铝锶热还原Sc2O3制备铝钪中间合金

以Sc2O3为原料,液态铝锶合金为还原剂及合金基体,在nNaF·AlF3-NaCl-KCl熔盐体系中通过铝锶热还原制备了Al-Sc中间合金.主要考察了ScF3添加量、温度和时间对Sc含量及收率的影响.结果表明,熔盐中添加1％(质量分数,下同)的ScF3,反应温度900℃,反应时间45 min,制得了Sc含量在2％以上的Al-Sc中间合金,Sc的直收率可达74.25％.SEM,EDS和XRD分析结果表明,中间合金由黑白两相组成,白色间断相为不规则形状的Al3Sc第二相粒子,黑色连续相为铝基.     

微量Al-RE对Zn-2%Ni合金的组织细化研究

研究了RE，Al及Al-RE合金对Zn-2％（质量分数，下同）Ni合金组织中Zn-Ni合金相粒子的细化作用，利用扫描电镜（SEM）及能谱分析（EDS）等方法分析了合金凝固组织特点。结果表明：在Zn-2％Ni合金中，加入0．02％～1％RE会产生新的Zn—RE—Ni合金相粒子，对Zn-Ni合金相粒子没有明显的细化作用；加入0．02％～1％Al，虽然对Zn-Ni合金粒子有细化作用，但此合金组织不适宜在热镀锌中运用。在铝浓度较低（〈0．1％）时。凝固组织中的合金相粒子尺寸不均匀；当铝浓度较高（〉0．2％）时，高熔点、低密度β-NiAl相核心长大，合金相粒子易上浮，出现比重偏析；加入0．02％～0．2％Al-RE时，能形成细小弥散而均匀分布的异质晶核β-NiAl相，促进了γ-Ni2Zn5相的生成，获得细小且均匀分布的γ-Ni2Zn5相。Al-RE合金细化效果明显优于RE和Al，其最佳加入浓度为0．05％～0．1％。     

稀土-铁催化剂催化还原烟气中SO2制硫磺

以煤气为还原气,以Fe为主活性金属,稀土为助剂催化还原冶炼烟气中SO2制取硫磺,研究了不同稀土、不同稀土含量及不同催化剂制备方式对稀土-过渡金属催化剂催化还原SO2制硫磺活性的影响,并考察了其反应机制.结果表明:不同稀土对Fe/Al2O3催化剂有不同的改性作用,Sm和Dy的加人大大提高了催化剂的活性,在360 ℃时,smFe/Al2O3的硫产率增大到86.62%,比同温度下Fe/Al2O3的提高了40.5%;在400℃时,DyFe/Al2O3的硫产率增大到91.62%.比同温度下Fe/Al2O3的提高了26.4%;REFe/Al2O3催化剂的活性与稀土含量有一定的关系,对SmFe/Al2O3催化剂,稀土Sm的最佳含量为1.0%;不同方式制备的稀土催化剂活性不同,对硫产率来说其大小顺序为:钐铁溶液混浸>先浸钐后浸铁>先浸铁后浸钐;煤气还原SO2的反应机制为中间产物机制.     

铝钛硼稀土中间合金的微观组织及其细化纯铝机制研究

采用氟盐与稀土铝水反应法制取Al5Ti4RE1B中间合金,对其进行物相、微观组织和细化效果分析,通过深入观察细化处理后晶粒形貌和微区成分分析对细化机制进行了研究。XRD及EDS分析显示RE和TiAl3结合生成了Ti2Al20RE相,细化试验表明Al5Ti4RE1B比Al5Ti1B具有更强的细化能力。微观组织及面扫描结果显示细化后的晶粒呈菊花状,在花瓣的不同位置存在RE和Ti分布的不均匀性,热处理后晶粒花瓣减少,成分也趋于均匀。这是由于Ti2Al20RE相在铝液中逐渐溶解并释放出RE和Ti原子,而-αAl晶体以枝晶的方式生长,同时将稀土原子排到枝晶间,最终形成了菊花状组织及元素分布的不均匀性。     

镁电解槽中制备镁稀土合金的电解工艺及机制研究

在模拟镁电解槽中,采用电解法制备出稀土含量<10%的镁稀土合金;研究了熔盐中RECl3和CaCl2的含量、电解温度和阴极电流密度对合金中RE含量和电流效率的影响。并采用循环伏安实验和还原实验研究电解制备镁稀土合金的机制。研究结果表明,电解制备镁稀土合金最佳的工艺条件为:熔盐中RECl3和CaCl2的含量分别为3%和10%(质量分数),电解温度为948 K,阴极电流密度约为8 A.cm-2。其电解过程机制为:阴极上只电解出金属镁,而后金属镁把稀土元素还原出来,形成镁稀土合金。     

金属材料分析方法的选择和施行第六讲金属材料中稀土元素的测定(续)

2.萃取分离-CPA-mA分光光度法测定稀土总量(摘自国家标准GB/T 223.49-1994)[适用范围]:碳钢、合金钢、高温合金及精密合金[测定范围]:w(∑RE)0.001%~0.20%[方法提要](1)试样溶解:按试样中总稀土的估计含量称取0.100 0~1.000 0 g试样,置于烧杯中,溶于适量的浓盐酸和浓硝酸的混合     

Ca-Sm2O3-Fe体系生成Sm2Fe17的研究

对由Ca-Sm2O3-Fe体系通过还原扩散反应生成Sm2Fe17合金的过程进行热力学和动力学分析; 研究了产物Sm2Fe17合金的收率及Sm和残余CaO的含量. 结果表明 还原扩散法制备Sm2Fe17合金的收率较高, 均大于80%, 且残余CaO的含量极低, 均小于0.55%; 随着温度的上升和反应时间的延长, Sm2Fe17合金的收率和Sm2Fe17合金中Sm的含量均增大. 收缩核模型处理结果表明 液态Sm和固态Fe之间的包晶反应为整个还原扩散反应过程的控速步骤; 还原扩散反应的表观活化能为73.74 kJ·mol-1, 指前因子为7.79×10-3.     

稀土对镁-铝合金抗热裂性能的影响及其机制

研究了稀土（0.1%～1.2%,质量分数）对Mg-Al合金抗热裂性能的影响及其机制.结果表明： 往Mg-Al合金中添加稀土后,合金的抗热裂性能显著下降,其原因可归为： 稀土引起了Mg-Al合金晶粒粗化,使得热裂纹萌生所需的断裂应变降低;稀土减少了Mg-Al合金中的共晶组织,缩短了枝晶通道保持开通的时间,不利于合金进行补缩;而且稀土还提高了共晶反应的温度,使得凝固后期枝晶间液膜的强度有所下降;当α-Mg枝晶连成骨架时,分布在枝晶间的Al11RE3相容易堵塞枝晶通道,增加了合金补缩的难度;Al11RE3相与α-Mg基体的凝固收缩率不同,容易产生凝固收缩应力,促进热裂纹的萌生.     

氧化还原滴定法测定铝铬中间合金中铬

铝铬中间合金中铬含量较高(质量分数在2.0%～3.0%之间),采用二苯基羰酰二肼光度法测定铬[1],由于试液的吸取量太少易产生较大误差,无法保证结果准确度.本法采用氢氧化钠-过氧化氢溶解试样,硝酸酸化,在硫酸-磷酸介质中用过硫酸铵作氧化剂,将三价铬氧化成六价铬,用硫酸亚铁铵标准溶液滴定六价铬,测定铝铬中间合金及铝合金中高含量的铬.     

稀土碳锰纯净钢中夹杂物形成与转化的热力学计算及观察分析

用多相、多组元平衡的热力学计算方法, 对稀土碳锰纯净钢中夹杂物的析出和转化进行了计算. 结果表明, 稀土元素能有效地变质Al2O3夹杂, 在本实验所用材料的成分条件下, Al2O3完全消失的稀土含量为: 1600 ℃时, La>0.009%, Ce>0.01%; 1518 ℃时, La>0.012%, Ce>0.013%, 稀土变质Al2O3的产物主要为RE2O2S. 当La含量大于0.028%, Ce含量大于0.027%后, 体系中将会有RES产生, 但夹杂物仍然以RE2O2S为主. 对试样的扫描电镜观察和分析证实了热力学计算的结果.     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.