Mg-SiO_2体系制备Mg_2Si/AZ91D复合材料的研究

采用原位合成技术制备了Mg2Si/AZ91D复合材料,并通过光学显微镜(OM)、扫描电镜(SEM)、能谱仪(EDS)和X射线衍射仪(XRD)等对添加碱土、稀土元素的影响进行了研究。结果表明:AZ91D镁合金中加入SiO2(其中Si占合金质量的3%)后,出现多边形状或树枝晶状的初生Mg2Si相,以及汉字状的共晶Mg2Si相,树枝晶状Mg2Si的平均尺寸约25~50μm,汉字状Mg2Si的平均尺寸约12~15μm;Mg2Si对镁合金中的β-Mg17Al12相有细化作用。添加Ca,Sr,Y对Mg2Si形貌、尺寸有明显的改善,当添加0.9%Ca,0.1%Sr,0.5%RE(80%Y)变质处理后,Mg2Si形貌全部变为多边形状,平均尺寸约0.8~5μm。     

钪变质处理对A356合金凝固组织和性能的影响

采用稀土Sc对A356合金进行变质处理,研究了Sc对A356合金的初生α相和共晶硅形态及其力学性能的影响。结果表明:加入Sc在铝熔体中生成Al3Sc可以作为α-Al的非自发形核的核心,显著细化A356合金中的初生α相,由粗大的树枝晶形态变为细小的短枝晶和圆整的颗粒状形态,同时,Sc对共晶硅也具有显著的变质作用,使其由粗大的针片状变为细小的纤维状和蠕点状。当Sc的加入量为0.2%(质量分数)时,对A356合金中初生α相的细化作用和对共晶硅的变质作用即可达到最佳的效果,合金的铸态抗拉强度和伸长率分别提高23.7%和58.1%,在此基础上,继续增加Sc的加入量,对进一步改善合金微观组织和力学性能的作用不显著。     

P+Sr+Ce复合变质对高硅耐热铝合金组织与性能的影响

采用正交实验设计方法研究了Al-21Si-1.5Cu-1.5Ni-2.5Fe-0.5Mg合金P Sr Ce复合变质。正交实验表明变质剂的最佳加入量(质量分数)为:2%(CaH2PO4 2CaSO4) 0.2%Sr 0.2?,可一次细化初晶硅与共晶硅,并改善富铁相形态。X射线衍射分析与能谱分析表明,未变质合金中的针状富铁相为Al9FeSi3,复合变质使粗大针状富铁相消失,生成鱼骨状富铈富铁相Al8CeFe4。在最佳变质条件下,室温抗拉强度与300℃瞬时抗拉强度均比未变质合金提高约30%,扫描电镜观察发现拉伸断口由脆性的沿晶断裂变为混合断口,断口中有大量韧窝存在。     

富镧稀土对消失模铸造B319合金组织的影响

利用等离子发射光谱仪，差分扫描量热仪（DSC），电镜及金相分析等手段，研究了RE对消失模铸造B319铝合金组织的影响。结果表明，在消失模铸造条件下，0．15％RE可使B319铝合金的硅相得到较好的变质效果。但当RE＞0．2％时，会出现富稀土的粗大块状金属间化合物La3Al2Si2，而对机械性能产生不利影响。当Fe/Mn=1.2时，消失模铸造组织中存在中国文字状的α－Fe和针状β-Fe铁相以及Al2Cu相。AlCu相可以离异共晶的形式析出，β-Fe及Si相均可以作为Al2Cu相的形核基底。而在金属型铸造组织中，铁相则完全以铁状的β-Fe形式存在。研究还表明，0．02％Sr变质使B319合金共晶转变温度下降了7℃。而RE的加入会使合金的共晶温度升高，采用0．2％RE对B319合金进行变质处理，其共晶温度从570．0℃升高到了572．0℃。     

微量稀土对工业纯铝中杂质相的变质行为

采用SE,EDAX,TEM他稀土对工业纯铝中富Fe(Si)杂质相的变质作用及机制,结果表明：富铈混合稀土（RE）是一种有效变质剂,可使铝中杂质相由粗大长针（条）状或骨骼变细小的团球状或短棒状,且分布均均匀,提高了材料的力学性能（尤其是塑性）,其变质机制主要是因稀土在固／液界面前前沿的富集,导致了稀土进入杂质相形成（AlFeSiRE)的复杂化合物,或吸附在杂质相表面阻碍其长大,但过量稀土易导致第二相数量增多,降低材料塑性,其加入量应小于 0．07％（质量分数）。     

钕对Mg-5Al-1Si高温蠕变及组织性能的影响

研究了不同Nd含量对Mg-5Al-1Si镁合金的高温蠕变性能影响, 对析出相进行了分析, 研究了微观组织与力学性能的关系. 研究结果表明, 该合金中的主要强化相Mg2Si呈粗大的汉字状, 分布在晶界的周围, 在受到应力时, 这种汉字状相与基体的界面处易产生微裂纹, 降低合金的抗拉强度、塑性等力学性能. 在Mg-5Al-1Si合金中加入微量的Nd以后, 合金的组织得到明显的细化, 并使Mg2Si强化相形貌由粗大的汉字状转变为细小、弥散分布的颗粒状. 由于显微组织的改善, 使得Mg-5Al-1Si镁合金的室温和高温力学性能均有一定的提高, 并明显的改善了Mg-5Al-1Si的抗蠕变性能.     

La2-xMgNi9-5x (x=0～1.0)贮氢合金的晶体结构与电化学性能研究

系统研究了La2-xMgNi9-5x (x=0～1.0)合金的晶体结构与电化学性能. XRD及Rietveld全谱拟合方法分析表明, x=1.0时合金由单一相的LaMgNi4相组成, 其余合金均由LaMgNi4与 (La, Mg)Ni3相组成. 随x的减小, 合金中LaMgNi4相丰度递减, x=0.5时合金中主相变为PuNi3型 (La,Mg)Ni3. 在LaMgNi4相中, Mg占据4c位置, 而在(La, Mg)Ni3相中Mg占据6c位置. 电化学实验表明, 合金氢化物电极放电容量随x的减小而增加, 由x=1.0时的170 mAh*g-1增加至x=0.0时的392 mAh*g-1.     

钇对Mg-9Al-1Si合金蠕变抗力和微观组织的影响

研究了Mg-9Al-1Si-xY合金的高温蠕变性能及其微观组织与力学性能的关系。该合金中的主要强化相Mg2Si呈粗大的汉字状，分布在晶界的周围，在受到应力时，这种汉字状相与基体的界面处易产生微裂纹，降低合金的抗拉强度、塑性等力学性能。在Mg-9Al-1Si合金中加入微量的Y以后，合金的组织得到明显的细化，Mg2Si强化相形貌由粗大的汉字状转变为细小、弥散分布的颗粒状。显微组织的改善，使得Mg-9Al-1Si合金的室温和高温力学性能均有一定的提高，并明显改善了Mg-9Al-1Si的抗蠕变性能。     

电弧熔炼过程中LaFe_(13-x)Si_x合金的凝固组织和相形成研究

研究了电弧熔炼过程中LaFe13-xSix合金的凝固行为。应用XRD和扫描电镜分析了合金组织相组成和结构。结果表明:电弧熔炼铸锭随温度梯度出现分层;La(Fe,Si)13(简称:1∶13)相是包晶反应生成的,冷速和硅含量变化对合金的凝固行为有很大的影响,当Si含量x≤1.0时合金显微组织由α-(Fe,Si)相和共晶相La Fe Si(简称:1∶1∶1)相组成,α-(Fe,Si)(简称:α-Fe)相为主要相,随硅含量增加1∶1∶1相增多;x≥1.5时由α-Fe相、1∶13相和1∶1∶1相组成;随x增加1∶13相为主要相,1∶1∶1相减少;当x≥2.0时显微组织中1∶13相作为初生相析出,且随温度梯度和硅含量变化1∶13相的形貌不同。     

La-Fe-M(M=Al, Si)化合物磁热性能研究进展

介绍了La-Fe-M(M=AI,Si)化合物在磁热性能研究方面的最新进展。具有NaZn13型晶体结构,含高浓度Fe的La-Fe—M(M=AI,Si)化合物为良好的软磁材料;用少量的Co替代化合物中Si,Al元素可以将化合物的居里温度提高至室温;对La(Fe1-yCoy)xSi13-x化合物,适量的Si,Co组合可使化合物在室温产生可与Gd5Si2Ge2比拟的磁热效应;加入适量的间隙原子H,也可使La(FexSi1-x)13在室温的磁热性能远远大于金属Gd;对含Si量低及含Si量高的La(FexSi1-x)13化合物在相转变点附近由温度和磁场诱导相变的本质做了详细阐述。     

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.     

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%).     

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.     

Synthesis of N-substituted carbazolones from α-iodo enaminones via Pd(0)-catalyzed intramolecular coupling under microwave irradiation

A variety of N-aryl and N-alkyl carbazolones were conveniently achieved in good to high yields via Pd₂(dba)₃-mediated intramolecular coupling of N-substituted α-iodo enaminones under microwave irradiation. The Pd(0)-catalyzed cyclization was found to proceed favorably with the more electron-deficient phenyl ring during the reactions involving unsymmetrical N,N-diaryl α-iodo enaminones. This unique property enables the construction of carbazolone skeleton containing nitro substituted benzenoid ring.     

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.     

Synthesis of substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles by intramolecular nitrilimine cycloaddition

Both substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles have been synthesized by the 3+2 intramolecular dipolar cycloaddition of nitrilimines to alkynes. This cyclization has been extended to more versatile 3-bromo derivatives by the use of alkynylbromides as dipolarophiles.     

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.