SiO2对铝合金熔体直接氧化的影响

本文研究了在高温空气氛中涂覆在Al-Mg-Si合金表面的SiO₂对铝合金直接氧化的影响规律。实验揭示了SiO₂对Al-Mg-Si合金熔体直接氧化生长表面的形态的影响规律,发现SiO₂有助于Al₂O₃/Al复合材料以光滑的方式进行氧化生长,提高了材料的致密度。实验还发现,SiO₂可消减Al-Mg-Si合金熔体直接氧化所需的孕育期,缩短Al₂O₃/Al复合材料的生长时间。     

等离子体电解氧化法制备多孔TiO2/V2O5复合物膜层及其增强光催化产氢活性

较差的光催化产氢效率极大地阻碍了TiO₂光催化剂的工业化应用。为此,本文在含有NH₄VO₃的磷酸盐溶液中,采用等离子体电解氧化(PEO)法制备了多孔TiO₂/V₂O₅复合膜光催化剂,通过扫描电子显微镜(SEM)、能谱仪(EDS)、X射线衍射(XRD)、X射线光电子谱(XPS)和紫外可见漫反射光谱(UV-Vis DRS)对其组成、结构及光吸收性质进行了表征,并采用气相色谱评价了薄膜催化剂的光催化产氢性能,研究了电解液中NH₄VO₃含量对膜的结构、组成和光催化产氢性能的影响。结果表明:复合膜催化剂主要由锐钛矿和金红石型TiO₂组成,具有微孔结构,V₂O₅主要以无定形形式存在于膜中,与TiO₂有很强的相互作用,影响TiO₂的晶面间距。研究发现,元素V抑制了TiO₂的结晶和金红石型TiO₂的形成,扩大了薄膜的光学吸收范围。针对Na₂S+ Na₂SO₃溶液中的光催化产氢性能的研究显示,在质量浓度为1 g/L NH₄VO₃的电解液中制备的TiO₂/V₂O₅薄膜的光催化活性最高,优于近年来报道的其他光催化剂。光催化重复实验表明,该复合膜催化剂具有较高的稳定性和较为恒定的光催化活性。     

补加合金成分对铝合金熔体直接氧化生长的影响

为了控制DIMOX工艺中复合材料的生长速度和体积,采用压差法补加合金,使剩余铝合金熔体的成分得到调整并与正在氧化生长的Al₂O₃/Al复合材料层保持连续接触。试验研究了补加合金成分对Al-3Mg-10Si合金氧化生长的影响作用。结果表明:补加纯Al或低Mg、Si含量的铝合金,能够降低合金熔体的含镁量,缩短材料生长前沿合金熔体成分到达Al₂O₃-(Al,Mg)两相区的时间,促进传质过程,加速材料生长,有利于获取较大体积的复合材料。     

超临界流体干燥法制备TiO2/ Fe2O3 和TiO2/ Fe2O3/ SiO2 复合纳米粒子及光催化性能

以TiCl₄ 、Fe (NO₃ )₃·9H₂O 和Na₂SiO₃19H₂O 为原料, 采用溶胶凝胶法结合超临界流体干燥法(SCFD)制备了纳米级TiO₂/ Fe₂O₃ 和TiO₂/ Fe₂O₃/ SiO₂ 复合光催化剂。以光催化降解苯酚对所得催化剂的催化活性进行了评价。结果表明, 纳米TiO₂/ Fe₂O₃ 复合粒子与单组分TiO₂ 比较, 复合粒子光催化活性高于单组分的TiO₂, 6h 苯酚降解率高达95.9 %。SiO₂ 的加入可以抑制纳米粒子粒径的长大和晶相的转变, 增强TiO₂ 纳米粒子的热稳定性。复合光催化剂中Fe₂O₃ 最佳掺入量为0.06 %, SiO₂ 最佳掺入量为10 %(摩尔分数) 。并用XRD、TEM 和FTIR 等手段进行了表征。TiO₂ 以锐钛矿型形式存在, SiO₂ 以无定性形式存在。比较了不同制备方法制得的TiO₂/ Fe₂O₃ 复合光催化剂, 得出超临界干燥法制备的光催化剂具有粒径小、比表面积大、分散性好、光催化活性高等特点。采用超临界流体干燥可直接得锐钛型纳米复合光催化剂。     

Y2O3添加量对Al2O3/ZrO2共晶陶瓷显微组织及力学性能的影响

为探索第三组元Y₂O₃添加对Al₂O₃/ZrO₂共晶陶瓷显微组织与机械性能的影响,本文利用低温度梯度的高温熔凝法制备了直径为20 mm的Al₂O₃/ZrO₂(Y₂O₃)共晶陶瓷块体,采用SEM、EDS及XRD技术对共晶陶瓷进行微结构分析,并利用维氏压痕法对其硬度和断裂韧性进行测试。SEM结果表明,凝固组织由群集的共晶团结构组成,随着Y₂O₃添加量的增加,共晶团形态由胞状转变为枝晶状,内部相间距在1~2 μm范围内变化。力学测试表明,Y₂O₃摩尔分数小于1.1%时,由于组织内部存在低硬度m-ZrO₂及微裂纹缺陷,故陶瓷硬度较低,约为(9.53±0.22 )GPa;当Y₂O₃摩尔分数为1.1%时,陶瓷硬度最大,约为(18.05±0.27)GPa;当Y₂O₃的摩尔分数大于1.1%时,由于共晶团边界区内气孔缺陷及粗大组织增多,引起陶瓷硬度值略有下降。低Y₂O₃摩尔分数添加时,陶瓷断裂韧性相对较高,约为(6.30±0.16)MPa·m^1/2,这与其内部存在大量微裂纹缺陷有关;随着Y₂O₃添加量的增加,陶瓷的微裂纹数量减少、边界区内缺陷增多,断裂韧性降低。     

Al2O3/Al-4.5Cu-Ce合金复合材料的界面现象

本研究采用座滴法和电子探针探讨了Al-4.5Cu-Ce合金的表面张力及其与Al₂O₃的界面润湿性、界面结构、界面结合方式和强度.得出:饰降低Al-4.5Cu合金的表面张力,提高Al₂O₃/Al-4.5Cu合金的润湿性和界面剪断应力;铈改善润湿性的机制是在界面上的吸附与富集,未发现铈与Al₂O₃的界面反应产物,界面仍属于直接结合界面.     

纳米-Al2O3/SiO2加入量对MgO-Al2O3-SiO2复相陶瓷烧结机理的影响

为了探究纳米-Al₂O₃/SiO₂加入量对MgO-Al₂O₃-SiO₂复相陶瓷烧结行为的作用机理。以微米级MgO、纳米级Al₂O₃和SiO₂为主要原料制备陶瓷基复合材料。通过XRD和 SEM等检测手段对烧后试样的物相组成和微观结构进行测试与表征,重点研究Al₂O₃/SiO₂的加入对复相陶瓷物相组成、微观结构及烧结性能的影响。结果表明:随着Al₂O₃/SiO₂加入量的增大,试样烧后相对密度和烧后线变化率呈先增大后减小再增大的趋势,加入15%Al₂O₃/SiO₂(质量分数)的试样经1 500 ℃烧结后,其相对密度可以达到94%。引入的Al₂O₃/SiO₂与基体中的MgO生成镁铝尖晶石与镁橄榄石相,原位反应伴随的体积膨胀,抵消部分烧结过程中的体积收缩。Al₂O₃/SiO₂加入量为75%(质量分数)的试样经1 400 ℃烧结后,基体中有大量堇青石相生成,随着煅烧温度提高到1 500 ℃,堇青石分解所产生的高温液相促进了试样的烧结收缩。     

原位生成Al2O3/Cu复合材料的新工艺

采用一种新型工艺制备了Al₂O₃/Cu复合材料。高能球磨制备亚稳态的Cu-0.8 wt% Al合金粉,再将Cu₂O粉与其一起进行高能球磨,然后将复合粉末压坯在真空炉中同时进行氧化和烧结。该工艺省略了还原剩余Cu₂O的环节,氧化和烧结时间仅为1 h。生成的Al₂O₃的粒径约250nm,颗粒间距约500 nm,均匀弥散分布;该材料冷加工后性能接近SCM制品性能。该配比的Al₂O₃/Cu复合材料的热稳定性良好,在800℃下循环冷淬20次无裂纹;软化温度为700℃。     

ZA22/Al2O3复合材料切削加工表面质量的研究

采用硬质合金刀具研究了挤压铸造Al₂O₃短纤维强化ZA22合金复合材料的切削加工表面质量。发现在相同切削条件下,该复合材料表面质量优于ZA22合金。高的切削速度、低的进给量及低的切削深度有利于提高该复合材料的切削加工表面质量。随Al₂O₃纤维体积分数增大,复合材料切削加工表面粗糙度降低。     

亚微米Al2O3P/Al-Mg-Si复合材料时效行为

为了研究亚微米级Al₂O₃颗粒对基体合金时效过程的影响规律,在 6061 铝合金基础上调整Mg、Si含量,采用压力浸渗法,制备了Al₂O₃体积分数为30%的亚微米级Al₂O_3P/Al-2.26Mg-0.63Si复合材料。通过硬度试验、SEM和TEM等手段,研究了复合材料及其基体合金的时效行为。结果表明,Al-2. 26Mg-0.63Si 合金的时效过程比较明显,随时效温度的提高峰时效时间提前,190℃时出现时效软化现象。亚微米Al₂O₃颗粒的加入强烈抑制复合材料的时效过程,时效曲线未出现明显时效峰。分析认为,由于大部分Mg 元素被消耗在界面形成MgAl₂O_4,且基体中位错稀少,不利于溶质原子扩散,因此复合材料中沉淀相在过时效阶段仍停留在GP区状态,没有充分长大,时效析出受到抑制。     

Structure and Superconducting Properties of Cd0.8Ba2(Y0.7Ca0.4)Cu3.5Oy

A new Cd-containing superconductor with nominal composition ofCd_0.8Ba₂(Y_0.7Ca_0.4)Cu_3.5O _y was synthesized and investigated. The obtained Cd and Ca-doped 123 phase exhibits an orthorhombic (T _c=80 K) or tetragonal (T _c=65 K) modification depending on the reaction atmosphere. It was shown that the combined Cd and Ca substitution facilitates the 123 phase formation. The results of the EDX analysis, as well as the comparison of the obtained lattice parameters with those of undoped, Cd-doped, and Ca-doped 123 have shown that both Cd and Ca enter the 123 phase and form a new Cd–Ba–Y–Ca–Cu–O superconducting compound.     

Some thermodynamic aspects of the high-temperature transition in doped V2O3

Measurements of the entropy change are reported for the high-temperature metal-insulator (MI) transitions in the (V_1–xCr_x)₂O₃ and (V_1–xAl_x)₂O₃ systems. It is emphasized that the entropy of the I phase exceeds that of the M phase. Evidence is presented to show that the M and I phases coexist over a narrow temperature range. The transformation is attended by enormous hysteresis effects; these indicate that the lattice plays an important role in the transition. The probable role of Cr³⁺ and Al³⁺ as a dopant in the V₂O₃ lattice is briefly discussed. A phase diagram for the dilute V₂O₃-Al₂O₃ alloy system is presented.     

Chemical control of superconducting properties of (Y, Ca)(Sr, Ba)2Cu2.7Ga0.3O7?δ

The partial substitution of Ga at the Cu(1) (chain) sites of the YBa₂Cu₃O₇ structure allows synthesis at ambient pressure of Ba-free analogs, e.g., YSr₂Cu_2.7Ga_0.3O_7– . Materials with this composition have been found to be nonsuperconducting, but superconductivity has been induced by one or more of the following methods: Ca substitutions at the Y site; Ba substitutions at the Sr site; annealing in high-pressure oxygen. The influence of these chemical manipulations onT _c has been monitored and all methods have been found to enhanceT _c . The electronic effects of Ba substitutions have been deduced indirectly using powder neutron diffraction, and such substitutions appear to result in a redistribution of hole density into the Cu(1) sites from the superconducting CuO₂ planes.     

Microstructural study of YBa2Cu3O7/SrTiO3/YBa2Cu3O7 heteroepitaxial trilayer films grown on (100) SrTiO3 substrates

Detailed transmission electron microscopic study has been carried out on heteroepitaxial YBa₂Cu₃O₇/SrTiO₃/YBa₂Cu₃O₇ trilayer thin films grown on (100)SrTiO₃ substrates prepared by DC and RF magnetron sputtering. The microstructural results showed the existence of somea-axis-oriented YBCO grains 20–90 nm wide in thec-axis-oriented YBCO matrix. Some of thea-axis grains in the lower YBCO thin film layer have protruded into the above SrTiO₃ layer, which may cause short circuit between the two YBCO superconducting layers. This is unsuitable for the application of trilayer thin films for microelectronic devices. The defects on the surface of the substrates would also influence the growth quality of the YBCO thin films.     

Structural and magnetic study of nitrided Co74Fe8B12Si6 and Co74Fe4Mn4B12Si6 ribbons

The nitriding thermochemical treatment (NTT) is commonly used for steels. In this paper, the experimental conditions required for NTT, and the influence of such treatments on the structure and hysteresis loops of Co₇₄Fe₈B₁₂Si₆ and Co₇₄Fe₄Mn₄B₁₂Si₆ ribbons are reported. The results have been compared with those obtained with ribbons treated according to conventional thermal treatment (CTT) as well.     

Luminescence properties of Sn2P2Se6 crystals

A large family of Sn_2yPb_2(1−y)P₂S_6xSe_6(1−x) semiconductor-ferroelectric crystals were obtained by the Bridgman technique. The photoluminescence properties of the Sn_2yPb_2(1−y)P₂S_6xSe_6(1−x) family crystals strongly depend on their chemical composition, excitation energy and temperature. The influence of the Pb → Sn and S → Se isovalent substitutions on the luminescence properties of a crystal with the Sn₂P₂Se₆ basic composition was investigated. A broad emission band observed in the Sn₂P₂Se₆ crystal with a maximum roughly at 600 nm (at T = 8.6 K) was assigned to a band-to-band electron-hole recombination, whereas broad emission bands, peaked near 785 nm (at T = 8.6 K) and 1025 nm (at T = 44 K) were assigned to an electron-hole recombination from defect levels localised within the bandgap. Possible types of recombination defect centres and specific mechanisms of luminescence in the Sn₂P₂Se₆ semiconductor-ferroelectric crystals were considered and discussed on the basis of the obtained results and the referenced data.     

Electron-Impact Total Ionization Cross Sections of Hydrocarbon Ions

The Binary-Encounter-Bethe (BEB) model for electron-impact total ionization cross sections has been applied to CH2+, CH3+, CH4+, C2H2+, C2H4+, C2H6+ and H₃O⁺. The cross sections for the hydrocarbon ions are needed for modeling cool plasmas in fusion devices. No experimental data are available for direct comparison. Molecular constants to generate total ionization cross sections at arbitrary incident electron energies using the BEB formula are presented. A recent experimental result on the ionization of H₃O⁺ is found to be almost 1/20 of the present theory at the cross section peak.     

Synthesis of a novel langanite-type compound La3Al5.5Nb0.5O14 by the sol-gel process

Langanite (La₃Ga_5.5Nb_0.5O₁₄, LGN) and its isomorphs are a few piezoelectric materials which have the unique temperature compensation and piezoelectric properties. But the high Ga₂O₃ content makes them very expensive and limits their applications. We reported a new langanite-type compound La₃Al_5.5Nb_0.5O₁₄ (LAN) which has the advantage of no Ga₂O₃ content. Chemically homogeneous La₃Al_5.5Nb_0.5O₁₄ sol was synthesized using La (NO₃)₃·6H₂O, Al (NO₃)₃·9H₂O and niobium citrate as starting materials. Single-phased LAN powder was prepared by decomposition of a citrate polymer precursor and subsequent reactions at high temperatures. TG-DTA, XRD and FTIR were employed to investigate the transformation process of gel to LAN powder. The results showed that, after calcination at 900 °C, pure La₃Al_5.5Nb_0.5O₁₄ polycrystalline powder with a narrow particle size distribution was obtained, which has the same structure with La₃Ga_5.5Nb_0.5O₁₄.     

Low-temperature preparation of some perovskites La2MM′O6 (M,M′=Cr,Mn, Fe,Co, Ni,M≠M)

The low-temperature preparation of some La₂MM′O₆ compounds (M,M′=Cr, Mn, Fe, Co, Ni, M≠M′) by the decomposition of coprecipitated basic carbonates is described. Single phase compounds are formed. The stability of physical properties of these phases towards further heating depends on the M and M′ ions. The results are interpreted in terms of the stability of the M-M′ oxidation states. Communication No. 122 from the Solid State and Structural Chemistry Unit     

Use of oxygen isotope to study the transport mechanism during high temperature oxide scale growth

Abstract

The examination of high temperature (HT) oxide scale growth mechanisms was performed using secondary ion mass spectrometry (SIMS) and secondary neutral mass spectrometry (SNMS), in conjunction with ¹⁶O₂/¹⁸O₂ HT oxidation experiments. Cr₂O₃, NiO, ZrO₂ and Al₂O₃ were studied because they constitute excellent representative thermally grown oxide scales: they grow by cationic diffusion (Cr₂O₃, NiO), anionic diffusion (ZrO₂) or mixed anionic-cationic diffusion (Al₂O₃). The oxidation tests were performed first in ¹⁶O₂ and subsequently in ¹⁸O₂ at several temperatures (600–1000°C for NiO, 600°C for ZrO₂, 1000°C for Cr₂O₃ and 1100°C for Al₂O₃). The oxygen isotope distribution observed by SIMS and SNMS profiles are discussed and related with the HT oxidation mechanisms proposed in the literature.