熔盐电解LiCl-KCl-AlCl3-La2O3共析出制备Al-Li-La合金

研究了LiCl-KCl-AlCl3-La2O3熔盐体系中共析出制备Al-Li-La合金的可行性。研究表明,在LiCl-KCl熔盐中,AlCl3将La2O3氯化为LaCl3,使电解制备Al-Li-La合金顺利进行。借助循环伏安法对熔盐体系的电化学行为进行分析发现,对质量比为45∶45∶5∶2的LiCl-KCl-AlCl3-La2O3熔盐,当阴极电流密度大于0.25 A/cm2,可以实现Al、Li和La的共析出。通过研究电解温度、阴极电流密度和电解时间对合金组成的影响,得到了较佳的电解参数:电解温度650℃,在LiCl-KCl混合熔盐中加入质量分数为5%的AlCl3和2%的La2O3,阴极电流密度12.5 A/cm2,电解时间1 h。X射线衍射对合金分析测试表明,合金主要由Al2La和βLi组成。     

t-ZrO2/α-Al2O3超细晶复合粉体的低温燃烧合成

以Al(NO3)3*9H2O、ZrO(NO3)2*2H2O和Y(NO3)3*6H2O为原料,采用低温燃烧合成(LCS)法制备了多种不同ZrO2/Al2O3比的复合粉体,对其物相和形貌进行了表征.实验结果表明,采用LCS法在400℃合成的t-ZrO2/α-Al2O3复合粉体晶粒超细,其结晶程度随ZrO2/Al2O3比的增加逐渐降低,晶粒大小也随ZrO2/Al2O3比的变化而有规律地变化.     

在LiCl-KCl-AlCl3熔盐中直接电化学还原Sm2O3及Al-Sm合金的形成

在803 K LiCl-KCl熔盐中,研究了通过添加助剂AlCl3直接电化学还原Sm2O3和Al-Sm合金的形成。以SmCl3为原料作为参照,采用循环伏安和方波伏安方法,研究了Sm2O3在LiCl-KCl-AlCl3熔盐体系中的电化学行为。通过对比发现在两个体系中,峰的数量和位置基本一致,这说明在LiCl-KCl熔盐中,加入AlCl3之后,可以将Sm2O3有效氯化。计时电位结果表明,当阴极电流比-139.8 mA.cm-2更负时,Al和Sm共同还原。为了提取Sm,采用恒电流从LiCl-KCl-AlCl3-Sm2O3熔盐中电解得到Al-Sm合金样品,并进行XRD表征,结果表明可以通过调节AlCl3和Sm2O3的浓度得到不同相的Al-Sm合金。     

纳米Sm2O3掺杂CeO2粉末的制备和性能表征

以Ce2(CO3)3和Sm2O3为原料, 用改进的氨水-双氧水沉淀法制备了CeO2和(CeO2)0.8为基质(Sm2O3)0.2的纳米粉末.对干燥后的氢氧化物进行了TG/DSC热分析, 约650 ℃时Ce(OH)4完全转变为CeO2.XRD分析表明, 650 ℃焙烧的粉末为萤石结构, 说明Sm2O3已固溶到CeO2中.经TEM测试, 粉体颗粒大小在5～10 nm之间, BET测试的平均颗粒尺寸为11.2 nm.由TEM照片还可以看出粉体具有良好的分散性, 且无硬团聚体存在.     

Er3+, Yb3+:Y2O3激光陶瓷粉体制备与性能研究

以Y2O3,Yb2O3和Er2O3为原料,控制溶液的pH值为3-4左右,采用柠檬酸溶胶-凝胶法制备出Er,Yb∶Y2O3倍半氧化物激光陶瓷前驱粉体。对所得到的粉体进行XRD测试,结果表明最佳煅烧温度为1000℃,并且晶化完全。经过差热-热重分析表明,粉体在1000℃煅烧后不再失重。荧光光谱分析发现,荧光发射的最强峰位于1530 nm处,是Er^3＋的4^I13/2-4^I15/2谱相导致的荧光发射。     

纳米NiAl_2O_4前驱体的电化学合成

在乙醇溶液中,按Ni/Al电量比为1∶3依次电解铝片和镍片,制得复合氧化物纳米粉体NiO Al2O3的前驱体NiAl2(OCH2CH3)(8-y)(acac)y[acac为乙酰丙酮基].产物通过红外光谱、X射线衍射、电子透射显微镜进行了表征,同时研究了镍电极在铝醇盐溶液中的电化学行为,讨论了影响电合成镍、铝醇盐配合物的关键因素.实验表明,电解温度控制在54～60℃、导电盐Bu4NBr浓度为0.040～0.045mol/L时,电流效率约为93%.水解后的干凝胶粒径在10nm左右,为纳米NiAl2O4粉体的制备创造了条件.     

掺杂Sm_2O_3对Y-ZrO_2陶瓷烧结行为和性能的影响

一定量的Sm2O3粉末与3%Y2O3(摩尔分数)稳定的四方ZrO2粉体(Y-ZrO2)经球磨混合、造粒后,在钢模中压制成形,所得压坯在1450~1600℃下烧结后,得到不同Sm2O3掺杂量的Sm2O3掺杂Y-ZrO2(SY-ZrO2)陶瓷烧结体。对不同温度下烧结所得烧结体试样的相组成、密度、电导率、硬度以及抗弯强度等性能进行了测试分析。实验结果表明:将适量的Sm2O3掺入Y-ZrO2中,可以获得具有立方结构的SY-ZrO2陶瓷烧结体,且其密度、硬度和抗弯强度与Sm2O3的掺杂量有关;Sm2O3的加入提高了Y-ZrO2陶瓷的电导率,掺杂0.5%Sm2O3的SY-ZrO2陶瓷800℃时在空气中的离子电导率可达0.02 S.cm-1。本试验的初步实验结果显示,采用二元稀土氧化物(Sm2O3和Y2O3)复合掺杂ZrO2陶瓷材料,可以在保持其良好力学性能的同时,提高其电导率,拓展其应用领域。     

前驱物热稳定性对氧化铁/氧化锡制备的影响

氧化铁纳米复合材料具有优越的磁学和催化性能,近年来在癌症诊断及治疗[1-3]、污染治理[4-6]、电磁屏蔽[7-8]等多个领域得到广泛研究.目前有许多研究集中于如何对复合材料的组成、结构和形貌进行设计合成,例如:利用机械球磨法将SnO2和α-Fe2O3粉体混合制备α-Fe2O3/SnO2 复合材料[9];通过共沉淀法将SnO2复合在α-Fe2O3 的表面[4];或者在Fe3O4表面复合一层C和相应的盐,然后通过煅烧制备Fe3O4/ZrO2和Fe3O4/TiO2微球[10-11].     

水热共还原法制备La_2O_3掺杂W-Cu复合粉末工艺研究

以水热合成法为基础,制备了La2O3掺杂量为2.0%(质量分数)的W-20Cu复合粉体,并通过SEM,HRTEM,DTA/TG及XRD等手段对复合粉体的物相、形貌和微观结构进行了表征。结果表明:水热共沉淀法制备稀土La2O3掺杂W-Cu复合粉时,对应前驱溶液的最佳p H为5.5。与不加稀土相比,水热产物分解温度降低,470℃煅烧2 h后,La与W形成复合氧化物La2W3O12,且分解形成的WO3相依附La(OH)3生长,其结晶性提高。在推杆式还原炉850℃于H2介质中还原2 h后,煅烧粉完全被转化为W,Cu和La2O3,HRTEM表征发现La2O3吸附在W和Cu颗粒的表面,阻止晶粒的长大,有望提高还原粉体的烧结性能。     

水热法制备超细α-Fe_2O_3粉体

以FeCl3·6H2O和氨水为原料,通过水热反应及热处理制得超细球形α-Fe2O3粉体,用IR, XRD和TEM对其结构,物相和形貌进行表征.结果表明,当前驱体FeO2H加热到200 ℃时已经完全分解成α-Fe2O3;FeO2H在300 ℃灼烧3 h可得到粒径约为100 nm和15 nm的两种共存的超细球形α-Fe2O3粉体.     

Sc2MgGa2 and Y2MgGa2

Scandium magnesium gallide, Sc₂MgGa₂, and yttrium magnesium gallide, Y₂MgGa₂, were synthesized from the corresponding elements by heating under an argon atmosphere in an induction furnace. These intermetallic compounds crystallize in the tetragonal Mo₂FeB₂‐type structure. All three crystallographically unique atoms occupy special positions and the site symmetries of (Sc/Y, Ga) and Mg are m2m and 4/m, respectively. The coordinations around Sc/Y, Mg and Ga are pentagonal (Sc/Y), tetragonal (Mg) and triangular (Ga) prisms, with four (Mg) or three (Ga) additional capping atoms leading to the coordination numbers [10], [8+4] and [6+3], respectively. The crystal structure of Sc₂MgGa₂ was determined from single‐crystal diffraction intensities and the isostructural Y₂MgGa₂ was identified from powder diffraction data.     

Electrochemical study of (NEt4)2Cl2FeS2MoS2 and (NEt4)2Cl2FeS2MoS2FeCl2

Summary The ability of [MoS₄]^2–, anions to be used as ligands for transition metal ions has been widely demonstrated, especially with Fe²⁺. The present study has been restricted to linear complexes such as (NEt₄)₂ [Cl₂FeS₂MoS₂] and (NEt₄)₂[Cl₂FeS₂MoS₂FeCl₂]. Their electrochemical properties are described: upon electrochemical reduction, these compounds yield MoS₂, as a black precipitate, and an iron complex in solution, assumed to be [SFeCl₂]^2–. The electrochemical reduction goes through two electron transfers, coupled with the breakdown of the molecular skeleton: a DISPl and an ECE mechanism. Depending on the solvent, the following equilibrium may be observed: [Cl₄Fe₂MoS₄]^2–[Cl₂FeMoS₄]^2–+FeCl₂. The equilibrium constant, K_D, was evaluated by differential pulse polarography. K_D is tightly related to the donor number of the solvent.     

The alkali hypophosphites KH2PO2, RbH2PO2 and CsH2PO2

The structures of the hypophosphites KH₂PO₂ (potassium hypophosphite), RbH₂PO₂ (rubidium hypophosphite) and CsH₂PO₂ (caesium hypophosphite) have been determined by single‐crystal X‐ray diffraction. The structures consist of layers of alkali cations and hypophosphite anions, with the latter bridging four cations within the same layer. The Rb and Cs hypophosphites are isomorphous.     

Zur Kenntnis der Dialkalimetalldichalkogenide β-Na2S2, K2S2, α-Rb2S2, β-Rb2S2, K2Se2, Rb2Se2, α-K2Te2, β-K2Te2 und Rb2Te2

On Dialkali Metal Dichalcogenides β-Na₂S₂, K₂S₂, α-Rb₂S₂, β-Rb₂S₂, K₂Se₂, Rb₂Se₂, α-K₂Te₂, β-K₂Te₂ and Rb₂Te₂ The first presentation of pure samples of α- and β-Rb₂S₂, α- and β-K₂Te₂, and Rb₂Te₂ is described. Using single crystals of K₂S₂ and K₂Se₂, received by ammonothermal synthesis, the structure of the Na₂O₂ type and by using single crystals of β-Na₂S₂ and β-K₂Te₂ the Li₂O₂ type structure will be refined. By combined investigations with temperature-dependent Guinier-, neutron diffraction-, thermal analysis, and Raman-spectroscopy the nature of the monotropic phase transition from the Na₂O₂ type to the Li₂O₂ type will be explained by means of the examples α-/β-Na₂S₂ and α-/β-K₂Te₂. A further case of dimorphic condition as well as the monotropic phase transition of α- and β-Rb₂S₂ is presented. The existing areas of the structure fields of the dialkali metal dichalcogenides are limited by the model of the polar covalence.     

Formal [(2+2)+2] and [(2+2)+(2+2)] nonconjugated dienediyne cascade cycloadditions

[reaction: see text] Fluoranthene 2 and heptacycle 3 are easily accessible from the reaction of diyne 1 and norbornadiene (NBD) in the presence of the rhodium catalyst. The unusual [(2+2)+(2+2)] adduct 3 was confirmed by the X-ray crystal structure analysis.     

Crystal Structures of [Bu2Sn(O2PPh2)2], [Ph2Sn(O2PPh2)2], and [PhClSn(O2PPh2)OMe]2. Raman Spectra of [Ph2Sn(O2PPh2)2] and [PhClSn(O2PPh2)OMe]2

[(n‐Bu)₂Sn(O₂PPh₂)₂] ( 1 ), and [Ph₂Sn(O₂PPh₂)₂] ( 2 ) have been synthesized by the reactions of R₂SnCl₂ (R=n‐Bu, Ph) with HO₂PPh₂ in Methanol. From the reaction of Ph₂SnCl₂ with diphenylphosphinic acid a third product [PhClSn(O₂PPh₂)OMe]₂ ( 3 ) could be isolated. X‐ray diffraction studies show 1 to crystallize in the monoclinic space group P2₁/c with a = 1303.7(1) pm, b = 2286.9(2) pm, c = 1063.1(1) pm, β = 94.383(6)°, and Z = 4. 2 crystallizes triclinic in the space group , the cell parameters being a = 1293.2(2) pm, b = 1478.5(4) pm, c = 1507.2(3) pm, α = 98.86(3)°, β = 109.63(2)°, γ = 114.88(2)°, and Z = 2. Both compounds form arrays of eight‐membered rings (SnOPO)₂ linked at the tin atoms to form chains of infinite length. The dimer 3 consists of a like ring, in which the tin atoms are bridged by methoxo groups. It crystallizes triclinic in space group with a = 946.4(1) pm, b = 963.7(1) pm, c = 1174.2(1) pm, α = 82.495(6)°, β = 66.451(6)°, γ = 74.922(6)°, and Z = 1 for the dimer. The Raman spectra of 2 and 3 are given and discussed.     

Die Photoionenspektren von SCl2, S2Cl2 und S2Br2

Photoionization Mass Spectra of SCl₂, S₂Cl₂, and S₂Br₂ Photoionization mass spectra of SCl₂, S₂Cl₂, and S₂Br₂ have been measured. Heats of formation, bond energies, and ionization potentials of fragments have been calculated from appearance potentials.