铈对锰钒钢过冷奥氏体转变的影响

研究了稀土元素铈对锰钒钢中先共析铁素体转变和贝氏体转变的影响。测定了先共析铁素体形核率和恒温转变动力学曲线。同时,观察了组织转变特征。结果表明,铈明显地推迟先共析铁素体转变,降低形核率。此外铈也推迟贝氏体转变。     

稀土复合变质贝氏体/马氏体钢的研究

研究了稀土复合变质对贝氏体／马氏体复相铸钢组织和性能的影响。实验结果表明，钢中加入稀土，由于合金化、变质作用使钢的微观组织形态发生变化，经变质，钢的晶粒细化，空淬组织中板条马氏体、贝氏体比例增加，残余奥氏体数量提高，夹杂物形态改善，从而提高了钢的韧性和耐磨性。     

惰气熔融-红外吸收光谱法测定镧铈稀土钢中氧含量

高品质稀土钢要求进行精确低氧含量控制,而依据现有GB/T11261-2006标准进行氧含量测定,检测结果具有较大的不准确性。本研究以具有不同镧、铈稀土元素含量的稀土钢为对象,以其氧含量精确测定为目标,基于惰气熔融-红外吸收法,开展了分析功率、助熔剂和称样量对镧铈稀土钢中氧含量分析结果的影响研究。结果表明,对于不同镧、铈元素含量的稀土钢,需要采用不同的分析方法：当稀土钢中的镧、铈含量较低时,通过降低分析功率即可较为精确的测定稀土钢中的氧含量;对于镧、铈含量较高的稀土钢,在调控分析功率（分析功率在4000W～4500W）的基础上,需同时采用锡作为助熔剂,并将助熔剂与样品比例设定为1:1（称样量为0.3g～0.6g）,即可实现氧含量的精确测定。精密度验证实验结果显示,采用本研究所建立的方法,氧含量测试结果相对标准偏差（RSD）小于8.0%;采用钢标样进行回收率实验,回收率值在97%～108%,而加标回收率略有升高的原因在于助熔剂Sn降低了合金熔点,使少量难熔氧化物中的氧得到更充分释放。本研究所建立的分析方法可准确测定不同镧、铈元素含量稀土钢中的氧含量。     

稀土对高铬铸铁碳化物形态及相变动力学的影响

研究了稀土元素对高铬铸铁中碳化物的影响，并对加稀土、不加稀土的高铬铸铁试样的连续冷却转变（ＣＣＴ）曲线进行了测定。结果表明，稀土元素能破碎高铬铸铁中的碳化物，使碳化物由网状、长条状向岛状、块状过渡。同时，稀土元素提高了高铬铸铁的固态相变温度并缩短了贝氏体的孕育期。     

钢中的铈碳化物

本实验发现了钢中存在稀土碳化物,并用金相、电子探针、俄歇能谱、X射线衍射和电解分离方法进行了鉴定和分析。揭示了钢中铈碳化物的生成条件、分布、组成、光学性质、某些化学性质和高温下的转变。已证明在空气中高温下钢中的铈碳化物将变为含碳的CeO_2。钢中生成铈碳化物后会降低珠光体的含量。     

稀土复合变质对新型铸造热锻模具钢组织与性能的影响

研究了稀土复合变质对新型铸造热锻模具钢（CHD钢）组织与性能的组织。结果表明，稀土复合变质能细化晶粒，并且随着稀土量的增加。细化效果明显；加入适量的稀土复合变质后，夹杂物数量明显减少，夹杂物趋于球化并均匀地分布在钢中，形态和分布得以了改善，向钢中加入稀土进行复合变质，能促进贝氏体、奥氏体和位错亚结构的形成，细化马氏体板条。当残留稀土含量为0.02%时，CHD钢的硬度、强度变化不大，断裂韧性（KIC）和疲劳裂纹扩展门槛值（△Kth）有所提高，冲击韧性、延伸率、断面收缩率提高了近一倍，抗热疲劳性能也最好。     

碳锰洁净钢中镧和铈在晶界的行为

应用高分辨TEM，SEM和XRD研究碳锰洁净钢中镧和铈的存在形式、分布以及在晶界的行为。研究结果表明，镧和铈在洁净钢中存在固溶态、稀土夹杂物和稀土第二相。固溶稀土偏析在晶界，洁净钢中稀土仍有净化钢液和变质夹杂的作用。适量稀土能减少S和P在晶界的偏析，净化晶界提高钢的冲击韧性。过量稀土在晶界产生有害的稀土第二相，导致性能显著降低。     

电感耦合等离子体发射光谱(ICP-OES)法测定稀土钢中微量镧、铈

采用稀王水溶解样品,选择La 408.672 nm、Ce 456.236 nm为分析线,建立了电感耦合等离子体发射光谱(IC P-O ES)法测定稀土钢中微量镧、铈的方法.结果表明,各元素校准曲线线性良好,相关系数可达0.99999;方法测定范围为0.0001％ ～0.10％.检出限为镧0.00002％,铈0.0000...     

稀土对碳锰纯净钢耐腐蚀性能的影响

在碳锰纯净钢中加入稀土元素镧和铈, 用电化学方法测定了腐蚀电流icorr和点蚀特征电位Eb. 结果表明, 稀土种类和含量对碳锰纯净钢的腐蚀性能存在影响, 镧、铈的适宜含量分别为0.011%和0.014%左右. 稀土的作用与它引起的组织变化和对极化过程中试样表面状况的影响有关.     

铈对粒状贝氏体钢组织与性能的影响

研究了铈在低碳粒状贝氏体钢中的合金化作用，结果表明，铈能增大粒状贝氏体相奕的孕育相；影响粒贝相变的形核和长大方式：细化空冷粒贝组织。     

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.