热变形奥氏体静态再结晶行为的研究

本文利用双道次压缩的方法,在Gleeble1500热模拟实验机上研究了低碳钢SS400在变形间隔时间内奥氏体的软化行为,以便为制定合理的细化晶粒轧制工艺提供实验和理论基础.采用后插法计算了在不同真应变条件下的静态再结晶率.通过双道次压缩测试静态软化动力学实验的表明,实验钢变形后很容易发生静态软化.在真应变为0.4,0.2时,静态再结晶激活能分别是Qrec=189.3,179.2kJ/mol.     

基于CSP工艺铽对Q345B再结晶的影响

以CSP工艺生产的Q345热轧钢板为研究对象,采用Gleeble-1500D热模拟实验机进行单、双道次轧制模拟实验,研究了稀土铽(Tb)对Q345B钢再结晶行为的影响.结果表明,稀土铽(Tb)能够明显地推迟Q345B钢的动态再结晶,使对应峰值应力在低温轧制时提高约10%,而对980℃以上时的峰值应力影响不明显;980℃以上轧制时,稀土铽(Tb)能够明显的降低间隔时间1.5 s时的静态软化率,但随间隔时间的增加,稀土铽(Tb)对静态软化率的影响减弱;加入稀土铽能够提高完全再结晶区温度,扩大部分再结晶区.     

CSP工艺条件下稀土对低碳结构钢热轧过程中再结晶行为的影响

为研究稀土在CSP连续轧制过程中对低碳结构钢再结晶行为影响,采用Gleeble-1500热模拟机,对加稀土和未加稀土的低碳结构钢进行了单道次、双道次热压缩实验,并且对加稀土和未加稀土的低碳结构钢进行CSP工艺的模拟,比较金相照片及真应力-应变曲线。实验结果表明:稀土提高了低碳结构钢的动态再结晶临界应变εD,在一定温度下降低静态软化率;并且在CSP热轧过程中采用加入稀土的方法,最终获得较未加稀土试样更为细小的晶粒组织。     

稀土微合金元素对U71 Mn,REⅡ重轨钢动态再结晶的影响

采用Gleeble-1500D热模拟实验机.研究了不同变形条件下U71 Mn,REⅡ重轨钢动态再结晶行为及微合金元素RE对其的影响.实验结果表明:变形温度越高,变形速率越低,动态再结晶越容易发生;由于微合金元素RE的作用,使REⅡ的动态再结晶开始时间延长,变形奥氏体的动态再结晶的名义激活能提高,对奥氏体的动态再结晶起到抑制作用.     

铈对IF钢热变形行为的影响

利用Gleeble-1500D热模拟试验机对Ce微合金化IF钢在变形温度790~950℃,应变速率0.1~5 s-1,变形量50%条件下进行了单道次压缩试验,研究了变形条件对试验钢热变形行为的影响,结合热模拟组织金相分析及双曲正弦本构方程、动态再结晶动力学方程分析了钢中Ce含量对IF钢动态再结晶行为的影响。结果表明:随着变形温度的降低和应变速率的增加,试验钢的变形抗力增大;添加Ce后,试验钢的热变形激活能增大,由122.92 kJ·mol-1增加到182.75 kJ·mol-1;Avrami方程指数kd由3.796减小到3.377,动态再结晶分数Xd也相应减小,动态再结晶被抑制,并随着钢中Ce含量的增加,抑制作用越显著。     

Cu-0.8Mg-0.15Ce合金热变形行为与机制研究

通过Gleeble-1500D热模拟试验机,进行了Cu-0.8Mg-0.15Ce合金的等温压缩试验,变形温度范围为500～850℃,变形速率范围为0.001～10 s~(-1)。研究了不同条件下流变应力的变化规律、合金的热加工图以及合金变形机制,分析了变形温度、变形速率和流变应力之间的关系。结果表明:合金在热变形过程中,其真应力-真应变曲线表现出明显的加工硬化、动态回复和再结晶特点,随着变形温度的升高和变形速率的降低,其流变应力和峰值应力不断降低;可用双曲正弦本构关系来描述热变形过程中的流变应力,计算出合金热变形过程中的激活能为Q=281.47 kJ·mol~(-1),在此基础上构建了该合金的本构方程;合金在热变形过程中的最优加工参数为:变形温度800～850℃,变形速率0.001～0.1 s~(-1)。     

Mg-9Gd-2Nd-0.8Al合金热压缩行为及热加工图

采用光学显微镜、扫描电镜研究了铸态和均匀化态的Mg-9Gd-2Nd-0.8Al合金的显微组织,然后用Gleeble-1500D热模拟试验机对均匀化态合金在变形温度350～500℃,应变速率0.003～1 s^-1条件下进行了热压缩实验,计算了合金的变形激活能,构建并分析了合金的本构方程和热加工图。结果表明：铸态Mg-9Gd-2Nd-0.8Al合金主要由α-Mg基体和Mg₅Gd,Mg₄₁Nd₅,Al₂RE相组成,经均匀化处理后(510℃×12 h),Mg₅Gd和Mg₄₁Nd₅相基本溶解,Al₂RE相保持稳定。均匀化态合金的流变应力曲线表现出动态再结晶的特征,其流变应力和峰值应力随温度的升高或应变速率的降低而显著降低,合金的变形激活能为185.836 kJ·mol^-1。合金在本实验的变形条件范围内存在两个失稳区：变形温度350～375℃,应变速率0.003～0.012 s     

高锆含量Cu-1%Zr-0.15%Ce合金热变形行为研究

利用Gleeble-1500D热模拟机,在温度为550,650,750,850,900℃,应变速率为0.001,0.01,0.1,1,10 s~(-1)的条件下,对Cu-1%Zr-0.15%Ce合金的高温变形过程中的流变应力进行研究,分析了动态再结晶的演变机制。结果表明:变形温度和应变速率对合金的流变应力有显著的影响,在550~750℃之间具有典型的动态回复特征,850~900℃具有动态再结晶热变形特征。通过流变应力、应变速率和变形温度之间的关系,建立高温热变形流变应力本构方程,得到合金的热激活能为430.51 k J·mol~(-1),与纯铜热压缩变形过程相比,高Zr含量Cu-1%Zr-0.15%Ce合金热激活能提高了105%。     

Mg-Gd-Sc-Mn耐热镁合金的热变形行为

采用GLEEBLE-1500热模拟机对Mg-10．2Gd-0．8Se-1．7Mn合金在温度为573～773K、应变速率为0．001～1s^-1、最大变形程度为60％的条件下,进行高温压缩模拟实验研究。分析了合金流变应力和应变速率及变形温度之间的关系,计算了高温变形时的变形激活能和应力指数,为选择这种合金的热变形加工条件提供实验依据。采用金相显微镜分析了合金在不同温度下压缩变形的组织演变。结果表明：合金的稳态流变应力随应变速率的增大而增大,在恒定应变速率的条件下,合金的真应力随温度的升高而降低;合金的变形激活能随着变形温度的升高而增大,特别是在723K时迅速增大。合金在变形过程中发生了不同程度的动态再结晶,变形温度和变形速率对合金再结晶组织有明显的影响。根据实验分析,合金的热加工宜在673～723K范围内进行。     

Mg-10Gd-2Y-0.6Zr合金热压缩变形与其微观组织

采用热压缩模拟试验,对Mg-10Gd-2Y-0.6Zr镁合金在350～450℃,变形程度为40%,变形速率在0.001～0.5s-1条件下的热压缩变形规律进行了研究,对变形后的微观组织进行了金相分析,对显微组织中的第二相进行了扫描能谱成分分析,对变形后试样的硬度进行了测试,根据热加工动态回复再结晶的特点和稀土合金相的作用,分析了该合金的微观组织结构和变形行为.结果表明:热压缩变形温度和速率对合金硬度值总的影响不大,但在相同温度下,有速率越大硬度越大的趋势;该合金在350℃,400℃时变形速率为0.1 s-1时晶粒异常粗大,在400℃变形速率大于0.5 s-1或变形温度450℃,变形速率为O.1 s -1下进行热压缩,该合金可以得到组织结构均匀和热塑性成型良好的匹配.     

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%.     

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.     

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.     

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.     

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.     

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.     

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.