溶胶凝胶法制备（Eu^2＋，Dy^3＋）SrAl2O4

采用无机盐溶胶-凝胶法制备了颗粒均匀的形态为针状的(Eu2+,Dy3+)SrAl2O4纳米粉体.通过TG-DTA分析和X射线衍射和扫描电镜分析方法,对样品进行了微观结构和表面形态的表征.研究了纳米(Eu2+,Dy3+)SrAl2O4粉体在不同烧结温度下固相反应过程和成相规律.实验结果表明,当样品的烧结温度为500 ℃时是单一的Sr(NO3)2晶相;750 ℃左右生成了Sr3Al2O6,并伴有少量SrAl2O4晶体;1 100 ℃是生成了结晶度良好的针状纳米(Eu2+,Dy3+)SrAl2O4粉体.通过计算,样品粉体晶粒平均为80～100 nm.该晶体粒度随烧结温度升高而逐渐变大.     

SHS原理烧结合成不定形耐火材料的发热体系研究

通过对单一供氧剂体系，复合供氧剂体系的SHS反应产物外观特征和性能测定、物相分析以及尖晶石的生成情况，合成材料的显微形貌特征和能谱分析等特征的研究，得出：SHS原理制备不定形耐火材料时，发热体系采用复合供氧剂体系较单一供氧剂好，通过复合的方法，即碳酸盐－Fe2O3或碳酸盐－硝酸钠的复合，实现了高、中、低温分级供氧，效果明显好于单一供氧体系，其中碳酸盐Fe2O3的最好重量比为2：1，碳酸盐与硝酸钠的最好重量比约为4：1。文中还对发热体系的SHS反应进行了分析。     

溶胶-凝胶法制备纳米荧光粉Y4Al2O9:Eu3+的初步研究

用溶胶-凝胶法(sol-gel)制备了纳米荧光粉Y4Al2O9: Eu3+,用X射线粉晶衍射对其进行了物相鉴定,表明在900℃已经得到纯相的Y4Al2O9产物,并用透射电镜对其进行形貌和衍射分析,分析结果证明得到的产物为纳米粉末态晶体,产物Y4Al2O9:Eu3+粒径均匀,大致在20～50nm之间,平均粒径为30nm.并用荧光光度计对其荧光光谱进行了研究,光谱表明Eu3+在Y4Al2O9晶格中占据两种不同的位置.用λ =254nm的紫外光激发Y4Al2O9:Eu3+时,产生两条发光谱带,即由于5 D 0→7 F 1的跃迁产生在峰值λ =590nm处的橙色发光带,和5 D 0→7 F 2跃迁在峰值λ =610nm处的红色发光带.     

固相合成法制备六角薄板状CeO2纳米晶

以分子量为600的聚乙二醇(PEG600)为分散剂,通过Ce(NO3)3.6H2O和无水Na2CO3的固相反应制备出混相碳酸铈盐[Ce2O(CO3)2.H2O和Ce2(CO3)3.8H2O]前驱体,热分解该前驱体获得CeO2纳米晶。XRD研究表明,产物归属于立方晶系的方铈石相,空间群为Fm3m。混相碳酸铈盐前驱体的反应活性较高,350℃热处理已使其分解完全,获得平均晶粒度仅为6.5 nm的纯CeO2纳米粉体,600℃焙烧产物的平均晶粒度达到27.1 nm,该温度下获得的CeO2微粒呈薄板状,板面平滑,大体呈规整的六边形,板径主要在30 nm~40 nm之间,径/厚比为5~7。在透射电镜下直接观察到的平均颗粒度与采用Scherrer公式计算的平均晶粒度相近,反映出由此固相合成法制备的纳米粉体颗粒较为均匀,从团聚体生长出来的大颗粒较少。     

纳米铁还原高浓度硝基苯的实验

采用液相还原法制备纳米铁粒子,粒径约为50 nm,主要成分为ɑ-Fe。实验研究了纳米铁还原高浓度硝基苯的效果及反应动力学。结果表明:自制的纳米铁具有很高的活性,短时间内能将高浓度硝基苯彻底还原,效果远优于普通铁粉。当摩尔比满足n纳米铁∶n硝基苯=4∶1时,纳米铁还原硝基苯属于一级反应动力学,反应速率常数和半衰期分别为0.159 3 h-1和4.351 2 h。整个实验过程中,ρ(DO)在0.5 mg/L以下,pH值约为9.0,体系呈弱碱性的厌氧环境,有利于厌氧微生物的生长。纳米铁反应后的产物为Fe6(OH)12CO3和MgFe3O4,且以Fe6(OH)12CO3为主。纳米铁反应后较以前比粒径变化不大,分散性较好,但表面被严重腐蚀。     

溶胶—凝胶法制备纳米荧光粉Y4A2O9：Eu^3＋的初步研究

用溶胶－凝胶法（sol-gel)制备了纳米荧光粉Y4Al2O9:Eu^3 ，用X射线粉晶对其进行了物相鉴定，表明在900℃已经得到纯相的Y4Al2O9产物，并用透射电镜对其进行形貌和衍射分析，分析结果证明得到的产物为纳米粉末态晶体，产物Y4Al2O9：Eu^3 粒径均匀，大致在20－50nm之间,平均粒径为30nm。并用荧光光度计对其荧光光谱进行了研究，光谱表明Eu^3 在 Y4Al2O9晶格中占据两种不同的位置。用λ=254nm的紫外光激发了Y4Al2O9：Eu^3 时，产生两条发光谱带，即由于^5D0→^7F1的过产生在峰值λ＝590nm处的橙色发光带，和^5D0→^7F2跃迁在峰值λ＝610nm处的红色光带。     

TiO2-白云母纳米复合材料的制备及其表面化学特征

TiO2－白云母纳米复合材料属纳米薄膜材料，具有优异的珠光效应。本文利用化学液相沉积法制备出不同类型（单覆层、多覆层）的TiO2－白云母纳米复合材料，并利用扫描电子显微镜（SEM）和粉晶X射线衍射（XRD）、X射线光电子能谱（XPS）等手段对其进行了分析。SEM分析显示：所制备的TiO2－白云母纳米复合材料TiO2的颗粒直径在20－60nm之间，且颗粒均匀、界限清晰，表面平整。XRD分析表明：导晶剂Sn^4 对于提高TiO2向金红石转化起到了重要作用。XPS研究发现TiO2纳米镀层除Ti、O外还有以类同像替代Ti^4 形式存在的导晶离子Sn^4 和由载体白云母扩散的Si、Al、K成分。同时，表面O不足，偏离TiO2理想组成；随TiO2纳米镀层厚度的，TiO2逐渐接近理想成分；并且O（ls)、Ti(2p)向高结合能漂移，结合能增大，次外层比最外层组分具有较强的化学键合，最外层组分则表现出一定的化学活性。     

X射线粉晶衍射法分析磷化膜不同成分衍射强度比

利用X射线粉晶衍射法对金属板材及其磷化膜进行全谱和区段扫描,在确定镀膜中存在Zn2Fe(PO4)2.4H2O和Zn3(PO4)2.4H2O物相的基础上,求出Zn2Fe(PO4)2.4H2O的(100)和Zn3(PO4)2.4H2O的(020)衍射峰的计数强度,计算出样品磷化膜的磷比,从而判断出磷酸盐配比是否达到工艺要求。     

X射线衍射K值法测定氧化铁皮中游离α-SiO_2的含量

目前通常采用焦磷酸法和X射线衍射法测定游离α-Si O2的含量,其中焦磷酸法不能消除氧化铁皮中Fe O、Fe3O4和Fe2O3等焦磷酸难溶物质的影响,不适合用于测定氧化铁皮中的游离α-Si O2。本文建立了采用X射线衍射K值法测定氧化铁皮中游离α-Si O2含量的方法。以α-Al2O3作为参考物质,以α-Si O2(101)衍射峰和α-Al2O3(012)衍射峰作为测量谱峰,将α-Si O2和α-Al2O3(质量比1∶1)混合均匀制备成测量K值的试样,获得K值为7.86,应用此值分析已知游离α-Si O2含量的氧化铁皮样品,游离α-Si O2含量的测定值与实际值相符。该方法的测定范围为游离α-Si O2含量≥0.50%,且方便快速,能够满足进口氧化铁皮检验监管的工作需求。     

凹凸棒石-TiO2-磁性颗粒纳米复合材料的制备

为制备具有高效吸附、光催化性能,可磁分离回收催化剂的凹凸棒石-TiO2-磁颗粒纳米复合材料,本文研究了不同反应温度、不同量的氧化剂加量、不同的碱加入量对复合材料磁化率的影响,并利用透射电镜、X射线粉末衍射对制备的复合材料结构和微形貌进行了表征。实验结果表明,在70℃下,Fe2 ∶OH-∶NO3-质量比为1∶0.6∶0.056时,反应生成的产物再经500℃煅烧,获得的凹凸棒石-TiO2-磁性颗粒纳米复合材料的磁化率最高。高分辨透射电镜表征结果显示,经500℃煅烧获得的凹凸棒石-TiO2-磁性颗粒复合材料,其TiO2和磁性颗粒非常均匀地吸附在凹凸棒石表面。     

X射线荧光光谱法测定富含硫砷钒铁矿石中的主次量元素

以钴(钴玻璃粉形式)作内标元素,准确测定全铁含量;加入保护剂硝酸铵和稳定剂碳酸锂,使硫转化为硫酸盐,有效地防止硫的挥发损失。通过条件实验,确立了样品熔融温度和钴玻璃粉的用量。选择经筛选的仪器测定条件,用X射线荧光光谱法同时测定铁矿石中TFe、SiO2、CaO、MgO、Al2O3、TiO2、P、S、Mn、V2O5、As、K2O、Na2O、Cu、Ni等15种主次量元素。采用干扰曲线法对几乎完全重叠的TiΚβ谱线与VΚα谱线进行谱线重叠校正,用理论α系数法校正基体效应。建立的方法可以准确测定全铁和质量分数高达5.29%的S。采用多种标准物质和人工配制标准物质制作工作曲线,可以测定质量分数为5.00%的V2O5及0.1%的As,测定值与标准值符合较好,除低含量钠外方法精密度(RSD)<3.5%,分析误差符合实验质量要求。本法可以快速、准确地测定含砷的钒钛铁矿及含硫高的铁矿石中的主次量元素,满足了日常生产对铁矿石中硫和钒的测定要求。     

Fe2+在零价铁还原去除NO3-中的作用效应

零价铁（Fe0） 被广泛用于地下水中硝酸盐原位与异位修复,但二价铁（Fe2+） 的存在对具有氧化膜的Fe0还原硝酸盐的作用效应仍有待研究。以100 目的未经酸化的颗粒状零价铁作为还原剂,采用室内批试验方法,研究了Fe2+在零价铁还原去除NO3-系统中的作用效应。实验结果表明,Fe2+可显著提高Fe0对于NO3-的去除速率与去除效率,且Fe2+浓度越高,去除速率与效率越高;由于未经酸化的Fe0具有氧化膜,反应初期的NO3-还原速率较慢。Fe2+将零价铁表面的Fe2O3氧化膜转化为Fe3O4,加速电子由Fe0向NO3-的转移,促进NO3-还原。此外,在反应系统中加入Fe3O4,可进一步提高Fe0对于硝酸盐的去除能力,若Fe2+不存在,仅添加Fe3O4,NO3-的去除效率没有提高。     

星叶石族矿物的晶体化学

星叶石是碱性岩中分布较广泛的副矿物,成分富含碱金属K、Na及Ti,随其产出的地球化学条件,类质同象代换情况较复杂,形成许多成分异种。本工作之前对其组成和性质都不十分清楚,前人虽进行了一般矿物学研究,但未能确定所属晶系,B.C.索波列夫曾推断星叶石中Ti呈四面体配位,并与硅氧四面体组成复杂构造。     

山东蓝宝石的主要致色因素

山东蓝宝石颜色深暗,与其主要致色元素有着直接关系.对其化学成分进行分析认为:Cr2O3是红色、橙黄色、黄色的主要致色因素.而w(TiO2)低,w(TFeO)高,尤其是Fe3 大于全铁的90%,TFeO/TiO2比值大是山东蓝宝石颜色深暗的主要原因.对其紫外-可见光-近红外吸收光谱进行分析,进一步得出Cr3 离子的d-d电子跃迁、成对Fe3 离子、单Fe3 离子的d-d电子跃迁、Fe2 -Ti4 之间的电荷转移、Fe2 Fe3 之间的电荷转移等是山东蓝宝石致色的本质.代表绝大多数山东蓝宝石颜色的深蓝色蓝宝石,缺失紫外-可见光-近红外吸收光谱的575～711nm吸收带,即缺少Fe2 -Ti4 之间的电荷转移.因此,针对性地选择w(TiO2)高的蓝宝石进行改善,或是设法加入TiO2、减少Fe3 含量、在还原条件下改变其TFeO/TiO2的比值,应是目前山东蓝宝石改色的关键.     

含钙铝铁水解聚合产物的矿物学研究Ⅰ:形态和物相

用X射线粉晶衍射分析技术结合热重分析、红外光谱及电镜观察对合成的含钙聚合氯化铝铁(PAFCCa)及其合成前体含钙聚合氯化铝(PACCa)、含钙聚合氯化铁(PFCCa)的低温干燥样进行了表征.XRD衍射结果表明,Ca(Ⅱ) 分别与Al(Ⅲ)、Fe(Ⅲ)都能形成结晶化合物,在PACCa中结晶化合物主要是Ca3Al2(OH)12,在PFCCa中结晶化合物主要是Ca4Fe14O25,在PAFCCa中形成Al-Ca-Fe三相结晶化合物铁取代的氯钙矾石结构体,其组成是(Ca6(Al,Fe)2[(OH)4Cl2]3·20H2O).热重分析、红外光谱与电镜观察都支持了XRD的衍射结果.     

熔片制样-X射线荧光光谱法测定煤灰样品中主次量组分

采用混合熔剂熔融制备样片,用AxiosX射线荧光光谱仪测定煤灰样品中二氧化硅、氧化铝、氧化铁、氧化镁、氧化钙、氧化钠、氧化钾、二氧化钛、二氧化锰、五氧化二磷和三氧化硫等11种组分。重点研究了熔样比、熔样温度和标准样品的制备,解决了分析硫的难题。用基本参数法校正基体效应,分析方法的精密度(RSD,n=10)各组分均小于3%。用煤灰国家一级标准物质验证,结果与标准值相符。     

Determination of the Electrochemical Properties of a Soluble Aqueous FeS Species Present in Sulfidic Solutions

Field and laboratory data are presented that show a soluble FeS species(FeS_aq) exists in sulfidic seawater solutions, and is observedwhen the IAP exceeds the K_sp of amorphous FeS. TheFeS_aq yields a discrete signal (double peak) using square-wavevoltammetry and two one-electron waves in sampled DC polarographyexperiments at the Hg electrode. The aqueous FeS species reacts irreversiblyat the electrode as a single FeS subunit and not as a polymeric entity. Thepeak potential of FeS_aq occurs at -1.1 V whereas the peakpotential of Fe occurs at-1.45 V; the positive shift for Fe²⁺ reduction inFeS_aq indicates a change in geometry for Fe²⁺from octahedral to tetrahedral. The kinetics of electron transfer at theelectrode are determined to be similar for both Fe²⁺ andFeS_aq. Molecular orbital energy diagrams, further indicatethat Fe(II) does change from octahedral to tetrahedral geometry in solution.First, Fe(II) exists as octahedralFe in solution whichundergoes a substitution reaction of bisulfide for water. The resultingcomplex, Fe(H₂O)₅(HS)⁺, thentransforms to a tetrahedral complex on further addition of sulfide. Thisgeometry change is consistent with the formation of amorphous FeS thatconverts to mackinawite which has tetrahedral Fe(II). The process is entropydriven because of the water loss that occurs. The overall sequence can berepresented as: Soluble FeS species are important asreactants in the formation of iron-sulfide minerals including pyrite.     

Composition and Assemblage Characteristics of Magnetic Minerals in Layer S_(5-1) of Xifeng and Duanjiapo Sections

Magneticmineralsintheloess paleosolseriesaccountforabout 1 % -2 %ofthetotal (LiuTungshengandZhangZhonghu ,1 962 ) .Duetotheiraerolianorigin ,themagneticmineralsarecomplicatedincomposition ,largeingrainsizerange ,andsignificantlydifferentincrystallinity .Asaresult,researchonthesemagneticmineralswouldbesetwithalotofdifficulties.Previousre searchersemployedopticalmicroscopic ,X raydiffractionandM ssbauerspectrometrictechniquestostudythemagneticmineralsintheloess paleosolseries,andchieflyontheb…     

Bioreduction of hematite nanoparticles by the dissimilatory iron reducing bacterium Shewanella oneidensis MR-1

We examined the reduction of different size hematite (α-Fe₂O₃) nanoparticles (average diameter of 11, 12, 30, 43, and 99 nm) by the dissimilatory iron reducing bacteria (DIRB), Shewanella oneidensis MR-1, to determine how S. oneidensis MR-1 may utilize these environmentally relevant solid-phase electron acceptors. The surface-area-normalized-bacterial Fe(III) reduction rate for the larger nanoparticles (99 nm) was one order of magnitude higher than the rate observed for the smallest nanoparticles (11 nm). The Fe(III) reduction rates for the 12, 30, and 43 nm nanoparticles fell between these two extremes. Whole-cell TEM images showed that the mode of Fe₂O₃ nanoparticle attachment to bacterial cells was different for the aggregated, pseudo-hexagonal/irregular and platey 11, 12, and 99 nm nanoparticles compared to the non-aggregated 30 and 43 nm rhombohedral nanoparticles. Due to differences in aggregation, the 11, 12, and 99 nm nanoparticles exhibited less cell contact and less cell coverage than did the 30 and 43 nm nanoparticles. We hypothesize that S. oneidensis MR-1 employs both indirect and direct mechanisms of electron transfer to Fe(III)-oxide nanoparticles and that the bioreduction mechanisms employed and Fe(III) reduction rates depend on the nanoparticles’ aggregation state, size, shape and exposed crystal faces.     

Role of Fe(II) and phosphate in arsenic uptake by coprecipitation

Natural attenuation of arsenic by simple adsorption on oxyhydroxides may be limited due to competing oxyanions, but uptake by coprecipitation may locally sequester arsenic. We have systematically investigated the mechanism and mode (adsorption versus coprecipitation) of arsenic uptake in the presence of carbonate and phosphate, from solutions of inorganic composition similar to many groundwaters. Efficient arsenic removal, >95% As(V) and ∼55% in initial As(III) systems, occurred over 24 h at pHs 5.5-6.5 when Fe(II) and hydroxylapatite (Ca₅(PO₄)₃OH, HAP) “seed” crystals were added to solutions that had been previously reacted with HAP, atmospheric CO_2(g) and O_2(g). Arsenic adsorption was insignificant (<10%) on HAP without Fe(II). Greater uptake in the As(III) system in the presence of Fe(II) was interpreted as due to faster As(III) to As(V) oxidation by molecular oxygen in a putative pathway involving Fe(IV) and As(IV) intermediate species. HAP acts as a pH buffer that allows faster Fe(II) oxidation. Solution analyses coupled with high-resolution transmission electron microscopy (HRTEM), X-ray Energy-Dispersive Spectroscopy (EDS), and X-Ray Absorption Spectroscopy (XAS) indicated the precipitation of sub-spherical particles of an amorphous, chemically-mixed, nanophase, Fe^III[(OH)₃(PO₄)(As^VO₄)]·nH₂O or Fe^III[(OH)₃( PO₄)(As^VO₄)(As^IIIO₃)_minor]·nH₂O, where As^IIIO₃ is a minor component.The mode of As uptake was further investigated in binary coprecipitation (Fe(II) + As(III) or P), and ternary coprecipitation and adsorption experiments (Fe(II) + As(III) + P) at variable As/Fe, P/Fe and As/P/Fe ratios. Foil-like, poorly crystalline, nanoparticles of Fe^III(OH)₃ and sub-spherical, amorphous, chemically-mixed, metastable nanoparticles of Fe^III[(OH)₃, PO₄]·nH₂O coexisted at lower P/Fe ratios than predicted by bulk solubilities of strengite (FePO₄·2H₂O) and goethite (FeOOH). Uptake of As and P in these systems decreased as binary coprecipitation > ternary coprecipitation > ternary adsorption.Significantly, the chemically-mixed, ferric oxyhydroxide-phosphate-arsenate nanophases found here are very similar to those found in the natural environment at slightly acidic to circum-neutral pHs in sub-oxic to oxic systems, such phases may naturally attenuate As mobility in the environment, but it is important to recognize that our system and the natural environment are kinetically evolving, and the ultimate environmental fate of As will depend on the long-term stability and potential phase transformations of these mixed nanophases. Our results also underscore the importance of using sufficiently complex, yet systematically designed, model systems to accurately represent the natural environment.