稀土元素对低碳Si-Mn-V钢马氏体自回火及低温回火分解过程的影响

采用透射电镜、膨胀仪和显微硬度测定等方法对含稀土和不含稀土的Si-Mn-V低碳钢马氏体自回火和低温回火分解过程进行了研究。结果表明,Si-Mn-V钢低碳马氏体自回火析出的碳化物既有ε-碳化物,又有θ-Fe_3C相,二者可以同时并存。而钢中含有少量稀土元素可以抑制低碳马氏体自回火碳化物的析出,影响自回火碳化物的析出类型。透射电镜原位动态观察还表明,稀土元素抑制了低碳马氏体在低温回火阶段的分解。     

钇基稀土合金在超高硬度堆敷金属中的应用研究

运用OM，SEM，XRD探究了重钇基稀土合金在超高硬度堆敷金属中的作用。钇基稀土合金对堆敷金属中析出的碳化物有变质球化作用。增加碳化物在基体中弥散分布的程度。稀土钇与氧、硫结合在净化堆敷金属的同时，改善了堆敷金属中夹渣物的形态。最终结果表明适量钇基稀土合金加入可以在对堆敷金属硬度提高的同时，改善其冲击功。     

稀土对于H13钢中大尺寸非均质形核碳化物的影响

通过加入不同的稀土含量对于H13钢中大尺寸碳化物的形核核心进行改质,研究了稀土对于形核核心的改质机理以及不同稀土含量对于形核核心的改质情况,并利用Factsage软件对于改质机理及完全改质形核核心的合理稀土加入量进行了理论计算。结果表明:稀土对于H13钢中大尺寸碳化物的形核核心具有良好的改质效果,随着稀土含量的增加,碳化物的形核核心的改质顺序为MgO·Al_2O_3—CeAlO_3—Ce_2O_2S或Ce_2O_3。错配度理论计算和实验表明MgO·Al_2O_3和CeAlO_3都能作为H13钢中大尺寸碳化物的形核核心,Ce_2O_2S和Ce_2O_3有效地抑制了大尺寸碳化物的非均质形核。合适的稀土加入量,MgO·Al_2O_3会被完全改质为稀土氧化物或稀土硫氧化物,达到减少H13钢中大尺寸碳化物数量的效果。热力学计算表明钢中氧含量越低,完全改质所需的稀土含量越少。     

稀土对20Mn钢等温相变及组织形态的影响

研究了不同稀土含量对20Mn钢等温相变及组织形态的影响。随钢中稀土含量的增加,先共析铁素体析出的孕育期缩短,完成珠光体相变所需时间延长;针状铁素体量减少直至消失;珠光体片间距变密且相对转变量减少;粒状贝氏体中碳化物易于偏聚。稀土减小原奥氏体晶界能和相界面能,稀土原子偏聚在相界面上阻碍碳原子的扩散,以及可能形成高熔点稀土碳化物而减少奥氏体中碳的固溶量,是产生上述结果的主要原因。     

稀土对管线钢中碳化物溶解与析出行为的影响

以X80管线钢为研究对象,研究了稀土对含铌钢奥氏体化与析出行为的影响。利用热力学固溶度积公式,计算了铌碳化物的溶解温度;借助显微组织观察与硬度测试,对比分析了稀土对高温下奥氏体晶粒粗化及不同温度淬火回火后硬度的影响;通过热模拟实验并利用透射电镜,研究了稀土对实验钢在热变形过程中铌碳氮化物析出行为的作用机制。结果表明:稀土元素的加入降低了碳氮化物的固溶温度,促进了Nb(C,N)等第二相粒子的固溶,稀土能够促进热变形过程中Nb(C,N)的析出,从而提高铌元素的析出强化效果。     

稀土对莱氏体钢共晶碳化物粒化的影响

研究了稀土对莱氏体钢中共晶碳化物热处理粒化的影响，探讨了稀土元素的作用机制。结果表明：稀土细化了莱氏钢中奥氏体晶粒和共晶碳化物，使离异共晶数量增多，减少了Ｃｒ、Ｍｏ合金元素偏析，并使Ｍ７Ｃ３（Ｍ＝Ｆｅ、Ｃｒ）碳化物中孪晶等晶格缺陷增多，从而降低碳化物的稳定性，促进了共晶碳化物的粒化动力学过程，得到良好的粒化效果。     

微合金钢中稀土对沉淀相和性能的影响

在Nb(Ti,V）微合金钢中，主要沉淀相分别为Nb(C,N),(Nb,Ti)(C,N)和V（C，N）。稀土降低沉淀相完全溶解的温度，增大奥氏体中沉淀相析出的孕育期，降低析出速率，抑制奥氏体中沉淀相的析出，在铁素体相区，稀土提高沉淀相的析出速率和数量，促进沉淀相的析出，其中稀土对铌沉淀相析出的作用影响最强。锻态钢中，稀土有促进细化球化析出相的作用，随稀土含量增加，沉淀相析出数量增加，但过量稀土，促进作用又减弱，稀土在保持微合金钢强度的情况下，显著改善其冲击韧性，尤其是低温韧性，微合金钢中添加适量稀土可获得更佳的综合性能。     

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。     

稀土对钢中碳化铌溶解和析出行为的影响

通过透射电镜，Ｘ射线衍射分析，电解相分析及热模热等手段，研究了稀土对控轧含Ｎｂ钢析出相－碳化铌的结构，溶解和析出行为的影响，实验结果表明，钢中加入稀土后，碳化铌颗粒变小且弥散分布，在９００－９５０℃碳化铌析出达最高值，随温度升高析出量急骤下降，１２００℃时碳化铌基本溶解，在奥氏体化温度下，稀上有抑制碳化铌析出的作用，随稀土量增加其作用愈显著，稀土使碳化铌在奥氏体区析出时间增长，沉淀析出速度降低。     

稀土对WC颗粒增强铁基体复合涂层组织结构的影响

采用氩弧熔覆技术在45号钢表面制备一层稀土WC颗粒增强铁基体耐磨复合涂层。通过扫描电镜(SEM)、X射线衍射(XRD)和能谱仪(EDS)等测试分析手段研究了稀土的引入对复合涂层中基体组织及碳化物的影响,并与未加稀土进行了比较。结果表明:引入稀土后,一方面优化了熔覆层组织中碳化物颗粒分布,降低了熔覆层组织中碳化物颗粒的团聚、桥接,且颗粒分布均匀;另一方面改善了熔覆层的组织,细化晶粒,减弱了熔覆过程中产生的树状晶,抑制了WC颗粒的溶解和鱼骨状碳化物的生成。在熔覆层组织中碳化物颗粒相主要有三种存在形式:原始未熔WC颗粒、与基体形成的复式碳化物及在凝固过程中重新结晶的W2C(或WC)。     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

A carbanion induced synthesis of highly congested pyrazole and imidazole containing heterocycles

An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Selective synthesis of 4,5-dihydroimidazo- and imidazo[1,5-a]quinoxalines via modified Pictet–Spengler reaction

An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction.