焙烧条件对Ce离子价态影响的XPS研究

在均相沉淀法制备含铈化合物的过程中,利用XRD和IR尤其是XPS研究了含Ce化合物在不同焙烧温度条件下产物的结构、铈离子的价态变化、化合物表面性质及其内核电子构型。XRD结果表明,焙烧温度的不同可产生不同的铈基化合物,导致产物中Ce离子价态的变化,IR结果也证实了这一点。单纯均相沉淀法得到的产物为三价的斜方晶系的单晶Ce_2O(CO_3)_2·H_2O(Ⅲ)微粒;将三价的Ce_2O(CO_3)_2·H_2O加热到200℃,产物转化成高价态六价化合物CeO(CO_3)_2·H_2O(Ⅵ);加热温度再升高到250℃,产物转化为稳定的四价化合物CeO_2(Ⅳ)。XPS通过对3种不同价态化合物的O(1s),Ce(3d),Ce(4d)峰进行精细扫描,研究了产物的表面性质及其内部电子构型,比较结果证实了不同价态铈化合物的形成是由于内核价电子构型的差异引起的。     

EXAFS研究硫酸硫脲反萃季铵氰化金的机理

季铵盐可以直接从氰化浸出液中萃取金 ,但反萃困难。酸性硫脲通空气反萃体系是目前从季铵盐中反萃氰化金最有效的体系 ,但对其机理的研究很少。文章采用扩展X射线吸收精细结构 (EXAFS)等方法研究了硫酸硫脲从负载氰化金季铵盐中反萃金的机理。研究结果表明 ,在反萃过程中 ,硫酸、硫脲和硫脲金都能以中性分子进入有机相 ,中性缔合在季铵盐反萃过程中不可忽视。反萃机理如下 :(1)硫酸和硫脲首先进入有机相被萃取 ;(2 )在有机相中 ,硫脲争夺金的氰根配位 ,使氰化金变成硫脲金 ,同时游离出来的氰根与硫酸中的氢离子作用变成氢氰酸 ,在鼓空气搅拌条件下氢氰酸被空气迅速带走排除 ;(3)硫脲金配合物在有机相和水相中分配 ,大部分硫脲金进入水相 ,从而达到反萃的目的。     

表面活性剂对均相沉淀法制备单晶Ce2O(CO3)2￠H2O微粉形貌及 形成机理的影响

在尿素及硝酸铈的混合溶液中分别加入表面活性剂CTAB、 PEG19000、OP-10,利用均相沉淀法合成了不同形貌的CeO2超细前驱体Ce2O(COa)2·H2O,采用X射线衍射及透射电子显微镜等测试手段,对产品的物相和形貌进行了表征．实验结果表明,所得产品均为斜方晶系的单晶Ce2O(CO3)2·H2O,且表面活性剂的加入使晶体的晶化程度明显提高;添加不同的表面活性剂得到不同形貌尺寸的产物: 阳离子型表面活性剂CTAB对Ce2O(CO3)2·H2O晶体的形貌影响不大,所得产物尺寸变小,且分散性得到一定的改善;非离子型表面活性剂对所得产物的形貌影响显著．加入PEG19000和OP-10分别得到了形状排列有序的、尺寸较均匀的、较规则无团聚的微米棒及具有紧密结合中心的发散状的花样微粒．不同形貌前驱体的形成与晶粒形成生长机理的改变有关．     

利用红外光谱分析有机羧酸在均相反应中的配位作用机理

利用红外(IR)光谱、X射线衍射(XRD)及透射电子显微镜(TEM)等手段,对有机羧酸在尿素及硝酸铈的均相反应混合溶液中所起的配位作用进行了分析,并对产品的物相和形貌进行了测试与表征。实验结果表明：在尿素及硝酸铈的混合溶液中分别加入一元羧酸硬脂酸,二元羧酸酒石酸和三元羧酸柠檬酸时,一元羧酸硬脂酸在混合溶液中只起表面活性剂的作用,其产物为斜方晶系的单晶Ce₂O(CO₃)₂·H₂O微粉,且表面活性剂硬脂酸的加入使得晶体的晶化程度明显提高;而二元羧酸酒石酸与三元羧酸柠檬酸在均相反应中则起螯合剂的作用,分别与Ce3+形成螯合物酒石酸铈和柠檬酸铈,这些结果的造成是由于其反应机理的不同所导致的。     

酒石酸络盐均相沉淀法制备CeO2纳米晶的研究

以硝酸铈、酒石酸铵为原料,采用络合均相沉淀法制备了CeO2纳米晶.研究了酒石酸铈络合物的形成和沉淀的操作方式等因素的影响.用XRD,TEM和SEM等测试方法对样品进行了表征.从样品的SEM照片可以看到形貌为蓬松泡沫状多孔性立体结构,经HRTEM观察小颗粒具有很清楚的晶格条纹,说明这些小颗粒为CeO2纳米晶.     

利用红外光谱法分析洗衣粉的成分

采用热的无水乙醇作为溶剂将洗衣粉的无机和有机成分分开,利用红外(IR)光谱法进行分析。通过IR分析并经多晶粉末X射线衍射法(XRD)物相分析可以确定洗衣粉无机相主要成分为碳酸钠、硫酸钠以及4A沸石。IR分析表明有机相主要成分为十二烷基苯磺酸钠,核磁共振氢谱(~1H NMR)确认为支链十二烷基苯磺酸钠。     

钶铁矿型MnNb2O6的熔盐法合成、钒掺杂与磁性研究

采用了熔盐法新工艺制备了纯相与掺钒的MnNb₂O₆粉晶,利用X射线衍射仪(XRD),扫描电子显微镜(SEM),能谱分析(EDX),透射电子显微镜(TEM)、高分辨透射电镜(HRTEM)和电子衍射(SAED)分析了其物相、形貌及微结构.结果表明合成产物为正交晶系钶铁矿型MnNb₂O₆;在不同的熔盐中合成出了棒状、片状与长方体形貌的纯相产物.讨论了温度与掺杂对结构与形貌的影响,HRTEM与SAED分析表明了产物的各向异性生 关键词： 熔盐法 结构与形貌 掺杂 反铁磁性     

CeO_2纳米晶的制备及其谱学性能研究

以硝酸亚铈为原料,浓氨水为沉淀剂,在80℃反应3 h并陈化9 h制备得到了纯CeO2纳米晶.XRD分析结果表明产物属于立方晶系.透射电镜观察发现产物呈六边形结构,推测为多面体形CeO2的投影,粒径在10 nm左右,分散性良好.沉淀剂浓度、反应温度及陈化时间等对产物的纯度及形貌有明显影响.碱浓度降低或陈化时间缩短都导致产物中出现Ce(OH)3杂质;延长陈化时间,产物粒径增大;若反应温度低于40℃,产物中出现大量Ce(OH)3杂质.拉曼光谱研究表明,纯CeO2纳米晶在465 cm-1处有一振动峰,对应于立方萤石结构的F2g拉曼位移,而含有Ce3+杂质的产物则在600 cm-1处还出现一小峰.荧光光谱研究发现,在波长为400 nm的激发光下,CeO2纳米晶在465 nm附近出现一个不对称发射光谱峰.     

蓝宝石基片上制备双面Tl_2Ba_2CaCu_2O_8超导薄膜

在蓝宝石基片上,以CeO2为缓冲层制备了高质量的双面Tl2Ba2CaCu2O8(Tl-2212)超导薄膜。以金属铈靶作为溅射源生长了c轴取向的CeO2缓冲薄膜,并对CeO2薄膜进行了高温处理,有效改善了其结晶质量和表面形貌。采用两步法制备了双面的Tl-2212超导薄膜。XRD测试显示,薄膜为纯的Tl-2212相,且其晶格c轴垂直于衬底表面。超导薄膜的Tc为106K,Jc(77K,0T)为3.5MA/cm2,微波表面电阻Rs(77K,10GHz)为390μΩ。     

钪钇石型β-Mn2V2O7的水热合成、结构表征与反铁磁性

用水热法新工艺在温度为200—220℃,pH值为6—9条件下合成出Mn₂V₂O₇粉晶.利用X射线衍射(XRD)、扫描电子显微镜(SEM)、能谱分析(EDS)、透射电子显微镜(TEM)、高分辨透射电镜(HRTEM)和电子衍射(SAED)分析了其物相、形貌及微结构,结果表明:合成产物均为单斜晶系的钪钇石型β-Mn₂V₂O₇;当合成温度为200℃时,pH值为6—7时合成产物的形貌为 关键词： 水热法 2V₂O₇')" href="#">β-Mn₂V₂O₇ 结构与形貌 反铁磁性     

Effect of ultrasound on the structural and textural properties of copper-impregnated cerium-modified zirconium-pillared bentonite

In this study, the synthesis of zirconium-pillared bentonite modified with cerium was performed via two different methods by the application of conventional and ultrasonic treatments during the intercalation stage. To synthesise copper-impregnated pillared clays by wet impregnation, cerium-modified zirconium-pillared clays were used as supportive materials after being calcined at 300 °C. Ultrasonic treatment significantly decreased the required processing time compared with the conventional treatment of the synthesised pillared bentonites. Chemical analysis confirmed the incorporation of Zr⁴⁺, Ce⁴⁺ and Cu²⁺ species into the pillared bentonites. X-ray diffraction (XRD) patterns of zirconium- and cerium/zirconium-pillared bentonites prepared by conventional treatment show that one large d-spacing above 3.5 nm corresponds to the mesoporous delaminated part, and another small d-spacing above 1.7 nm is indicative of the microporous pillared part. Zirconium- and cerium/zirconium-pillared bentonites prepared via ultrasonic treatment exhibited similar results, with the same high d-spacing but with a second low-intensity d-spacing above 1.9 nm. The delaminated structures of the pillared bentonites synthesised by both methods were conserved after copper impregnation. Nitrogen-adsorption isotherm analysis showed that the textural characteristics of products synthesised by ultrasonic treatment were comparable to those of products synthesised by conventional treatment. Fourier-transform infrared spectroscopy (FTIR) analyses showed the presence of Brønsted- and Lewis-acid sites, and zirconium-pillared clays synthesised by conventional treatment exhibited increased numbers of Brønsted- and Lewis-acid sites after cerium addition and copper impregnation. However, the products synthesised by ultrasonic treatment exhibited an increased number of Brønsted- and Lewis-acid sites after cerium addition, but a decreased number of acid sites after copper impregnation.     

Cerium and boron chemistry in doped borosilicate glasses examined by EELS

Spatially resolved measurements of boron coordination and cerium valency in a doped borosilicate glass with crystalline nano-precipitates are described. The fine structure of the boron K-edge and the white-line ratio of the cerium M-edge doublet were evaluated from EELS line scans. Due to high beam sensitivity it was found that reliable boron-coordination measurements in some of the glasses studied required extrapolation of results acquired after different periods of irradiation back to a zero-irradiation. However, borosilicates that contained heavy alkali atoms were found to suffer very little structural change. The Ce valency of a 4% (molar) doped alkali-borosilicate glass was found to be mixed +III/+IV in the glass matrix and purely +IV (indicative of CeO2) in the precipitates. A significant dependency of the valence results on the data processing method was found and explained.     

基于养护龄期的煅烧煤矸石细集料砂浆X射线衍射及扫描电镜分析

采用X射线衍射法(XRD)和环境扫描电镜(SEM)分析方法,研究了不同煅烧温度下煤矸石细集料的活性,针对活性最高的700 ℃高温煅烧煤矸石细集料砂浆的水化产物、微观结构和强度进行了探讨,并分析了砂浆强度随养护龄期(3,7,14,28,60和90 d)增长的变化规律。试验研究表明：煤矸石细集料随着煅烧温度的升高,其活性逐步增加,当煅烧温度达到700 ℃左右时,煤矸石细集料的活性达到最高,当煅烧温度继续升高时,活性呈下降趋势。经过700 ℃高温煅烧的煤矸石细集料具有明显的火山灰活性,其活性组分SiO₂和Al₂O₃能与水泥水化产物发生一定程度的二次水化反应,通过对不同养护龄期的活性最高的700 ℃高温煅烧煤矸石细集料砂浆XRD和SEM分析可知,随着养护龄期的增长,二次水化反应将更加充分,而且水化产物的数量也逐步增多,与早龄期的水泥砂浆相比,生成物相更为稳定的水化产物填充在砂浆的微观孔隙中,能够进一步改善砂浆的微观结构,增强砂浆的界面性能,使砂浆内部结构更加均匀,煅烧的煤矸石细集料和水泥砂浆更趋为一个坚固连续的整体,水泥硬化砂浆的后期强度有较大增幅,活性最高的700 ℃高温煅烧煤矸石细集料火山灰效应明显。     

准球心弧线摆动高速抛光用的高纯氧化铈

本文阐述了准球心弧线摆动高速抛光中与聚氨基甲酸乙酯抛光模相匹配的高纯氧化铈抛光粉经烧制处理后的抛光效率,添加剂的作用以及回收处理。     

Corrosion behaviors in physiological solution of cerium conversion coatings on AZ31 magnesium alloy

In this paper, a non-toxic Ce-based conversion coating was obtained on the surface of bio-medical AZ31 magnesium alloys. The micro-morphology of the coating prepared with optimal technical parameters and immersed in physiological solution (Hank's solution) in different time was observed by scanning electron microscopy (SEM), composition of the cerium conversion coating and corrosion products in Hank's solution were characterized by X-ray photoelectron spectroscopy (XPS) and energy dispersive spectroscopy (EDS), respectively. In addition, the corrosion property in Hank's solution was studied by electrochemical experiment and immersion test. The results show that the dense Ce-based conversion coating is obtained on the surface of AZ31 magnesium alloys in optimal technical parameters and the conversion coating consists of a mass of trivalent and tetravalent cerium oxides. The cerium conversion coating can provide obvious protection of magnesium alloys and can effectively reduce the degradation speed in Hank's solution. Also the degradation products have little influence on human body.     

An in situ iron-57 Mössbauer spectroscopic investigation of the reduction of ironcerium oxide catalysts in different gaseous reducing agents

The formation of iron-cerium oxide catalysts by the treatment in hydrogen or carbon monoxide of air-dried precipitates has been monitored in situ by⁵⁷Fe Mössbauer spectroscopy. The results show that the initial calcination of the precipitates in air induces phase segregation and the formation of small concentrations of large particle α-iron(III) oxide in combination with cerium dioxide. Treatment of the solid in hydrogen at 450°C results in the facile reduction of α-Fe₂O₃ to metallic iron which is unaffected by exposure to a reactant gaseous mixture of carbon monoxide and hydrogen. Exposure of the biphasic material formed in air to carbon monoxide at similar temperatures induces the reduction of α-Fe₂O₃ to Fe₃O₄ and metallic iron and the subsequent formation of iron carbide. The carbided catalyst is not changed by exposure to a mixture of carbon monoxide and hydrogen. In distinct contrast the cerium orthoferrite of composition CeFeO₃ suffers only slight reduction when treated in hydrogen and shows a very limited amenability to carbide formation when treated in carbon monoxide.     

Theoretical studies of Ir5Th and Ir5Ce nanoscale precipitates in Ir

Experimentally, it is known that very small amounts of thorium and/or cerium added to iridium metal form a precipitate, Ir₅Th/Ir₅Ce, which improves the high-temperature mechanical properties of the resulting alloys. We demonstrate that there are low-energy configurations for nanoscale precipitates of these phases in Ir, and that these coherent arrangements may assist in producing improved mechanical properties. One precipitate/matrix orientation gives a particularly low interfacial energy, and a low lattice misfit. Nanolayer precipitates with this orientation are found to be likely to form with little driving force to coarsen. The predicted morphology of the precipitates and their orientation with the matrix phase provide a potential experiment that could be used to test these predictions.     

纳米粉体CeO_2∶Eu~(3+)的溶胶-凝胶绿色合成及其发光性质

采用溶胶-凝胶法,以硝酸铈为原料,加入适量淀粉为分散剂,并通过氨水来调节溶液p H值,合成稀土Eu~(3+)掺杂的CeO_2红色纳米粉体。通过X射线衍射仪、场发射扫描电子显微镜、荧光分光光度计等手段研究不同煅烧温度对粉体结构、形貌、发光及显色性能的影响。结果表明,所得样品为立方晶系的萤石结构,空间群为Fm3m,颗粒呈近似球形,粒径范围在10~60 nm之间。随着煅烧温度的升高,CeO2晶粒尺寸逐渐增大,荧光粉的红色发光也逐渐增强。经800℃烧结后,近紫外(370 nm)和蓝光区(468 nm)的光都能对粉体有效地激发,这有利于其在固态照明中的应用。在溶胶-凝胶制备过程中,采用淀粉作分散剂,具有工艺简单、绿色环保的优点,有利于纳米氧化铈粉体的大规模制备。     

蠕变镍基单晶高温合金微观结构与界面特征的X射线小角散射研究

利用SAXS技术对蠕变过程中不同尺度范围的微观结构变化分析表明X射线小角散射(SAXS)与中子小角散射(SANS)测量的二维散射图具有明显的差异,由散射强度曲线的变化说明了蠕变过程中二次析出γ'相形貌和不同区域尺寸特征的改变情况.分析结果表明二次析出γ'相存在两类特征尺寸,在蠕变过程中沿[100]或[010]方向的变化趋势类似,均是在第一和第二阶段有所减小,在第三阶段又有所增大,相较而言,特征尺寸较大的γ'相变化也较为显著.二次析出γ'相在蠕变第二阶段元素扩散最严重,相表面最粗糙,在第三阶段两相界面又进一 关键词： 单晶高温合金 二次析出γ'相 X射线小角散射 微观结构