Mg-Zn-Zr-RE系镁合金中的稀土相分析

用光学显微镜、电子探针、X射线衍射及电手显微分析等手段研究了Mg Zn Zr RE合金铸态及挤压态的稀土相。在铸态组织中,稀土及锌均富集于晶界,形成三元金属间化合物Mg_3RE_2Zn_3(W)相及Mg_3REZn_6(Z)相,在0.8Y和0.79RE合金中以Z相为主,而在2.56RE合金中W相多于z相;挤压型材中均存在W和Z相。铸态合金经350℃保温并挤压后,合金发生如下相变:Mg+Mg_3REZn_6(Z)→MgZn+Mg_3RE_2Zn_3(W)实验测定了Z相为六方结构,其a=0.640～0.642nm,C=1.029～1.031nm。     

富钇混合稀土和热处理对Mg—Zn—Zr系镁合金的组织及相结构的影响

富钇混合稀土对Mg-Zn-Zr系镁合金的铸造组织及组成相无显著影响。MB25合金(含高纯金属钇)和MB26合金(含富钇混合稀土)的铸造组织都是在α-Mg晶界上分布着大量的Z+β网状共晶化合物相(以Z相为主),其区别在于铸态MB26合金的晶界共晶相中溶有少量的镧、铈、错、钕、钆和镝等多种稀土元素。均匀化处理和挤压热加工都能使铸态MB26合金发生不同程度的相变,并在不同程度上改变铸态合金的组织和相结构。随着从挤压到均匀化处理温度的提高,其相变过程是从Z相中锌的扩散相变开始到β、W共晶相各自完成共析转变结束。     

钇对Mg-0.8Zr-0.35Zn基合金组织及高温性能的影响

采用XJG-04型金相显微镜、 JCXA-733电子探针、 D/max-rB型X射线衍射仪及WDW-200型电子万能实验机研究了Y对Mg-0.8Zr-0.35Zn基合金铸态、固溶时效组织及高温(250 ℃)性能的影响. 结果表明: Y能细化Mg-0.8Zr-0.35Zn基合金铸态及热处理态组织, 加入Y形成新相Mg24Y5. 在250 ℃时, 随着Y含量增加合金高温抗拉强度增大, 延伸率及断面收缩率降低; 高温拉伸断口SEM图像显示脆性断裂趋势增大, 断裂由延性向解理方式发展.     

往复挤压准晶增强快速凝固Mg92.5Zn6.4Y1.1合金

采用往复挤压工艺将快速凝固Mg92.5Zn6.4Y1.1合金薄带在330℃挤压2道次和4道次,然后正挤压制成Φ10 mm的棒材。用OM,TEM,XRD及DTA研究了往复挤压过程中准晶相I-Mg3YZn6弥散析出及对力学性能的影响。研究表明,往复挤压有利于快速凝固Mg92.5Zn6.4Y1.1合金薄带的焊合,获得组织致密、均匀、高强韧合金。往复挤压2道次,相组成为-αMg和准晶I-Mg3YZn6,脱溶析出纳米准晶相较少;4道次相组成为-αMg和准晶I-Mg3YZn6及MgZn相,脱溶弥散析出的纳米I-Mg3YZn6准晶相及MgZn相较多。往复挤压提高材料的拉伸性能,其主要原因是细晶强化和析出强化。     

Mg—Zn—Zr—Y系镁合金的X射线衍射分析

采用X射线衍射方法,对铸态Mg-Zn-Zr-Y系列合金基体相(α-Mg)的面间距(d值)变化及析出相进行了研究。结果表明,α-Mg的d值随着钇含量的增加先增大,随后变小。在不含钇的合金中,析出相主要是MgZn及MgZn_2;在含钇合金中,钇小于0.94 wt％时,晶界相主要是Z相;钇含量高于0.94 wt％后,逐渐转变为以W相为主。除了上述相外,在含钇合金中还出现Y-Zn及Mg-Y相。     

锌含量对铸态Mg-10Y-xZn-0.5Zr镁合金微观组织和力学性能的影响EI北大核心CSCD

采用光学显微镜、扫描电镜、X射线衍射仪、透射电镜、电子拉伸实验机等研究了铸态Mg-10Y-xZn-0.5Zr(x=1,1.5,2(%,质量分数))合金的微观组织和力学性能。结果表明:铸态Mg-Y-Zn-Zr合金组织主要由α-Mg,LPSO相和W相组成,其中LPSO相的化学式为Mg_(12)YZn,W相的化学式为Mg_(3)Zn_(3)Y_(2)。LPSO相主要呈块状或层片状,随着Zn含量的增加,块状LPSO相体积分数逐渐增多,同时合金的屈服强度逐渐增加。当Zn含量为2%时,LPSO相形貌表现出以块状相为主,铸态Mg-10Y-2Zn-0.5Zr合金具有最佳的综合力学性能,其屈服强度、抗拉强度和延伸率分别为123.9,206.2 MPa和12.06%。块状LPSO相体积分数的增加是合金力学性能提高的主要原因。     

锌对稀土镁合金组织与力学性能的影响

采用OM, XRD, SEM和EDS等试验手段研究了Zn对稀土镁合金Mg-4Y-1Ca(%,质量分数)微观组织和力学性能的影响。结果表明:随着Zn (x=1%, 3%, 5%)的加入, Mg-4Y-1Ca合金中生成的Mg_(24)Y_5二元相逐步转变为Mg_3Y_2Zn_3(W相)+Mg_(12)YZn(X相)三元相,铸态组织细化,第二相沿晶界成网状分布;经热挤压变形后,合金再结晶后晶粒细化明显,第二相弥散分布于基体和晶界上,强度提高的同时伸长率也获得较大提升,其中Mg-4Y-1Ca-5Zn合金表现最为显著。得益于Zn添加对再结晶晶粒细化和W相、 X相弥散强化的共同作用, Mg-4Y-1Ca-5Zn合金经热挤压处理后具有较佳的综合力学性能,屈服强度、抗拉强度和伸长率分别达到198 MPa, 271 MPa和24.6%。     

退火温度对La0.75Mg0.25Ni3.5Co0.2贮氢电极合金的结构及电化学性能的影响

为了改善La-Mg-Ni系合金电极的循环稳定性,对铸态合金La0.75Mg0.25Ni3.5Co0.2在0.3 MPa压力氩气保护下进行不同温度的退火（1123,1223和1323 K）,保温时间均为10 h。系统研究了退火温度对合金的微观结构及电化学性能的影响。X射线衍射（XRD）和扫描电镜（SEM）研究结果表明,合金具有多相结构,当铸态及1123 K温度退火后合金主要由LaNi5,（La,Mg）2（Ni,Co）7相以及少量的LaNi2相组成。当退火温度为1223和1323 K时,合金中LaNi2相消失,合金主要由LaNi5,（La,Mg）2（Ni,Co）7及（La,Mg）（Ni,Co）3相组成。随退火温度提高,合金最大放电容量单调下降,但合金的循环稳定性得到改善。退火处理改善合金循环稳定性的原因在于退火后合金组织均匀,晶粒增大,在KOH电解质溶液中增强合金电极抗氧化腐蚀能力,抑制合金颗粒粉化。     

钇对Mg-5Zn-2Al合金组织和力学性能的影响

利用金相显微镜、电子万能试验机、扫描电镜和X射线等手段,研究了不同含量的Y对Mg-5Zn-2Al镁合金铸态及热处理状态下组织及力学性能的影响.结果表明:合金主要由α-Mg基体相、Mg32(Al,Zn)49相及Al3Y相组成,并且A13Y稀土相随着合金中加Y量的增加而增多.在铸态及热处理条件下,合金的力学性能(抗拉强度和延伸率)均呈现先下降后上升的变化趋势.在铸态条件下,当加Y量为0.3%时合金的抗拉强度达到最大,为205 MPao当加Y量为0.9%时,合金的延伸率达到最大,为14.6%.经过T6热处理后,合金的抗拉强度较铸态均得到了明显提高,而延伸率有所下降.加Y量为0.9%的Mg-5Zn-2Al镁合金的抗拉强度和延伸率均达到最大值,分别为234 MPa和11.4%.     

钇对ZA-27锌合金老化性能的影响

采用金相、扫描电镜、 X射线衍射、电子探针及盐水浸蚀、热蒸汽浸蚀等方法, 对不同钇含量的ZA-27锌合金进行了显微组织及抗老化性能的研究.研究结果表明, 在ZA-27合金中添加适量的稀土钇, 钇可与铝生成细小的YAl3相, 为α相提供凝结核, 使α相形核量增加, 在结晶过程中, α相枝晶不能充分发育, 从而起到细化晶粒、减少偏析的作用; 同时, 还可与锌生成弥散、细小的钇锌相, 从而改变晶界状况, 提高合金的抗老化性能.当钇稀土含量较高时, 由于在晶界与晶内均有大块钇锌相生成, 破坏了合金晶界的致密度, 并增加了相界面, 从而使合金的抗腐蚀性能有所下降.     

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.     

Understanding the Diels-Alder reactivity of 1,2-azaborine analogues

The Diels-Alder reactivity of 1,2-heteroborines (H₄C₄B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed.