Using Pd-salen complex as an efficient catalyst for the copper-and solvent-free coupling of acyl chlorides with terminal alkynes under aerobic conditions

The palladium-salen complex palladium(Ⅱ) N,N'-bis{[5-(triphenylphosphonium)-methyl]salicylidene}-1,2-ethanediamine chloride was found to be a highly active catalyst for the copper- and solvent-free coupling reaction of terminal alkynes with different acyl chlorides in the presence of triethylamine as base,giving excellent ynones under aerobic conditions.

Microwave-assisted chemoselective copper-catalyzed amination of o-chloro and o-bromobenzoic acids using aromatic amines under solvent free conditions

Copper-catalyzed synthesis of N-aryl anthranilic acid derivatives using effective amination of 2-chloro and 2-bromobenzoic acid under microwave irradiation is reported. Some of the advantages of this method are high chemoselectivity, short reaction times, ease of work up procedure and elimination of the need for acid protection. 2009 Published by Elsevier B.V. on behalf of Chinese Chemical Society.

Free cupric ions in contaminated agricultural soils around a copper mine in eastern Nanjing City, China

To determine the environmental free metal ion activity was a recent hot issue. A method to measure low-level free cupric ion activity in soil solution extracted with 0.01 mol/L KNO3 was developed by using cupric ion-selective electrode （ISE） and calibrating with Cu-buffer solution. Three copper buffers including iminodiacetic acid （IDA）, ethylenediamine （EN）, and glycine （Gly） were compared for calibrating the Cu-ISE curves in the range of free cupric ions （pCu^2＋） 7-13. The Cu-EN buffer showed the best electrode response and thus was applied as the calibration buffer. The pCu^2＋ of 39 contaminated agricultural soils around a copper mine was measured, ranging from 5.03 to 9.20. Most Cu in the soil solutions was found to be complexed with dissolved soil organic matters, averaging 98.1%. The proportion of free Cu^2＋ ions in the soil solutions decreased with the increasing of solution pH. Soluble Cu and free Cu^2＋ ions concentrations were analyzed by multiple linear regressions to evaluate the effects of soil properties on metal levels and speciation. The results showed that soil solution pH was the most significant factor influencing pCu^2＋ （with R^2 value of 0.76）, while not important for the soluble Cu concentration.

Study of the Effect of Acetic Acid and Phosphate on Copper Corrosion by Immersion Tests

It was reported that hemispheric corrosion occurred in copper tubes in an acetic acid environment. When hemispheric corrosion occurred, corrosion could easily progress if water then flowed into the copper pipe, and countermeasures were needed. Therefore, we studied the copper corrosion caused by acetic acid. The present work investigated the relationship between the corrosion form of copper and acetic acid concentration using phosphorous-deoxidized copper, and reported that hemispherical corrosion was observed at acetic acid concentrations of 0.01 to 1 vol.% (0.002 to 0.2 mol·L-1) in the immersion test. In this study, the effects of acetic acid and phosphate on copper corrosion were examined using oxygen-free copper in immersion tests. The results suggested that different concentrations of phosphate in acetic acid solutions and the presence or absence of acetic acid and phosphate affected the corrosion of copper, resulting in different corrosion forms and corrosion progress.

Experimental investigation of Tie6Ale4V titanium alloy and 304L stainless steel friction welded with copper interlayer

The basic principle of friction welding is intermetallic bonding at the stage of super plasticity attained with self-generating heat due to friction and finishing at upset pressure. Now the dissimilar metal joints are especially popular in defense, aerospace, automobile, bio-medical,refinery and nuclear engineerings. In friction welding, some special alloys with dual phase are not joined successfully due to poor bonding strength. The alloy surfaces after bonding also have metallurgical changes in the line of interfacing. The reported research work in this area is scanty. Although the sound weld zone of direct bonding between Tie6Ale4 V and SS304 L was obtained though many trials, the joint was not successful. In this paper, the friction welding characteristics between Tie6Ale4 V and SS304 L into which pure oxygen free copper(OFC) was introduced as interlayer were investigated. Boxe Behnken design was used to minimize the number of experiments to be performed. The weld joint was analyzed for its mechanical strength. The highest tensile strength between Tie6Ale4 V and SS304 L between which pure copper was used as insert metal was acquired. Micro-structural analysis and elemental analysis were carried out by EDS, and the formation of intermetallic compound at the interface was identified by XRD analysis.

Electrochemical formation of holmium-copper alloys on copper cathode in molten KCl-HoCl_3

Cyclic voltammetry, open circuit potential— time curve after potentiostatic electrolysis and potential step chronoamperometry were used to investigate the electrochemical formation processes of holmium-copper alloys on copper cathode in molten HoCl3-KCl. Intermetallic compounds HoCu5, HoCu4, HoCu2 and HoCu are formed in sequence and then the metallic Ho is deposited when Ho3+ is reduced on copper electrode in molten KCl-HoCl3 at 1066 K. The first charge-transfer reaction is reversible. The structure of holmium-copper alloy film deposited on copper electrode by potentiostatic electrolysis was characterized by X-ray diffraction. The standard free energies of formation for the intermetallic compounds HoCu5, HoCu4, HoCu2 and HoCu are - 95.5, - 92.6, - 73.8 and - 44.0 kJ/mol, respectively. The diffusion coefficient and diffusion activation energy of Ho atom in the alloy are estimated to be 10-10- 10-11 cm2/s and 75.35 kJ/mol, respectively, from the chronoamperometry data.

One-step synthesis of carbon-supported copper nanoparticles from biomass for N-arylation of pyrazole

Carbon-supported copper catalyst was prepared for the first time in one-step with copper nitrate and corn stalk through calcination under different temperatures. Uniformly dispersed nanoparticles were obtained and were identified to be Cu（0） and Cu（Ⅰ） in XRD patterns. Excellent catalytic activity and selectivity were achieved in the N-arylation of pyrazole under ligand and protection gas free conditions. About90.4% of product yield was achieved with only 0.5 mol% of copper catalyst（Cu-C-300）, which was considerably more efficient than previous reports. XPS results suggested that the N-arylation of pyrazole activity was closely related to the surface Cu（Ⅰ） species.

环境艺术设计用铜合金的表面改性处理研究

为了提升环境艺术用铜合金的耐腐蚀性能,提升艺术观赏性,对环境艺术设计用铜合金进行了表面改性处理,对比分析了打磨态、酸洗态、无铬钝化态和铬酸盐钝化态铜合金的表面物相组成、表面形貌,以及盐雾腐蚀、失重腐蚀和电化学腐蚀性能。结果表明,无铬钝化和铬酸盐钝化处理后的铜合金表面都形成了钝化膜,且铬酸盐钝化处理后铜合金表面形成了致密钝化膜;盐雾腐蚀后,无铬钝化态和铬酸盐钝化态铜合金的表面腐蚀程度会相对打磨态和酸洗态腐蚀较轻;在相同腐蚀时间下,腐蚀失重从小到大顺序为:铬酸盐钝化态<无铬钝化态<酸洗态<打磨态;无铬钝化态和铬酸盐钝化态铜合金的腐蚀电位相对打磨态、酸洗态更正,腐蚀电流密度相对小一个数量级,打磨态、酸洗态、无铬钝化态和铬酸盐钝化态的缓蚀率分别为32.32%、51.66%、89.34%和96.84%,铜合金的耐腐蚀性能从大到小顺序为:铬酸盐钝化态>无铬钝化态>酸洗态>打磨态。

Xe^(23+)离子束轰击低温工况下的无氧铜表面解吸性能研究

强流重离子加速器运行时产生动态真空效应引起束流寿命缩短,需安装无氧铜束流准直器来降低该效应。为探究无氧铜材料在离子束轰击下的解吸性能,本工作设计并研制了满足低温工况的解吸率测试装置,在兰州重离子加速器国家实验室利用Xe^(23+)离子束完成了无氧铜温度在4.2 K、20 K、77 K和300 K,以及束流能量为0.58 MeV/u、0.96 MeV/u和1.3 MeV/u的在束试验。结果表明,离子束轰击无氧铜表面时解吸出最多的分子为H_(2),其次分别为H2O、CO、CO_(2)、Ar和O_(2);当温度为4.2 K、束流能量为0.58 MeV/u时无氧铜解吸出H2的比例为87.74%。在同一能量下,随着无氧铜表面温度的升高,解吸率呈增加趋势,能量为0.58 MeV/u时,4.2 K下无氧铜的解吸率仅为25 mol/ion,小于300 K时的600 mol/ion,表明温度越高其解吸产额越大。在同一温度下,随着束流能量的升高无氧铜表面解吸率增加,但增加趋势逐渐减缓,解吸产额趋向饱和。

硫代硫酸盐法浸金研究进展

硫代硫酸盐法浸金具有浸出速率快、成本低、环保性较好等优点,被认为是最有可能替代氰化浸金的提金方法。本文从浸金原理、实验条件及产业化情况等方面系统介绍了5种含铜体系(Cu^(2+)-NH_(3)-S_(2)O_(3)^(2⁻)体系、Cu^(2+)-EDTA-S_(2)O_(3)^(2⁻)体系、Cu^(2+)-en-S_(2)O_(3)^(2⁻)体系、Cu^(2+)-LH-24⁻-S_(2)O_(3)^(2⁻)体系、Cu^(2+)-Gly-S_(2)O_(3)^(2⁻)体系)和2种不含铜体系(Cl⁻-NH_(3)-S_(2)O_(3)^(2⁻)体系、Fe^(3+)-C_(2)O_(4)^(2⁻)-S_(2)O_(3)^(2⁻)体系)的研究进展,并对硫代硫酸盐法浸金的不同浸金体系进行对比分析。最后,总结了硫代硫酸盐法浸金在工业应用方面存在的难题及解决措施,以期为产业化应用提供理论借鉴。

乳糜泻与微量元素相关性研究进展

乳糜泻是一种由遗传易感个体摄入麸质引起的自身免疫病,主要累及小肠,引起小肠绒毛萎缩。许多乳糜泻患者因肠道炎症出现各种营养素吸收障碍,导致体内营养失衡,包括各种微量元素失衡。虽然微量元素在人体中含量很少,但因其特殊生理功能,对人体健康具有重要作用。部分乳糜泻相关并发症与不同微量元素失衡有关。此外,研究发现多种微量元素在乳糜泻发生、发展中发挥作用。本文就乳糜泻患者中一些重要微量元素水平,以及近年各种微量元素在乳糜泻发病机制、病情评估和治疗中作用的研究进展作一综述。

4~5 K铟片填充下无氧铜材料接触热阻实验研究

在陆续开展的深空探测任务中,高精度光学探测设备需要长期稳定的深低温工作环境。传热界面由于传热介质的热阻而存在一定的传热温差,为确保设备的工作环境,避免探测效率下降、精度下降和噪声干扰增加等严重后果,对无氧铜和不锈钢两种深低温温区常用的固体导热材料的界面接触热阻进行了实验测试。在真空、4~5.2 K、压力为3 077 N、铟片为填充物的条件下,测量了粗糙度为Ra=3.2的不锈钢-无氧铜接触热阻。结果表明:无氧铜界面间接触热阻在10^(-5)~10^(-4) m^(2)·K/W量级,且随温度的升高和粗糙度的减小而减小;无氧铜和不锈钢间的接触热阻在10^(-2) m^(2)·K/W量级。

浸镀时间对镀钯无氧铜线镀层质量的影响

采用直接镀法和扫描电子显微镜研究了影响无氧铜线镀钯层质量的因素。结果表明:浸镀时间和纳米钯粉含量对无氧铜线镀钯层质量有显著影响。当镀液中纳米钯粉的质量分数为2%、表面活性剂OP-10的质量分数为3%时,在室温浸镀15 min以上的无氧铜线表面纳米钯颗粒团聚较少,几乎无露铜现象;纳米钯粉和OP-10的质量分数分别增加至4%和6%时,在室温浸镀20 min的无氧铜线镀层质量最好。此外,当镀液温度升高至约60℃时,浸镀15 min的无氧铜线镀层不均匀,漏铜现象明显。在450℃真空退火后,镀钯铜线的镀层界面结合强度和平整度提高。

压延率对无氧铜板高温退火的组织及性能影响

高导热AMB陶瓷基板的覆铜厚板性能直接影响基板的电性能和力学性能。通过对无氧铜原料板的加工、微观组织调整以及陶瓷与铜板的活性焊料复合,达到AMB陶瓷覆铜基板最优的组织状态和电学与力学性能。首先对无氧铜板原料进行450℃和650℃再结晶退火0.5 h处理,得到两种原始的铜板组织。其次,对原始铜板进行压延率为15%、30%、45%、60%、75%的压延和800℃/1 h的退火处理,研究了退火铜板的微观组织及力学性能和电学性能。结果表明:当压延率在15%~75%时,随着压延率增加,晶粒逐渐被拉长变成扁平状,再变成纤维状;硬度随着压延率增加逐渐增大,铜板的延伸率逐渐减小,抗拉强度在压延率为15%~60%时逐渐增大,压延率达到75%时出现了小幅度降低。当在800℃退火1 h后,铜板表面晶粒尺寸随着压延率的增加逐渐减小,晶粒分布更加均匀,其大小稳定在400~800μm之间。铜板在压延率为15%~60%时的抗拉强度基本保持不变;当压延率到达75%时,抗拉强度出现小幅度降低。铜板硬度随着压延率增加基本保持不变。当压延率从15%变为75%时,铜板的电阻率有小幅度上升。

氢氧含量对低氧铜扁线焊接性的影响研究

目的研究TIG焊接过程中低氧铜扁线氢、氧含量对扁线焊接接头的影响。方法以规格为3 mm×2 mm的无氧铜扁线和不同氢、氧含量的低氧铜扁线为研究对象,采用氩弧焊接(TIG)方式,系统研究了不同种类扁线母材及焊接接头的微观组织和焊后力学、电学性能。结果无氧铜扁线经TIG焊接后,焊接接头处没有产生明显的气孔,焊接接头性能良好,其抗拉强度及塑性均与母材的相当。低氢低氧、低氢高氧扁线焊接接头出现少量的气孔,破断力值分别为678 N和654 N。而高氢低氧、高氢高氧扁线焊接接头出现大量的大气孔,破断力值分别为208.7 N和126 N。不同氢氧含量的低氧铜扁线焊后导电率无明显变化。结论低氧铜扁线焊接接头内部气孔的数量和尺寸受氢、氧含量的影响,相比之下氢元素的影响更大。

太赫兹低损耗金刚石-无氧铜输能窗研究

首次开展太赫兹金刚石-无氧铜盒型输能窗研究,利用低损耗的无氧铜材料代替传统可伐合金材料,显著降低输能窗传输损耗、提高器件输出功率。为降低无氧铜与金刚石热膨胀系数严重不匹配造成的封接应力,提出一种多槽应力释放结构,将金刚石表面封接应力由210 MPa减小至50 MPa,小于金刚石与无氧铜组合抗拉件的平均封接强度116.2 MPa。根据设计结果,开展金刚石-无氧铜输能窗封接试验,氦漏率≤1×10^(-11)(Pa·m^(3))/s,实现了气密封接。测试金刚石-无氧铜输能窗传输损耗为0.7 dB,比采用金刚石-可伐输能窗的传输损耗减小2 dB,即输出功率可以提高60%,为研制大功率太赫兹源奠定了重要关键技术基础。

压延铜箔的无氰电镀镍铜黑化处理工艺

为了研究出相较于电镀纯镍黑化工艺成本更低的电镀镍铜黑化工艺,以NiSO_(4)·6H_(2)O、CuSO_(4)·5H_(2)O、H_(3)BO_(3)、(NH_(4))_(2)S_(2)O_(8)和C_(6)H_(15)NO_(3)为镀液基本成分,通过加入添加剂,使金属在铜箔表面沉积形成光陷阱结构,从而实现电镀镍铜使铜箔黑化的目的。研究了镀液成分及工艺参数对黑化箔镀层亮度的影响,对黑化箔镀层的成分进行了测试,并对黑化箔镀层结构进行了观察分析。研究结果表明:电镀镍铜的黑化箔镀层中Cu代替Ni形成镀层,黑化箔镀层成分为NiCu;通过加入添加剂可以使电镀时使用的电流密度降低,达到了降低成本的目的。

预浸对烧结钕铁硼HEDP电镀铜的影响

[目的]烧结钕铁硼(Nd Fe B)的电镀前处理技术还不够成熟,开发适宜的前处理工艺极其重要。[方法]在电镀铜前,先采用以羟基乙叉二膦酸(HEDP)为主配位剂的溶液对NdFeB进行预浸。预浸液组成和工艺条件为:HEDP 20~30 g/L,氢氧化钾20~25 g/L,碳酸钾10~15 g/L,葡萄糖酸钾1~2 g/L,乙酸0.5~1.0 g/L,室温,时间60 s。通过电化学测试对比了Nd Fe B基体有无预浸处理时,铜在其表面的电沉积行为,并通过金相显微镜、扫描电镜、能谱仪和荧光光谱测厚仪,对比了有无预浸处理的Nd FeB基体表面Cu镀层的宏观和微观表面形貌、截面形貌、元素分布及厚度分布均匀性。[结果]Nd Fe B基体预浸后表面被活化,静态电位降低。预浸液能够填满基体表面的孔隙并形成一层水薄膜,在后续电镀铜时保护基体不被腐蚀。预浸处理的Nd Fe B基体表面所得Cu镀层均匀、致密,不易氧化发黑,结合力和耐蚀性较好。[结论]对烧结钕铁硼进行预浸处理,能够保证其在后续电镀铜过程不被腐蚀,提高Cu镀层的综合性能。

HEDP浓度对烧结钕铁硼碱性无氰镀铜的影响

[目的]烧结钕铁硼(NdFeB)磁体在声电磁性器件中的应用日益广泛,但其耐蚀性较差,一般需要进行有效的表面处理以提高其耐腐蚀性能和使用寿命。[方法]采用以羟基乙叉二膦酸(HEDP)为主配位剂的碱性无氰体系对烧结Nd Fe B磁体表面电镀铜。研究了HEDP质量浓度对Cu镀层外观、表面粗糙度、厚度、结合力和耐蚀性的影响。[结果]HEDP的质量浓度为100~150 g/L时所得Cu镀层表面较光亮,厚度约为1.55μm,表面粗糙度较低,结合力和耐蚀性最佳。[结论]适宜的HEDP浓度有利于获得综合性能较好的Cu镀层。

稀土钇对无氧铜铸锭组织和性能的影响

采用直读光谱仪、氧氮氢分析仪、显微硬度计和涡流电导率仪等,研究了稀土Y对无氧铜铸锭组织、力学性能和导电性能的影响规律。结果表明,添加稀土Y可以显著降低无氧铜铸坯中O、S、P和Zn等杂质元素的含量;随着稀土Y含量的提高,试验铸锭的晶粒尺寸先增大后减小且分布更均匀,维氏硬度先降低后升高,导电率则先升高后降低。