of SO₄ ^2– increasing with the number of cycles; and (iii) the magnetic hyperfine pattern exhibited by the series of low-temperature spectra of the rust is quite different from that observed in the rust formed under similar corrosive environments on iron and weathering steel. This latter finding is correlated with a slow rate of transformation of the Fe³⁺ species formed at the early stages of corrosion into -FeOOH, the usual final product of this type of corrosion processes. The sulphate anions, abundant inside the electrolyte during the wet periods, could be incorporated to the ferrihydrite structure being responsible for the Mössbauer spectral pattern recorded from the corrosion products at low temperatures.     

Raman and IR spectroscopy study of corrosion products on the surface of the hot‐dip galvanized steel with alkaline mud adhesion

The corrosion products formed on hot‐dip galvanized steel sheets for the automobile application with adhesion of alkaline mud containing different Cl⁻ ion contents are investigated by means of Raman and infrared (IR) spectroscopy. Results show that the Cl⁻ ion content in alkaline mud has great influence on the corrosion behavior of the galvanized steel. The Cl⁻ ions are responsible for the formation of the Zn₅Cl₂(OH)₈· H₂O layer on the surface of the steel at the early stage of corrosion. The rest of the Cl⁻ ions then penetrate and interrupt corrosion product layer resulting in pitting corrosion. Subsequently, the red corrosion product of α‐FeOOH (shaped as needle‐like structure) is formed, which then transforms into black rust of Fe₃O₄ (having a shape of slim needle). It is interesting to find out that pitting depth is inversely proportional to the Cl⁻ ion content. However, corrosion rate decreases with the increase of the Cl⁻ ions in mud. Copyright © 2009 John Wiley & Sons, Ltd.     

Portable Raman study on the conservation state of four CorTen steel‐based sculptures by Eduardo Chillida impacted by urban atmospheres

Weathering steel, and particularly CorTen steel, is a very used material for modern artworks exhibited outdoors. One of the characteristic that makes this material so attractive to artists is the property to develop a protective rust layer composed by iron oxides which preserves its metallic core from atmospheric corrosion. This study was conducted to evaluate the conservation state of four CorTen sculptures by Eduardo Chillida, located in different places of Bilbao city (north of Spain) and affected by different factors (environmental among others) by using Raman spectroscopy. Measurements were performed in situ with a handheld Raman spectrometer mounted on a tripod with x–y–z axes motorization at the micron level. The most common oxyhydroxides detected were lepidocrocite (γ‐FeO(OH)), goethite (α‐FeO(OH)), hematite ( ‐Fe₂O₃) and magnetite (Fe₃O₄), being goethite the most stable phase. All the iron oxyhydroxides were identified in all of the studied sculptures but their relative amounts were different for each sculpture. The consequences of the marine aerosols exposure in the steel surface were also studied, detecting limonite (FeO(OH)·nH₂O) and akaganeite (β‐FeO(OH)). The results confirmed that the evolution of the rust layer present on the analyzed weathering steels is different, depending both on the exposure and the particular type of the steel. Copyright © 2012 John Wiley & Sons, Ltd.     

Judd-Ofelt Analysis of Photoacoustic Spectra of Powdered Neodymium Compounds

Photoacoustic (PA) spectra of powdered neodymium oxide: Nd₂O₃ (A type), neodymium hydrated chloride: NdCl₃-6H₂O and neodymium fluoride: NdF₃ are reported. PA band shifts as compared to their positions in aqueous Nd(III) ion have been used to calculate the nephelauxetic parameters of their compounds. The variation of these parameters and correlation with the nature of metal-ligand bonding have been discussed. A novel method is introduced to determine relative values of Judd-Ofelt parameters and oscillator strengths of powdered samples using PA spectroscopy. It is found that a linear correlation exists between relative values of τ₂ and relative oscillator strengths of hypersensitive transitions of the title compounds. It can be hoped that the new method of PA technique may serve for the Judd-Ofelt quantitative analysis of powdered rare earth compounds.     

Study of the corrosion products formed on a multiphase CuAlBe alloy in a sodium chloride solution by micro-Raman and in situ AFM measurements

The corrosion products formed on a multiphase Cu-11.40Al-0.55Be (wt.%) alloy in 3.5% NaCl at open circuit potential, and their evolution with immersion time were studied mainly by micro-Raman and in situ AFM measurements. The aluminium content of each phase affects the formation of the corrosion products on them. After 1 day of immersion, γ₂ precipitates were more susceptible to dealuminization, while α′ phase exhibited a high corrosion stability. The corrosion products evolved with immersion time, and CuCl₂ and a Cu₂O/CuO double layer film were the stable products formed on all the phases after long times.     

火成岩中长石含量与其特征光谱间响应关系研究

长石是地表岩石最重要的造岩矿物,在地壳中的比例高达60%,几乎是所有火成岩的主要矿物成分。随着高光谱技术的发展,国内外众多学者研究主要造岩矿物含量与其特征光谱的响应关系,对遥感岩矿识别以及矿化蚀变信息提取提供了多种可能性。该研究以USGS光谱库里18个火成岩样本为基础数据,研究长石的特征光谱及其与含量之间的定量关系。通过原始光谱反射率及其变换(包括小波三层分解高频分量、小波二层分解、去包络线后光谱、去包络线后小波三层分解高频分量及去包络线后小波二层分解),研究其与长石的含量之间的相关关系,结果表明：(1)分析六种光谱反射率的变换,去包络线后小波三层分解高频分量的光谱反射率与长石含量的相关关系最好,且相关系数正负不断变化,根据相关系数极值获得长石的特征谱带为431,570,972,1 456,1 856,2 292.9和2 481 nm;(2)原始光谱反射率与长石含量的相关性曲线趋势较为平缓,而经小波分解得到的高频分量后,趋势明显,经去包络线及小波分解得到高频分量后,相关性曲线的变化趋势愈加明显,由此可见,自变量的微小变化就会引起因变量变化,当岩石中长石的含量极小时,小波分解处理能够提高模型的精度。将长石含量与特征光谱的关系量化,运用多元逐步线性回归分析以及最小二乘法建模,建立6个线性回归模型和6个最小二乘法回归模型,结果表明：(1)去包络线后的光谱比原始光谱建立的回归模型精度更高,经过小波二层分解后的低频分量建模的回归模型精度优于未进行小波分解的光谱,其中去包络线后小波二层分解低频分量建立的回归模型效果最佳。(2)多元线性回归建立的模型精度优于最小二乘法,同时筛选对因变量影响较大的自变量,972,1 456,1 856,2 292.9以及2 481 nm。因此选择去包络线后的光谱进行多元线性回归法进行分析长石含量与光谱反射率之间关系,考虑到不同的特征吸收波段对长石含量的影响因子不同,可以利用长石的特征光谱定量反演某一区域内的长石的含量,对识别矿物具有重要意义。