混合稀土基大块非晶合金的制备及力学性能

用铜模铸造法成功制备出直径为3mm以混合稀土金属Mm（Mischmetal）为基的Mm55Al25Ni10Cu5Co5大块非晶合金。利用XRD和DSC等手段对该合金的形成能力及热稳定性进行了分析。结果表明：该合金具有很好的非晶形成能力及热稳定性，存在明显的玻璃转变温度Tg、宽的过冷液相区△Tx=Tx-Tg（〉60K）及高的约化玻璃转变温度Trg=Tg／Tm（〉0．67）。同时，该合金强度较高，其压缩断裂强度（σf）为676MPa，比La55Al25Ni10Cu5Co5大块非晶提高94MPa。另外，Mm55Al25Ni10Cu5Co5大块非晶合金的成本较低。     

三乙酸甘油酯玻璃化转变的焓弛豫与介电弛豫研究

脆性较高的玻璃形成分子液体通常在焓弛豫和介电弛豫动力学上表现出明显的差异性, 为了深入理解这一问题, 本文针对具有较高液体脆性的三乙酸甘油酯对比研究了焓弛豫与介电弛豫行为. 利用这两个技术分别研究了结构弛豫动力学过程的非Arrhenius 与非指数特征, 液体脆性因子与非指数性因子的对比显示很好的一致性. 分析表明分子的柔性有可能对这两种弛豫过程中分子运动的相关性产生明显的影响. 讨论了玻璃形成液体的分子结构与动力学参数之间的关联.     

Nd60Fe20Al10Co10非晶粉末晶化过程及动力学研究

利用机械合金化制备出Nd60Fe20Al10Co10非晶粉末,采用示差扫描量热仪(DSC),X射线衍射(XRD)和振动样品磁强计(VSM)考察了Nd60Fe20Al10Co10非晶的晶化转变过程及其对磁性能的影响规律,用Kissinger方程计算了Nd60Fe20Al10Co10的晶化激活能,从晶化动力学的角度讨论了玻璃形成能力与晶化反应速率常数的关系。结果表明,Nd60Fe20Al10Co10合金的晶化过程为:非晶+α Fe→非晶+α Fe+Nd→非晶+α Fe+Nd+未知相Mx→α Fe+Nd+未知相Mx+Co2Nd+AlCo。晶化激活能E约为173kJ·mol-1。非晶相的的弛豫无序结构是Nd60Fe20Al10Co10具有硬磁性的原因。完全晶化后硬磁性迅速消失。     

Mg65Cu25Gd10和Mg65Cu20Zn5Gd10基大块非晶合金的制备及其力学性能

利用铜模喷注法可以制备出直径为5 mm的Mg65Cu25Gd10的非晶合金,将Mg65Cu25Gd10的Cu用Zn部分代替后,制备出的Mg65Cu20Zn5Gd10合金的非晶形成能力（GFA）并未得到提高。在室温下,Mg65Cu25Gd10的非晶合金有很高的强度,而在玻璃转变温度附近,在温度大于403 K时,.ε=5×10^-4s^-1和2.5×10^-4s^-1两种应变速率下的流变应力小于100 MPa,塑性很好,非常适合塑性成型。     

电感耦合等离子体质谱法测定镁合金中的多种元素

用电感耦合等离子体质谱(ICP-MS)法测定了镁合金中的Be、Al、Ca、Fe、Mn、Ni、Cu、Zn、Ag、Cd、Sn、La、Ce、Pb14种元素,进行了稳定性实验以及Cu、Zn、Ni、Mg、Al基体实验,考察了共存元素的干扰.镁合金标准物质测定值与参考值符合较好,方法检出限为0.0002～0.3346 μg/g,相对标准偏差RSD＜10%.     

Ni-Cu/La2O3催化剂上甲烷部分氧化制合成气

用浸渍法制备了不同Cu质量分数的Ni Cu/La2O3双金属催化剂，考察了金属浸渍顺序和Cu质量分数对催化剂甲烷部分氧化性能的影响,并通过BET、XRD、TPR和SEM等技术对催化剂进行了表征。结果表明,在甲烷部分氧化制合成气反应中，Cu助剂的添加对Ni/La2O3催化剂的活性有一定的改进作用，其中浸渍顺序对催化剂的性能影响很大，共浸渍制备的催化剂活性相对较好；Cu质量分数为5%~7%时催化剂有较好的活性和稳定性；XRD等测试表明,Cu和Ni金属由于相同的晶型结构及离子半径在制备过程中形成了双金属固溶体，提高了活性组分Ni的分散度，减少了Ni晶粒的烧结聚集长大，从而提高了催化剂的活性和稳定性。     

快速凝固AlNiCuNd纳米/非晶复合材料的制备及显微组织研究

采用熔体单辊旋淬法制备了快凝Al87Ni7Cu3Nd3合金条带,利用差热扫描热力学(DSC)分析、X射线衍射(XRD)分析等手段对比研究了快凝合金条带及其不同退火态材料的晶化行为.选择合适工艺条件,对快凝合金条带进行等温加热退火,采用高分辨透射电镜(HRTEM)观察分析了等温退火态材料显微组织特征.结果表明,快凝Al87Ni7Cu3Nd3合金薄带呈现出完全均匀的非晶态结构.随加热温度升高,非晶态薄带的晶化过程包括两个主要的相转变: α-Al晶体从非晶基体中析出的初始晶化以及有Al3Ni,Al11Nd3和Al8Cu3Nd形成的第二次晶化过程.在低于310 ℃下加热,快速凝固Al87Ni7Cu3Nd3金属玻璃中发生的主要相转变是富Al非晶的初始晶化.110 ℃等温退火态薄带主要是由α-Al加残余非晶相的两相组成,α-Al晶体纳米颗粒均匀弥散分布在残余非晶基体上.而在310 ℃热暴露后的退火试样中,在除α-Al晶体外的残留非晶相中开始出现极少量的Al3Ni金属间化合物.     

典型含氮螯合树脂对铜镍离子吸附分离特性的研究

选择典型含氮螯合树脂IRC747作为高选择性吸附剂,系统研究其对单组份及双组份Cu(II)与Ni(II)的吸附分离行为。单组份静态实验结果表明,静态吸附等温线和动力学过程可以采用Langmuir方程和Lagergren二级动力学方程拟合。通过分析吸附作用前后树脂理化结构,推测螯合树脂与重金属离子的配位结合形式是以N原子和磷酸羟基上的O原子组成的五元环,并通过DFT理论模型进行了计算验证。在Cu(II)/Ni(II)双组份体系中,Cu(II)和Ni(II)的竞争吸附行为可用Extended Langmuir模型较好地描述。高浓度Ni(II)条件下,Cu(II)在IRC747树脂上有更好的吸附选择性能,在前230BV、245BV出水中,Ni(II)纯度分别高达100%、99.999%,经过简单的电解浓缩处理后可回收利用,并设计高纯镍制备工艺流程,为树脂在高纯金属制备方面提供了理论和技术上的支持。     

Ni-Zr-Al基非晶合金催化剂的苯加氢催化性能

 利用快速凝固技术制备了Ni23.3Zr6.7Al64Cu2.3Ce3.7非晶态合金,用碱洗抽Al的方法进行活化,制成了Ni-Zr基非晶态合金催化剂(A＞50 m2/g), 并考察了其对苯加氢反应的催化性能. 结果发现,这种新型催化材料的比活性高出常规Raney Ni催化剂约375%. 反应动力学分析表明,苯加氢反应级数对氢基本上表现为一级,表观反应活化能约为31.2 kJ/mol, 并推导出苯加氢反应的动力学方程.     

碳纳米管-Mg65Cu25Gd10非晶复合材料玻璃转变的动力学性质

制备了Mg65Cu25Gd10大块非晶合金及其碳纳米管（CNTs）复合材料，对两种材料进行了不同扫描速率下的差热扫描量热分析，研究了加入CNTs对材料玻璃转变和晶化动力学效应的影响。结果表明：加入CNTs后，复合材料的玻璃转变和晶化行为仍然具有动力学效应，但加入的CNTs减小了材料晶化行为对升温速率的依赖程度；同时，加入CNTs加大了材料发生玻璃转变时需要克服的能量势垒，增大了峰值温度时的晶化反应速率常数，从而降低了材料的玻璃形成能力（GFA）；对CNTs降低GFA的原因也进行了探讨。     

10-Alkyl-10-demethylcolchicines

It is shown that colchicine ( 4 ) can regiospecifically be transetherified at C(10) by heating in ROH in the presence of (RO)₄M (M = Ti, Zr; cf. Scheme 2). (PrO)₄Zr in PrOH gives better yields than (PrO)₄Ti in PrOH, and also in the catalytic variant of the conversion is (PrO)₄Zr more effective than (PrO)₄Ti.     

Diaryldichalcogenide radical cations

One-electron oxidation of two series of diaryldichalcogenides (C₆F₅E)₂ (13a–c) and (2,6-Mes₂C₆H₃E)₂ (16a–c) was studied (E = S, Se, Te). The reaction of 13a and 13b with AsF₅ and SbF₅ gave rise to the formation of thermally unstable radical cations [(C₆F₅S)₂]˙⁺ (14a) and [(C₆F₅Se)₂]˙⁺ (14b) that were isolated as [Sb₂F₁₁]^– and [As₂F₁₁]^– salts, respectively. The reaction of 13c with AsF₅ afforded only the product of a Te–C bond cleavage, namely the previously known dication [Te₄]²⁺ that was isolated as [AsF₆]^– salt. The reaction of (2,6-Mes₂C₆H₃E)₂ (16a–c) with [NO][SbF₆] provided the corresponding radical cations [(2,6-Mes₂C₆H₃E)₂]˙⁺ (17a–c; E = S, Se, Te) in the form of thermally stable [SbF₆]^– salts in nearly quantitative yields. The electronic and structural properties of these radical cations were probed by X-ray diffraction analysis, EPR spectroscopy, and density functional theory calculations and other methods.     

10,10-二吡啶甲基-9,10-二氢蒽的合成研究

蒽酮1和氯甲基吡啶盐酸盐2在甲苯中回流反应生成10,10-二吡啶甲基-9(10H)蒽酮(3),收率63％～68％;3用硼氢化钠还原生成10,10-二吡啶甲基-9,l0-二氢蒽-9-醇(4),收率87％～90％;蒽醇4在酸催化下发生歧化反应,得到还原产物10,10-二吡啶甲基-9,10-二氢蒽(5)和氧化产物蒽酮3.该歧化反应受催化剂、溶剂和反应温度等影响.当蒽醇4用三氟化硼为催化剂、甲苯为溶剂、回流反应,5的收率达到74％.所合成的新化合物都经1H NMR,13C NMR,MS和元素分析表征确认.     

Evidence for homo-conjugation between two revolving 14pi-electron systems in 10b-methyl-10c-[2-(10b,10c-dimethyl-10b,10c-dihydropyrenyl)]-10b,10c-dihydropyrene

Ring contraction followed by an elimination reaction on anti-9-methyl-18-trans-2-(10b,10c-dimethyl-10b,10c-dihydropyrenyl)-2,11-dithia[3,3]metacyclophane gave the desired compound 10b-methyl-10c-[2-(10b,10c-dimethyl-10b,10c-dihydropyrenyl)]-10b,10c-dihydropyrene. 1H NMR spectroscopic analysis indicated a ring current effect over a considerable distance from the macro-molecular plane of each of the aromatic rings with the two pi systems freely rotating. Bathochromic shifts and peak broadening in its electronic spectrum clearly supports the presence of through-space pi-pi interactions between the two aromatic rings. This should serve as a good model to verify homo-conjugation effect in such a novel system where the two pi systems are freely revolving.     

One-pot synthesis of VO x /Al 2 O 3 as efficient catalysts for propane dehydrogenation

Vanadium oxides, as highly efficiently catalysts, are widely applied in various catalytic reactions, such as the dehydrogenation of light alkanes and epoxidation of alkenes. In this paper, a series of VO _x /Al ₂ O ₃ catalysts were fabricated by the 1-pot method for catalytic propane dehydrogenation. The results indicated that the VO _x /Al ₂ O ₃ catalysts with loading of 10 wt.% vanadium exhibited optimized catalytic performance. The as-prepared catalysts were characterized by N ₂ adsorption-desorption, XRD, TEM, H ₂ -TPR, and XPS to explore the texture properties, morphology, and electronic environment of vanadium. In addition, several vanadium catalysts were also prepared by the incipient wetness impregnation (IWI) method to compare their catalytic performance with the 1-pot synthesized catalysts. The catalysts synthesized by the 1-pot method exhibited higher selectivity of propylene and longer catalyst lifetime at high propane conversion when compared to the counterpart synthesized by the IWI method.     

A hexanuclear gold carbonyl cluster

The hexanuclear gold carbonyl cluster [PPh₄]₂[Au₆(CF₃)₆Br₂(CO)₂] (4) has been obtained by spontaneous self-assembly of the following independent units: CF₃AuCO (1) and [PPh₄][Br(AuCF₃)₂] (3). The cyclo-Au₆ aggregate 4, in which the components are held together by unassisted, fairly strong aurophilic interactions (Au···Au ∼310 pm), exhibits a cyclohexane-like arrangement with chair conformation. These aurophilic interactions also result in significant ν(CO) lowering: from 2194 cm^–1 in the separate component 1 to 2171 cm^–1 in the mixed aggregate 4. Procedures to prepare the single-bridged dinuclear component 3 as well as the mononuclear derivative [PPh₄][CF₃AuBr] (2) are also reported.     

Crystalline transition in Nylon 10 10

Variable‐temperature X‐ray diffraction was used to monitor the crystalline transition of Nylon 10 10. It could be found that the α‐phase of the sample transforms into a γ‐phase at about 135°C, if the sample is heated from room temperature to a high temperature, which is the so‐called Brill transition of Nylon 10 10. In addition, Nylon 10 10 was found to crystallize directly in a kind of α‐phase from the melt at high temperature, which is much different from the behavior of Nylon 66 and Nylon 10 12. Upon further cooling to room temperature, Nylon 10 10 preserved the α‐phase revealing two peaks in its XRD patterns. However, if the Nylon 10 10 sample with γ‐form was not melted, but immediately cooled from a temperature between T_B and T_m, the reverse transition from γ‐form to α‐form could be observed at about 130°C, indicating reversible Brill transition of Nylon 10 10.     

Conducting polyfurans by electropolymerization of oligofurans

Polyfurans have never been established as useful conjugated polymers, as previously they were considered to be inherently unstable and poorly conductive. Here, we show the preparation of stable and conducting polyfuran films by electropolymerization of a series of oligofurans of different chain lengths substituted with alkyl groups. The polyfuran films show good conductivity in the order of 1 S cm^–1, good environmental and electrochemical stabilities, very smooth morphologies (roughness 1–5 nm), long effective conjugation lengths, well-defined spectroelectrochemistry and electro-optical switching (in the Vis-NIR region), and have optical band-gaps in the range of 2.2–2.3 eV. A low oxidation potential needed for polymerization of oligofurans (compared to furan) is a key factor in achievement of improved properties of polyfurans reported in this work. DFT calculations and experiments show that polyfurans are much more rigid than polythiophenes, and alkyl substitution does not disturb backbone planarity and conjugation. The obtained properties of polyfuran films are similar or superior to the properties of electrochemically prepared poly(oligothiophene)s under similar conditions.