稀土对盐浴渗钒动力学的影响

在盐浴渗钒中添加稀土对表面渗钒有明显的催渗作用,渗钒速度约提高３０％－４０％,。对９５０℃经不同时间渗钒的试样测定渗层度（ｘ）。将ｘ及所对应时间（ｔ）代入经验公式ｘ＾ｎ＝Ｋｔ（ｌｎｘ＝ｌｎＫ／ｎ＋ｌｎｔ／ｎ）,经一元线性回归处理可知,ｘ与ｔ之间满足ｘ＾２＝Ｋｔ抛物线关系,添加稀土可以加快渗剂反应而增大渗剂钒势。稀土的强还原性使钢件表面的氧化还原而活性其表面,稀土渗入钢基体和ＶＣ渗层,会增大晶体缺陷密度,使碳原子扩散易于进行,稀土的添加可降低碳原子扩散激活能,起到催渗的效果。     

稀土对TC4钛合金固体渗硼的影响研究

采用稀土-硼共渗法对TC4钛合金基体表面在1000,1050和1100℃分别保温5,10,15,20 h进行了固体粉末渗硼实验,通过扫描电镜(SEM)、能谱(EDS)分析与X射线衍射分析(XRD)研究TC4钛合金稀土-硼共渗后的组织形貌和物相组成,讨论了稀土对TC4钛合金渗硼层相组成、硬度及耐磨性的影响。结果表明,渗层由外表层的TiB2和伸向基体的齿状的TiB组成,渗层厚度最高可达25μm;XRD分析表明,TC4钛合金稀土-硼共渗后形成TiB2与TiB双相硼钛化合物层,稀土的加入使得TiB2的含量增大;EDS分析得出表层B和Ce元素含量较高,稀土促进B原子在基体表面的吸附使其浓度增大;渗层的显微硬度呈梯度分布,稀土-硼共渗渗层的TiB2到TiB晶须硬度值的变化范围为3300HV0.01~1800HV0.01;共渗渗层的耐磨性也显著提高。     

气体法低温稀土多元共渗的研究

从自制的多种渗剂中,筛选了含稀土的最佳渗剂,实现了气体法低温稀土、硼、碳、氮、氧多元共渗。获得了组织、性能和层深远优于其它低温化学热处理的渗层。用金相、扫描电镜、光电子能谱和正电子湮没等技术,对渗层进行了较系统的分析,对稀土的催渗等基本理论问题进行了探讨。     

稀土对低温固体硼碳氮共渗作用的研究

采用Ｘ射线衍射仪,恒电位仪,摩擦磨损试验机等设备,研究了低温硼碳氮稀土（Ｂ－Ｃ－Ｎ－ＲＥ）共渗工艺及共渗层的组织性能,并与硼碳氮（Ｂ－Ｃ－Ｎ）共渗工艺及组织性能进行了比较。在适当范围内,稀土具有明显的催渗作用;与Ｂ－Ｃ－Ｎ共渗相比,Ｂ－Ｃ－Ｎ－ＲＥ共渗层的耐蚀性明显提高。对稀土元素的作用机制作了初步的探讨。     

镧－硼复合润滑添加剂的协合润滑机理

实验室和工业试验表明，含镧的润滑添加剂二烷基二硫代磷酸镧（ＬａＤＤＰ）和一种有机硼酸酯（ＯＢ）具有显著的协合润滑作用，将两种化合物复合加至润滑油中，可显著改善油品的抗磨减摩性能。采用俄歇电子能谱（ＡＥＳ）和Ｘ射线光电子能谱（ＸＰＳ）研究其协合润滑机理。结果表明，ＬａＤＤＰ和ＯＢ具有协合润滑作用的主要原因，除了在摩擦表面生成硫酸盐、磷酸盐、氧化镧和单质硼等表面膜起润滑作用外，更重要的是镧的存在对硼的摩擦扩散起到了“摩擦催渗”作用，使摩擦亚表面硼的含量增加，并形成Ｌａ－Ｂ摩擦共渗层，进一步提高材料表面硬度，从而改善耐磨性能     

固体法稀土硼钒共渗的研究

研究了CeCl3对固体粉末法B－V共渗的动力学,民分,组织和性能的影响,在渗剂中添加CeCl3不仅具有明显的催渗作用,使渗大速度提高40％以上,并且Ce作为组元渗入工件表面后形成CeFe2新相,还使渗层硬度和耐磨性有较大提高,稀土是通过提高渗剂中的硼势和钒势,。活化渗件表面,降低硼和钒原子的扩散活能来提高B和V的渗入速度的。     

稀土对3Cr2W8V钢多元共渗及金相组织的影响

(一)实验方法 经调质处理尺寸为10×10×10mm的3Cr2W8V钢试样,在7kW井式滴控坩埚炉中,采用滴注式气体共渗工艺,共渗介质为自配的稀土渗剂,稀土加入量为5g/L,在580℃进行共渗处理。 用Plasma 300 ICP和X射线衍射仪分析检测稀土;用显微硬度法确定渗层深度和显微硬度分布。     

稀土元素在钢的化学热处理中作用机理研究

根据稀土元素在化学热处理中的作用，研究稀土元素渗入到钢表层的扩渗机制和在化学热处理中的活化催渗机理。在８６０℃稀土碳氮共渗过程中，稀土的扩散系数为１．０６×１０￣（－１４）ｍ￣２／ｓ。     

WC-Co硬质合金稀土-硼共渗的高温动态相分析

用高温X射线衍射装置对以B4C为供硼剂、以Y2O3为催WC－20Co硬质合金渗硼表面进行了从室温到1300℃连续升温渗硼过程的XRD动态物相分析，探讨了稀土－硼共渗机制。结果表明，在真空烧结升温期间，从WC－Co压坯表面B4C分解出来的活性硼原子除在压坯表面上形成硼化物外，所形成的高浓度活性硼原子还向压坯内钴中扩散形成三元含硼相W2Co21B6化合物。同单独渗硼相比，钇在稀土－硼共渗过程中有拓宽渗硼温度范围、促进B4C脱碳分解和活性硼原子向压坯内扩散等催化渗硼作用。     

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。     

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.