An Electroless Copper Plating Process Using Glyoxylate as Reductant

研究了以乙醛酸为还原剂的化学镀铜工艺、镀层结构和形貌。其镀液组成和操作条件为:28.0 g/l CuSO4.5H2O,44.0 g/l EdTA-2nA,10.0 Mg/lα,α'-联吡啶,10.0 Mg/l亚铁氰化钾,9.2 g/l乙醛酸,PH为11.5~12.5,θ为40~50℃。实验结果表明,化学镀铜溶液较稳定;镀液温度和硫酸铜质量浓度提高,铜沉积速率增大;较高的镀液温度下,化学镀铜反应的活化能较低,镀液稳定性下降;镀液PH在11.5~12.5可获得较好的铜镀层;随乙醛酸和络合剂质量浓度提高,铜沉积速率变化不大,但过量的乙醛酸导致镀液的稳定性降低;铜镀层为面心立方混晶结构,呈光亮的粉红色块状形貌,有较高的韧性。An electroless copper plating process using glyoxylate as reductant was developed,structure and surface morphology of the deposit were also studied.The bath composition and operating conditions were:28.0 g/L CuSO4 · 5H2O,44.0 g/L EDTA · 2Na,10.0 mg/L α,α'-bipyridyl,10.0 mg/L potassium ferrocyanide,9.2 g/L glyoxylate,pH 11.5--12.5,temperature 40--50 ℃.Experimental results showed that:the electroless copper plating bath was quite stable;the copper deposition rate would increased in case of bath temperature and copper sulfate concentration increased;the bath stability would decreased due to lower activation energy of copper deposition in case of higher temperature;the qualified copper coating could be obtained only at a proper bath pH range of 11.5--12.5;the copper deposition rate would not be affected by concentrations of glyoxylate and complexing agent evidently,whereas excessive content of glyoxylate would cause the bath stability decreased;the copper coating had a FCC mixed crystal structure with blocky grains、pink/bright appearance and good ductility.国家自然科学基金(20873114;20833005);国家重点基础研究发展规划项目(973)(2009CB930703

Comparison between the Electroless Copper Plating Processes Using Sodiu m Hypophosphite and For maldehyde as Reductants

比较并评价了以甲醛和以次磷酸钠为还原剂的化学镀铜工艺。结果表明,次磷酸钠镀铜液的稳定性高于甲醛镀铜液,次磷酸钠镀液的沉积速率高于甲醛镀液。以甲醛为还原剂的镀层晶粒细小,而以次磷酸钠为还原剂的镀层呈团粒状。甲醛镀铜层铜的质量分数接近100%,次磷酸钠镀铜层中铜的质量分数为93.9%,镍的质量分数为6.1%,镀层为铜-镍合金。以甲醛为还原剂的化学镀铜层的电导率、抗拉强度、延伸率等物理性能均优于次磷酸钠化学镀铜层。The processes of the electroless copper plating using sodium hypophosphite and formaldehyde as reductants were compared and evaluated.The results show that the electrolyte using sodium hypophosphite as reducing agent is more stable than that using formaldehyde as reducing agent;the electroless deposition rate of the sodium hypophosphite solution is higher than that of the formaldehyde bath;the deposit grains are very fine and dense when using formaldehyde as reductant,and the other is of agglomerate morphology;the copper content in formaldehyde's deposit is nearly 100%(wt),and the deposit from sodium hypophosphite bath contains 93.9%(wt) copper and 6.1%(wt) nickel;the conductirity,tensile strength and ductibility of formaldehyde's deposit are better than that from the sodium hypophosphite solution.国家科技攻关计划资助项目(2004BA325C

Connectivity Performance Simulation of VANET Routing Protocol

结合动态渗流理论对车载自组织网连通性能进行分析,利用nS2仿真平台,针对不同的车辆密度和车辆运行速度,对传统的路由协议(AOdV、dSdV、dSr)进行仿真,分析了影响其网络性能的因素。研究表明,为保持连通性,需要满足一定的节点密度;与dSr和dSdV协议相比,AOdV更适合于车载自组织网。The VANET connectivity performance is analyzed with dynamic percolation theory.By using NS2 simulation platform,the traditional routing protocols(AODV、DSDV、DSR) are simulated with different vehicle density and vehicle speed,and the influencing factors of network performance are analyzed.The results show that connectivity is associated with the node density,and AODV is more suitable for VANET compared with DSR,and DSDV routing protocol.福建省自然科学基金重点项目(2008H0032);集美大学优秀青年骨干教师基金资助项目(2008B002);福建省自然科学基金资助项目(2008J04008

钾修饰的MoO_3/SiO_2催化剂的XRD和TPR表征

采用XRD和TPR测试技术表征了一系列不同K与Mo摩尔比的MoO3/K2O/SiO2催化剂。XRD表征结果显示,随着元素K的加入,多钼物种逐渐被破坏,最终形成了单钼的K2MoO4物种。TPR表征显示,催化剂表面的钼物种有2种结构,即八面体的Mo(Oh)和四面体的Mo(Td)。八面体Mo(Oh)的还原峰在770 K附近,而四面体Mo(Td)还原峰在1 000 K附近;无K的MoO3/SiO2催化剂的低温还原峰出现在840 K,少量元素K的添加削弱了Mo与SiO2之间的作用,使得低温还原峰温度降低到770 K附近;随着元素K添加量的进一步增加,Mo(Oh)物种逐渐减少而Mo(Td)物种逐渐增多,从而使得催化剂表面的Mo更难被还原。高硫合成气制甲硫醇的活性随着钼基催化剂八面体(Oh)钼物种的增加而增加

Traumatic superficial temporal artery aneurysm:analysis of 7 cases

目的探讨外伤性颞浅动脉瘤的诊断和治疗方法。方法回顾性分析7例外伤性颞浅动脉的临床表现、手术方法和治疗结果。所有病例均因外伤后额部或颞部进行性增大肿物就诊,无颞浅动脉瘤破裂出血病例,全部病例在局部麻醉下切除动脉瘤囊肿,其中1例为分叉部梭形动脉瘤。结果病理报告均为假性动脉瘤,动脉外膜存在。无术后头皮缺血、坏死发生。结论根据外伤史、颞浅动脉走行上搏动性肿物的特点,颞浅动脉瘤即可明确诊断。动脉壁中膜弹力层断裂,局部因动脉血流搏动冲击膨出形成可能是颞浅动脉瘤形成的另一个机制。动脉瘤切除术是治疗颞浅动脉瘤的有效方法。Objective To explore the diagnosis and treatment for traumatic superficial temporal artery pseudoaneurysm.Methods Clinical manifestations, operation and prognosis of 7 patients with traumatic superficial temporal artery pseudoaneurysm were analyzed retrospectively.There was the same complaint of progressive swelling mass on the frontal or temporal area post brunt injury, but no complaint of rupture of the aneurysm in all the patients.All the patients underwent resections of the aneurysm capsule under local anesthesia, including one fusiform aneurysm at the bifurcation of the superficial temporal artery in 1 case.Results All the cases were pseudoaneurysm with intact outlayer of the artery.There was no complication of scalp ischemia or necrosis.Conclusion Traumatic superficial temporal artery pseudoaneurysm can be diagnosed according to the history of head injury and progressive pulsatile swelling or mass on the line of the superficial temporal artery.It may be another mechanism of forming pseudoaneurysm that breakdown of the elastic layer in the tunica media of the arterial wall and beating of arterial blood flow arterial lead to lumen enlargement on the local point.Resection of the aneurysm is an effective way of the treatment

Cyanide-free copper electroplating in sulfite/thiosulfate bath

采用黄铜和不锈钢为基体,以SO 32-/S 2 O32-为还原剂和配位剂,胺化合物为配位剂,研究了一价铜无氰镀铜工艺,其镀液组成和操作条件为:CuCl2.2H2O 16.0--21.3 g/l,232SO-/S 2 O3-0.475 MOl/l,胺化合物0.76 MOl/l,H3bO3 36 g/l,葡萄糖0.38 MOl/l,光亮剂(有机胺类化合物)0.04 Ml/l,温度40°C,PH 8(以kOH调节),搅拌,电流密度0.5--2.0 A/dM2。讨论了温度、PH、铜离子质量浓度和光亮剂体积分数对镀层质量及电流效率的影响,分别采用扫描电镜和X射线衍射表征了镀层的表面形貌和结构。结果表明,控制合适的条件可使电流效率超过90%。使用本工艺电镀时,应采用较高的镀液PH,但镀液在存置时宜控制在较低的PH。添加剂能提高镀液的整平性能,使铜镀层只出现(111)和(200)晶面,光亮度提高,晶粒更细小、致密,颗粒分布均匀。A cyanide-free copper electroplating process with sulfite/thiosulfate as reducing and complexing agents,amine compound as complexing agent and cuprous ions as main salt was studied using brass and stainless steel as substrates.The bath composition and operation conditions are CuCl2.2H2O 16.0-21.3 g/L,sulfite/thiosulfate 0.457 mol/L,amine compound 0.76 mol/L,H3BO3 36 g/L,glucose 0.38 mol/L,brightener(organic amine compound) 0.04 mL/L,temperature 40 °C,pH 8(adjusted with KOH),agitation,and current density 0.5-2.0 A/dm2.The effects of temperature,pH,mass concentration of copper ions and volume fraction of brightener on the deposit quality and current efficiency were discussed.The structure and surface morphology of the deposit were characterized by SEM and X-ray diffraction,respectively.The results showed that the current efficiency can reach over 90% by appropriately controlling the conditions.The bath pH should be relatively high in operation,but relatively low during storage.The additive can improve the leveling performance of the bath,lead to the unique formation of(111) and(200) oriented faces of copper deposit,increase the deposit brightness,and make grains smaller,more compact and more uniformly distributed.广东省教育部产学研结合专项资金项目(2006D90404019);福建省科技计划重点项目(2008H0086);国家自然科学基金项目(20873114

Preliminary pharmacodynamic study of STS as an adjuvant ofthe chemotherapy drugs in Vitro and in Vivo

目的：研究硫代硫酸钠（STS）是否能在体内、外作为化疗药的辅药。方法：应用MTT法研究STS分别与AdM、MMC和CddP等6种抗癌单药合用时对bEl-7402和MgC80-3细胞的细胞毒性作用；应用小鼠肝癌腹水瘤（H22）模型判断STS与AdM等3种药合用时的抗癌疗效；20例人原发性肝癌病人肝动脉插管化疗（AdM、MMC和CddP）前30MIn静脉推注STS（125~25g/M2）考察STS作为化疗药辅药的作用。结果：除了CddP以外，STS（500μg/Ml）与AdM等5种抗癌单药合用时对抗癌药的抗肿瘤细胞活性无明显影响（P＞005）。当不同剂量STS（350Mg/kg、35Mg/kg）分别与AdM（6Mg/kg）、MMC（14Mg/kg）和CddP（45Mg/kg）合用或仅这3种化疗药合用时，这3组腹水瘤小鼠的存活期比对照组者显著延长（P＜0001），但3组之间无明显区别（P＞005）。人肝癌肝动脉插管化疗时，STS与AdM、MMC和CddP抗癌药合用，肝癌治疗总有效率达60%，且可减少70%病人的恶心、呕吐等副作用。结论：在体内，低浓度的STS（125~25g/M2）可与AdM，MM？Objective: To study whether sodium thiosulfate (STS) can be used as an adjuvant of the chemotherapy drugs. Methods: The cytotoxicity of STS combined with ADM, MMC, CDDP, 5Fu, MTX and VCR (1PPC/ml) respectively on the cells of BEL7402 and MGc803 was studied by MTT test in vitro.The ascitic hepatoma (H22) in mice were adopted to determine the anticancer effect of STS adjuvant of ADMMMC and CDDP.Being treated with STS(12525 g/m2) 30 min before drug administration,20 patients of hepatocellular carcinoma (HCC) were carried on transcatheter arterial chemoembolization with ADMMMC and CDDP to observe the adjuvant effect of STS. Results: The anticancer activity of ADM and the other agents respectively adjuvant with STS (500 g/ml) were not obviously influented (P >005), but that for CDDP was influented .It was proven that the survival time of ascitic hepatoma treated with ADM (6 mg/kg),MMC (14 mg/kg) and CDDP (45 mg/kg) alone or three drugs in addition to STS (350 mg/kg,35 mg/kg) respectively was not significantly different (P >005).The survival time of each groups was significantly longer than that of control group (P< 0001).It have also been proven that STS adjuvant of ADM, MMC and CDDP was not decreased the chemotherapry effect (RR=60%) by transcatheter arterial chemoembolization in HCC, simultaneously it alleviated the nausea and vomiting in 70%patients. Conclusion: The study provides evidence that in vivo, STS (12525 g/m2) can be used as an adjuvant of chemotherapy drugs,such as ADM,MMC, including CDDP, and so on , for decreasing nausea and vomiting effects, espacially for transcatheter chemotherapy .福建省“八五”肝癌攻关课

A New Mathematics Model of the Temperature Programmed Analysis Technology

以表面作用包括表面吸/脱附以及表面反应本征速率方程为基础,提出新的程序升温分析技术(TPAT)的数学模型。与经典的理论模型相比,这种新的TPAT理论模型更接近实际的程序升温分析实验过程。设计和进行特定催化剂的TPd、TPr及TPO实验,得到相应的程序升温谱图,采用新的TPAT理论模型模拟上述谱图,计算出相应的表面作用活化能等重要热力学参数。结果表明,新的理论模型具有良好的模拟性能,平均相对误差(Ard)小于1%。Based on the surface effect including surface adsorption/desorption and intrinsic kinetics rate equation,a new mathematical model of the temperature programmed analysis technology was proposed.This model is different from the classical TPAT theory models,which indicates much more coincidence with the actual reactions than other models.TPAT(TPD,TPR and TPO) experiments were designed and carried out to receive their profiles.Based on these profiles of TPAT and the simulated experiments,the novel theory model was designed and the thermodynamics parameters(such as activation energy,etc.) were deduced and calculated by this model.The results show that this model has excellent simulation with the actual experiments,and the average relative errors are easily controlled less than 1%

Solvent effect on the synthesis of monodisperse amine-capped Au nanoparticles

通讯作者地址: Zheng, NF (通讯作者) Xiamen Univ, Coll Chem & Chem Engn, State Key Lab Phys Chem Solid Surfaces, Xiamen 361005, Peoples R China.A remarkable solvent effect in a single-phase synthesis of monodisperse amine-capped Au nanoparticles is demonstrated. Oleylamine-capped Au nanoparticles were prepared via the reduction of HAuCl4 by an amine-borane complex in the presence of oleylamine in an organic solvent. When linear or planar hydrocarbon (e.g., n-hexane, n-octane, 1-octadecylene, benzene, and toluene) was used as the solvent, high-quality monodisperse Au nanoparticles with tunable sizes were obtained. However, Au nanoparticles with poor size dispersity were obtained when tetralin, chloroform or cyclohexane was used as the solvent. The revealed solvent effect allows the controlled synthesis of monodisperse Au nanoparticles with tunable size of 3-10 nm. (C) 2013 Nan-Feng Zheng. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.MOST of China 2011CB932403,2009CB930703, NSFC 21131005,21021061 ,20925103 ,20923004 , Fok Ying Tung Education Foundation 12101

A nanoparticulate polyacetylene-supported Pd(Ⅱ) catalyst combining the advantages of homogeneous and heterogeneous catalysts

负载型的金属催化剂虽然分离方便,但在反应活性、选择性以及催化剂的结构表征方面均明显不如相应的均相催化剂.将均相催化剂通过不同的化学键固载于高比表面积载体是实现均相催化剂多相化的重要途径,这样可使催化剂兼具均相和多相催化剂的优势.然而要将均相催化剂锚定于特定载体上,通常涉及较为复杂的合成反应,对载体也有严格的要求.因而该法仅仅适用于实验室研究,难以实现规模生产.因此,提供一种简便有效地制备兼具均相和多相催化剂优势的催化剂合成方法非常必要.本文报道一种简便的制备聚乙炔纳米颗粒负载Pd(Ⅱ)催化剂(nP-Pd(Ⅱ))的方法,所制催化剂在水相中的SuzukI-MIyAurA偶联反应中表现出极高的活性,同时具有便于分离、容易放大制备的特点.在室温下,将乙炔气通入PdC l2-4的水溶液中迅速变得浑浊,静置后容器底部有棕色沉淀,同时溶液变为无色透明.固体产物使用水、乙醇等溶剂进行洗涤;干燥之后收集既得聚乙炔纳米颗粒负载的Pd(Ⅱ)催化剂nP-Pd(Ⅱ).使用透射电子显微镜、红外(Ir)及拉曼吸收光谱、X射线衍射(Xrd)、X射线光电子能谱(XPS)以及X射线吸收光谱(EXAfS)等手段对nP-Pd(Ⅱ)进行了详细表征.结果显示,在nP-Pd(Ⅱ)中Pd并非以Pd纳米颗粒形式存在;Xrd中没有未Pd纳米晶的特征衍射峰.Ir等表征证明乙炔在Pd的催化作用下发生聚合作用,生成了聚乙炔.EXAfS结果表明,Pd分别和氯原子以及C=C双键进行配位;同时,没有观察到Pd–Pd键的生成,进一步证明了Pd未被还原为Pd纳米颗粒.XPS也印证了Pd(Ⅱ)的价态.形貌上,nP-Pd(Ⅱ)为直径2–3nM的颗粒,其中的Pd原子均匀分散于聚乙炔纳米颗粒上,使其在反应过程中能够充分地与底物接触,从而在SuzukI-MIyAurA偶联反应中表现出极高的活性.更重要的是,由于“憎水效应“,nP-Pd(Ⅱ)在溶液中以微米级的聚集体形式存在,因而反应后通过离心或者静置从反应体系中分离出来.因此,在nP-Pd(Ⅱ)催化剂中,每个Pd原子都是潜在的活性中心,这与典型的均相催化剂相似;同时,其独特的形貌使其具备了多相催化剂便于分离的特点.因此,nP-Pd(Ⅱ)是一种兼具均相和多相催化剂优点的催化剂且其催化剂的制备方法极为简便.乙炔是常用的工业气体,溶剂采用水,制备在室温下即可完成,我们也成功地制备出克级规模的高活性、稳定性的nP-Pd(Ⅱ)催化剂.A novel nanoparticulate polyacetylene-supported Pd(Ⅱ) catalyst(NP-Pd(Ⅱ)) for use in the aqueous Suzuki-Miyaura cross coupling reaction was successfully synthesized by simply treating an aqueous solution of PdC l42- with acetylene under ambient conditions.Electron microscopy, Fourier transform infrared spectroscopy, Raman spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy and X-ray absorption spectroscopy were employed to characterize the NP-Pd(Ⅱ) structure in detail.These analyses demonstrated that the Pd atoms in the NP-Pd(Ⅱ) were present as Pd(Ⅱ) and were coordinated with both the Cl atoms and the C=C bonds of the polyacetylene.Both the homogeneous distribution of the Pd(Ⅱ) along the polyacetylene backbone and the aggregation of the NP-Pd(Ⅱ) in solution work in conjunction to make this material an ideal catalyst, combining the advantages of both homogeneous and heterogeneous catalysts.supportedbyMinistryofScienceandTechnologyofChina(2011CB932403;2015CB932303); theNationalNaturalScienceFoundationofChina(221420102001;21131005;21390390;21333008)~