高性能含镨快淬(Nd,Pr)12(FeCoZr)82B6粘结磁体的制备

采用过快淬加晶化退火处理的方法,研究了含有Pr的近正分快淬(Nd,Pr)12(FeCoZr)82B6粘结磁体制备工艺,粘结出的磁体磁性能为:Br=0.669T,Hci=811kA·m-1,Hcb=434kA·m-1,(BH)m=75kJ·m-3。合金快淬态的组成和显微结构、晶化退火温度、晶化退火时间直接影响磁体的磁性能,以24m·s-1速度快淬,并在655℃退火10min,可获得最佳磁性能。实验制备的粘结快淬(Nd,Pr)12(FeCeZr)82B6磁体(密度6 1g·cm-3)磁性能为:Br=0 669T,Hci=811kA·m-1,Hcb=434kA·m-1,(BH)m=75kJ·m-3     

添加镝的Nd-Fe-B纳米晶单相合金的微结构与磁性能研究

采用单辊快淬法制备了Nd12.3-xDyxFe79.7Zr0.8Nb0.8Cu0.4B6.0(x=0,0.5,1.5,2.5)合金纳米晶单相永磁薄带,研究了合金薄带晶化处理后,成分、组织结构与磁性能之间的关系.X射线衍射分析(XRD)表明,淬态合金主要由非晶相和Nd2Fe14B相组成,完全晶化后由Nd2Fe14B相和少量α-Fe组成.高分辨透射电镜(HRTEM)分析表明,经充分退火后,Nd2Fe14B晶体完整,晶粒间几乎没有边界相.随着Dy含量增加,晶粒尺寸细化,矫顽力大幅提高.x=0.5合金综合磁性能最佳,经过700℃晶化处理10min后,其磁性能为Jr=1.09 T,Hci=1048kA·m-1,(BH)max=169.5 kJ·m-3.     

Nd10.1Fe(83.7-x-y)CoxZryB6.2永磁材料结构和磁性能的研究

采用熔体快淬及晶化热处理工艺制备Nd10.1Fe(83.7-x-y)CoxZryB6.2纳米晶永磁材料. 在快淬速度为18 m·s-1时, 经710 ℃/4 min晶化处理后, Nd10.1Fe76Co5Zr2.7B6.2粘结磁体出现最佳磁性能, 分别为Br=0.67 T, JHc=754 kA·m-1, (BH)max=75.1 kJ·m-3. 粘结磁体的磁性能对于快淬速度非常敏感. 随着合金元素的添加, 出现最佳磁性能的快淬速度逐渐减少. 为了得到最佳磁性能, 除了选择合适的快淬速度外, 添加合适的合金元素变得非常重要.添加Zr元素抑制了亚稳相的析出以及细化了晶粒尺寸.比较不加Zr元素的Nd10.1Fe78.7Co5B6.2, 添加Zr元素晶化温度增加了9 ℃, 表明Zr元素也增加了快淬薄带的热稳定性.     

Fe基非晶和纳米晶合金晶化及电化学腐蚀行为

应用单辊甩带法制备非晶态Fe78Si13B9和Fe73.5Si13.5B9Nb3Cu1薄带,并以非晶晶化退火法制备出纳米晶Fe73.5Si13.5B9Nb3Cu1薄带.利用X射线衍射(XRD)仪和示差扫描量热计(DSC)对该非晶薄带的非晶特性及其晶化过程进行了研究.并用电化学极化曲线的方法和电化学阻抗技术研究了非晶态Fe78Si13B9和纳米晶Fe73.5Si13.5B9Nb3Cu1合金在1mol/LNaOH溶液里的电化学腐蚀行为,用SEM对极化测试后的试样形貌进行了观察;同时还研究了不同的热处理温度对材料结构及在1mol/LNaOH溶液里耐腐蚀性能的影响.结果表明,该非晶薄带的晶化过程分为两步;纳米晶比非晶合金的耐腐蚀性要好;且随着热处理温度的升高,非晶和纳米晶的耐腐蚀性能都得到提高.     

快速凝固AlNiCuNd纳米/非晶复合材料的制备及显微组织研究

采用熔体单辊旋淬法制备了快凝Al87Ni7Cu3Nd3合金条带,利用差热扫描热力学(DSC)分析、X射线衍射(XRD)分析等手段对比研究了快凝合金条带及其不同退火态材料的晶化行为.选择合适工艺条件,对快凝合金条带进行等温加热退火,采用高分辨透射电镜(HRTEM)观察分析了等温退火态材料显微组织特征.结果表明,快凝Al87Ni7Cu3Nd3合金薄带呈现出完全均匀的非晶态结构.随加热温度升高,非晶态薄带的晶化过程包括两个主要的相转变: α-Al晶体从非晶基体中析出的初始晶化以及有Al3Ni,Al11Nd3和Al8Cu3Nd形成的第二次晶化过程.在低于310 ℃下加热,快速凝固Al87Ni7Cu3Nd3金属玻璃中发生的主要相转变是富Al非晶的初始晶化.110 ℃等温退火态薄带主要是由α-Al加残余非晶相的两相组成,α-Al晶体纳米颗粒均匀弥散分布在残余非晶基体上.而在310 ℃热暴露后的退火试样中,在除α-Al晶体外的残留非晶相中开始出现极少量的Al3Ni金属间化合物.     

制备工艺对Pr2Fe14B/α-Fe纳米复合永磁材料组织与磁性的影响

用XRD,TEM和VSM等方法研究了快淬法制备的Pr2Fe14B/α Fe纳米复合永磁薄带的显微结构与磁性。比较了直接快淬和非晶晶化两种制备工艺对合金薄带显微结构和磁性能的影响。通过对Pr8Dy1Fe74.5Co10Nb0.5B6合金薄带高压退火,获得了Br=1.11T,Hci=816.0kA·m-1和(BH)max=188.8kJ·m-3的高性能。     

镨元素对(Nd,Pr)10.5(FeCoZr)83.5B6合金显微结构和磁性能的影响

研究了稀土元素Pr对快淬(Nd1-xPrx)10.5(FeCoZr)83.5B6(x=0,0.2,0.4,0.6,0.8,1.0)合金显微组织结构和粘结磁体磁性能的影响。通过部分过快淬获得由非晶和微晶共同组成的条屑,在实验优化的退火条件下晶化处理后,制备出最佳磁性能的系列粘结磁体。随Pr含量的增加,磁体的内禀矫顽力Hci单调上升,剩磁Br单调下降,(BH)m在x=0.6～0.8处达到最大值70.6kJ·m-3。Pr元素使合金非晶态的晶化转变温度和转化能降低,合金的显微组织结构变得较粗大和较不均匀,从而使快淬粘结磁体剩磁降低,但Pr2Fe14B化合物较高的磁晶各向异性场使磁体的内禀矫顽力提高。     

添加钛和碳对Nd9.4Fe79.6B11合金晶化方式、显微结构和磁性能的影响

研究了Ti和C添加对Nd9.4Fe79.6-xTixB11-yCy(x=0,1,2,4,6;y=0.5,1.5,3)合金晶化方式、显微结构和磁性能的影响规律。结果表明,适量Ti和C添加改变了合金的晶化方式,使-αFe相和Nd2Fe14B相同时从Nd9.4Fe75.6Ti4B10.5C0.5非晶基体中析出,避免了先析出相晶粒的长大,利于获得细小均匀的显微结构。适量Ti和C添加的Nd-Fe-B-Ti-C非晶合金在退火过程中易析出细小弥散的TiC和TiB2相,可作为形核质点促进形核,且可抑制晶粒长大,最终形成细小均匀的显微结构。综合性能较佳的Nd9.4Fe75.6Ti4B10.5C0.5合金退磁曲线具有优异的方形度,最佳退火条件下合金薄带的剩磁Br为0.91 T,矫顽力iHc为976 kA.m-1,磁能积(BH)max达135 kJ.m-3。文章最后对Ti和C添加合金微结构的形成机制进行了探讨。     

复合添加合金元素对纳米双相Nd2Fe14B/α-Fe永磁体微观结构和磁性能的影响

采用正交实验法系统地研究了复合添加合金元素Ga ,Nb ,Zr,Hf和Pr对纳米双相Nd9-xPrxFe86 .5-y -z -m -nGayNbzZrmHfnB4 .5(x =0 ,2 2 5 ;y ,z ,m ,n =0 .5 ,1.0 )快淬带微观结构和磁性能的影响。结果表明 :复合添加合金元素可以大大地降低Nd2 Fe1 4B和α Fe相的晶粒尺寸 ,并促使快淬带在低辊速下非晶化 ;在退火后样品带中 ,没有发现晶粒的不均匀长大 ,但大量添加合金元素会导致晶粒形貌不够理想。另一方面 ,由于各元素间的交互作用 ,复合添加合金元素使磁性能的变化规律非常复杂。实验发现 ,当Nb的含量为 0 .5 %时 ,增加Pr和Ga的添加量并降低Zr和Hf的添加量可以明显地改善磁性能。成分为Nd2 .2 5Pr6 .75Fe84 .5Ga1 .5Nb0 .5B4 .5的合金 ,在 15m·s- 1 辊速下获得的最佳磁性能为Jr=1.0 5 3T ,iHc=5 3 0 .9kA·m- 1 ,(BH) max=12 4kJ·m- 3。     

淬速和热处理对纳米双相Nd2Fe14B/α-Fe磁体的性能和微结构的影响

用熔体快淬法制备了高性能纳米双相耦合Nd2Fe14B/α-Fe磁体, 研究了快淬速率和热处理工艺对其磁性能和微结构的影响. 实验结果表明, 控制快淬速率在12 m*s-1时, 可直接得到显微组织均匀、α-Fe相粒子细小且均匀分布的纳米双相耦合Nd2Fe14B/α-Fe磁体. 低温退火处理后可消除由少量非晶相带来的成分不均匀性, 其最高磁性能为iHc=432.2 kA*m-1, Jr=1.08 T, (BH)max=115 kJ*m-3. 快淬速率提高, 非晶相体积分数增加, 在高温晶化热处理时软硬磁相析出不均匀, 个别α-Fe相粒子奇异长大, 尺寸达到100 nm左右, 这不利于软硬磁相间的交换耦合作用, 有损磁性能.     

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.     

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.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.