3-氨基-1,2,4-三氮唑自组装膜对黄铜的缓蚀作用

3-氨基-1,2,4-三氮唑(ATA)是一种环境友好型金属处理剂, 以其在黄铜表面制备了自组装单分子膜(SAMs), 用电化学方法研究ATA SAMs对黄铜的缓蚀作用及其吸附行为. 结果表明, ATA分子易在黄铜表面形成稳定的ATA SAMs, SAMs抑制了黄铜的阳极氧化过程, 改变了电极表面的双电层结构, 固/液界面双电层电容明显降低, 有良好的缓蚀效果. 研究结果还表明, ATA的吸附行为符合Langmuir吸附等温式, 吸附机理是典型的化学吸附.     

吡咯烷二硫代氨基甲酸铵自组装膜对铜的缓蚀作用

吡咯烷二硫代氨基甲酸铵(APDTC)是一种环境友好型金属缓蚀剂, 以其在铜表面制备了自组装单分子膜(SAMs), 用电化学方法研究在0.5 mol·L-1 HCl介质中APDTC SAMs对铜的缓蚀作用及其吸附行为. 结果表明, APDTC分子易在铜表面形成稳定的APDTC SAMs, 改变了电极表面的双电层结构, SAMs同时抑制了铜的阳极氧化过程和阴极还原过程, 铜电极的电荷转移电阻明显提高, 双电层电容明显降低. 电化学阻抗和极化曲线测试结果显示, 在0.5 mol·L-1 HCl介质中, 铜表面APDTC SAMs表现出良好的缓蚀效果. 研究结果还表明, APDTC的吸附行为符合Langmuir吸附等温式, 吸附机理是介于化学吸附和物理吸附之间的一种吸附.     

碳纳米管表面的无钯活化化学镀镍研究

本文提出碳纳米管表面无钯活化的化学镀镍方法.碳纳米管经硝酸氧化和碱中和后表面生成羧基,利用羧基吸附镍离子,之后吸附的镍离子被化学还原为镍的纳米微粒并成为化学镀镍的催化活性中心.红外吸收光谱和电子显微镜观察等证实了上述活化过程的机理.实验表明,新的活化方法对碳纳米管表面化学镀是切实可行的,文中同时对化学沉积层的不同形貌进行讨论.     

2-[3-(4-甲氧基苯氧基)丙基]-1,3-二乙酰硫基丙烷的合成

自组装单层膜(SAMs)技术是自20世纪80年代以来快速发展起来的一个新型有机成膜技术,它是通过表面活性剂的头基与基底之间产生化学吸附,在界面上自发形成的有序的单分子层[1].     

玻璃表面的无钯活化化学镀镍

在非金属基体上化学镀镍 ,一般要先在基体上形成一层化学镀的催化剂 ,传统工艺是采用PdCl2 SnCl2 活化 敏化法[1 ] 。该工艺处理过程复杂 ,而且使用有毒的PdCl2 ,其价格昂贵。因此无钯活化法将带来巨大的经济效益和社会效益。我们曾在这方面进行了有益的尝试 ,如将玻璃表面经喷雾热解形成ZnO ,然后吸附银盐 ,活化还原 ,再化学镀[2 ] 。李兵等[3] 研究了非金属材料无钯催化活化工艺。研究了活化时间及温度对覆盖度的影响 ,但未给出具体活化液配方。本文提出了玻璃表面的一种无钯活化镀镍液配方 ,该配方由醋酸镍、甲醇、柠檬酸钠和氨组…     

表面等离子体共振光谱研究蛋白质-高分子结合体在金表面的自组装

研究了蛋白质-高分子结合体在金片表面的自组装行为.首先制备了一种引发剂2-溴-2-甲基丙酸-2-氨氧基乙酯(ABM),该引发剂可以与5′-磷酸吡哆醛(PLP)活化的牛血清白蛋白(BSA)的氮端相连,进而得到大分子引发剂BSA-Br.最后以甲基丙烯酸寡聚乙二醇酯(OEGMA)为单体,利用原子转移自由基聚合法(ATRP)制备BSA-POEGMA结合体.利用红外光谱(FTIR)、紫外可见分光光度计(UV-Vis)、基质辅助激光解析串联飞行时间质谱仪(MALDI-TOF-MS)对各步产物进行表征.利用表面等离子体共振光谱(SPR)研究BSA-POEGMA结合体在金片表面的自组装行为,以及金片表面吸附的BSA-POEGMA结合体对其他蛋白质包括溶菌酶(Lys)和纤维蛋白原(Fib)的吸附效果影响.     

疏水球状碳酸钙的制备、表征及对聚丙烯力学性能的影响

以十二碳醇磷酸酯(DDP)为改性剂, 采用碳化法制备了分散性良好的球状碳酸钙粒子. 通过FESEM, XRD, FTIR及活化度和接触角测试对产物进行了表征. XRD分析结果表明, 随着DDP添加量的增加, 所得CaCO3由方解石型向文石型转变. FTIR结果表明, 改性剂与碳酸钙表面是以化学键合和物理吸附方式相结合. 当DDP含量达到2%时, 接触角为120.43°, 活化度达到99%, 碳酸钙粒子由亲水性转变为完全疏水性. 考察了反应温度和DDP含量对产物形貌与结晶行为的影响, 并对改性机理进行了初步探讨. 将产品填充到聚丙烯(PP)中, 测定了PP的力学性能.     

超声辐照乳液聚合制备聚丙烯酸正丁酯空心微球

利用超声辐照引发包覆乳液聚合制备了聚丙烯酸正丁酯(PBA)空心微球.TEM和DLS结果显示,空心微球粒径均一,壳层厚度均匀.FTIR结果显示,壳-核物质间以物理吸附相结合,没有形成化学键.同时,利用TEM和DLS研究了空心微球的形成机理,阳离子表面活性剂十六烷基三甲基溴化铵(CTAB)在CMC浓度以下首先吸附在纳米SiO2粒子表面形成双层结构,然后丙烯酸正丁酯(BA)单体增溶进入CTAB层间,在超声辐照引发、分散作用下包覆聚合形成均一的PBA-SiO2壳-核粒子,再利用HF溶液去除无机核,得到PBA空心微球.     

碱活化多孔碳用于分离甲苯及活化/吸附机理

采用生物质木质素磺酸钠(SLS)为碳源, 先与硬模板NaCl混合预碳化, 再加入活化剂NaOH在氮气保护下升温至850 ℃碳化, 得到SLS基碱活化的多孔碳吸附剂(SPCN). 将SPCN用于吸附液体石蜡中芳香烃甲苯, 对比研究了不同活化剂加入量对SPCN结构、 性质及吸附效果的影响. 结果表明, SPCN表面具有丰富的官能团和发达的微/介孔结构, 活化剂加入量对比表面积的影响为先增大后减小, 碱/碳质量比为1∶1时比表面积达到最大值(710.4 m ²/g); 吸附量与比表面积呈正相关, 样品SPCN-1的最大吸附量为2875.17 mg/g, 远高于商业吸附剂, 经5次吸附-解吸循环后仍保持92.5%的吸附效率. 探究了活化机理, NaOH、 碳质和气体发生氧化还原反应释放气体留下孔隙, 经充分酸洗、 水洗后得到永久孔道. 最后, 结合扫描电子显微镜(SEM)、 透射电子显微镜(TEM)、 拉曼光谱(Raman)、 X射线衍射(XRD)、 傅里叶变换红外光谱(FTIR)和比表面积分析等结果证明了吸附机理主要是孔隙填充效应、 范德华力、 π-π相互作用及电子供/受体作用的共同作用. 首次报道了SPCN应用的新方向并探究了活化与吸附机理, 制备方法简易、 经济, 产品循环稳定性好、 无污染, 有望用于工业化生产.     

密度泛函理论计算研究表面应力对钯催化乙炔选择性加氢活性与选择性的影响（英文）

在石油催化裂解过程中,除了生成乙烯、丙烯及丁烯等烯烃,还会产生部分炔烃.目前工业上通常采用炔烃选择性加氢转化为对应的单烯烃,以除去其中炔烃.由于产品烯烃中的炔烃等杂质含量需极低,这就对用于加氢催化剂的活性和选择性提出了很高的要求,即催化剂需要选择性吸附炔烃并加氢,而不损失其中的烯烃.经过前期大量的基础研究工作,目前工业中炔烃选择性加氢应用最广泛的催化剂是负载型钯基催化剂.然而,单独的钯金属选择性并不理想,因而对其选择性以及活性进行调控成为了当前关注的研究课题.本文采用密度泛函理论计算结合微观反应动力学模拟手段,研究了钯金属表面应力存在条件下的活性与选择性,以及形成次表层物种的可能性和形成后的活性与选择性.研究发现,改变钯金属的晶格参数与表面应力,反应物、表面反应中间体和产物的吸附能都会产生相应的变化,且吸附能与晶格参数的变化存在线性关系,晶格参数越大,吸附越强.利用表面反应过渡态能量与初始态能量之间的线性关系,相应的乙炔加氢生成乙烯的反应速率可以通过微观反应动力学模拟得到.结果显示,不同晶格参数的钯催化剂催化乙炔加氢生成乙烯的反应活性位于相应火山型曲线的强吸附侧,即减弱乙炔和氢的吸附强度可提高乙烯的生成速率.在此基础上,本文研究了不同表面应力的钯催化剂在次表面吸附不同覆盖度碳原子和氢原子的情况,发现晶格参数越大越有利于碳原子和氢原子在次表面的吸附.同时,研究发现在次表面碳掺杂的条件下,不同表面应力条件下的钯催化剂的活性均有所增强.此外,由于乙烯在所有研究的钯催化剂表面脱附比进一步加氢容易,因而乙烯都可以选择性生成.     

A New Activation Method for Electroless Metal Plating：Palladium Laden via Bonding with Self—Assembly Monolayers

A new activation method has been developed for electroless copper plating on silicon wafer based on palladium chemisorption on SAMs of APTS without SnCl2 sensitization and roughening condition.A closely packed electroless copper film with strong adhesion is successfully formed by AFM observation.XPS study indicates that palladium chemisorption occurred via palladium chloride bonding to the pendant amino group of the SAMs.     

超薄铜膜包覆的金刚石纳米复合粉体制备与表征

在氯化亚锡敏化、氯化钯活化的条件下,通过化学镀方法,成功地在纳米金刚石粉体表面制备了超薄铜膜.用X射线粉末衍射(XRD)和傅立叶红外吸收光谱(FTIR)表征了该Cu-金刚石纳米复合材料.此种复合材料在无水乙醇中超声分散5 min后的溶胶可稳定存放半年之久而不见沉降.     

Reactive coupling of 4-vinylaniline with hydrogen-terminated Si(100) surfaces for electroless metal and "synthetic metal" deposition

Pristine and resist-patterned Si(100) substrates were etched by aqueous HF to produce hydrogen-terminated silicon (H-Si(100)) surfaces. The H-Si(100) surface was then subjected to UV-induced reactive coupling of 4-vinylaniline (VAn) to produce the VAn monolayer-modified silicon (VAn-Si) surface. The VAn-Si surface was first functionalized with a "synthetic metal" by oxidative graft polymerization of aniline with the aniline moieties of the coupled VAn molecules. The composition and topography of the VAn-Si and polyaniline (PAn)-grafted VAn-Si (PAn-VAn-Si) surfaces were characterized by X-ray photoelectron spectroscopy and atomic force microscopy, respectively. The doping-undoping (protonation-deprotonation) and redox-coupling (metal reduction) behavior, as well as the electrical conductivity, of the surface-grafted PAn were found to be similar to those of the aniline homopolymer. The VAn-Si surface was also funtionalized by the electroless plating of copper. Not only did the VAn layer provide chemisorption sites for the palladium catalyst, in the absence of prior sensitization by SnCl2, during the electroless plating process, it also served as an adhesion promotion layer and a low-temperature diffusion barrier for the electrolessly deposited copper. Finally, micropatterning of the grafted PAn and of the electrolessly deposited copper were demonstrated on the resist-patterned VAn-Si surfaces.     

Reflective and conductive surface‐silvered polyimide films prepared by surface graft copolymerization and electroless plating

Argon plasma‐pretreated polyimide (PI) films were subjected to UV‐induced surface graft copolymerization with 4‐vinylpyridine(4VP) under atmospheric conditions. Electroless plating of silver was carried out effectively on the 4VP graft copolymerized PI (PI‐g‐P4VP) surface after PdCl₂ activation and in the absence of SnCl₂ sensitization (the Sn‐free process). The surface compositions of the modified PI films were studied by X‐ray photoelectron spectroscopy (XPS). XPS results showed that the PI‐g‐P4VP surface is ready for electroless deposition of silver via the Sn‐free process. The grafted 4VP layer with well‐preserved pyridine groups was used not only as the chemisorption sites for the palladium complexes (without the need for prior sensitization by SnCl₂) during the electroless plating of silver, but also as an adhesion promotion layer for the electrolessly deposited silver. The silver metallized PI films show high reflectivity and conductivity with a surface resistance of 1.5 Ω and a reflectivity of 91.3%, respectively. Copyright © 2007 John Wiley & Sons, Ltd.     

Electroless Deposition of Copper on Poly(tetrafluoroethylene) Films Modified by Plasma-Induced Surface Grafting of Poly(4-vinylpyridine)

Argon plasma-pretreated poly(tetrafluoroethylene) (PTFE) films were solution coated with a thin layer of poly(4-vinyl pyridine) (P4VP). Subsequent exposure of the films to argon plasma resulted in the grafting of P4VP on the PTFE films. Electroless plating of copper could be carried out effectively on the P4VP-grafted PTFE (P4VP-g-PTFE) surface after PdCl₂ activation and in the absence of SnCl₂ sensitization (the Sn-free process). The catalytic processes of the electroless plating of copper in the presence and absence of sensitization by SnCl₂ were also compared. The effect of glow discharge conditions on the P4VP concentration and the adhesion strength of the electrolessly deposited copper was investigated. The T-peel adhesion strength of the electrolessly deposited copper with the graft-modified PTFE film was improved in the absence of SnCl₂ sensitization and could reach about 3 N/cm. PdCl₂ activation and electroless deposition of copper could not be carried out on the pristine or the Ar plasma-treated PTFE surface in the absence of prior sensitization by SnCl₂. X-ray photoelectron spectroscopic (XPS) analysis revealed that the electrolessly deposited copper delaminated from the P4VP-g-PTFE film by cohesive failure inside the PTFE film.     

Zerovalent metal polymer composites. II. Metal–polymer microdispersions

Metallization of water-soluble polymers incorporating metal-binding ligand is achieved by binding palladium ions at substoichiometric quantities, followed by reduction to polymer–zero-valent palladium complex and deposition of transition metal ions by electroless plating solutions. The polymers studied include poly[N,N,N-trimethyl-N-(m- and p-vinylbenzyl)ammonium chloride], poly-L -glutamic acid, poly-L -lysine, and a copolymer of 2-phenylhydroquinone-2-amino-phthalic acid. Noble metal polyelectrolyte solutions were directly reduced with dimethylamineborane to stable microdispersions. The reactive nickel, cobalt and copper microdispersions were coated on KODAK ESTAR filmbase. Scanning electron microscopy (SEM), ESCA, and IR were used for material characterization. Conductivity and magnetic properties were also measured. Hydrophobic materials such as graphite and fluorinated graphite were metallized in organic solvents using hydrophobic trioctylammonium–tetrachloropalladate as the activating noble metal complex. The metallized conductive graphites were evaluated for their electrochemical properties.     

Preparation of Pd/ceramic composite membrane 1. Improvement of the conventional preparation technique

The Pd/ceramic composite membrane made is reported in this paper. The thin palladium film was deposited on the surface of a porous ceramic substrate by the conventional and improved electroless plating technique, respectively. The rate of palladium deposition increases and especially the sensitization and activation steps in the conventional electroless plating process has been omitted by an improved technique.     

Electroless plating of copper on Si(100) surfaces modified by surface‐initiated atom‐transfer radical polymerization of 4‐vinylpyridine

Surface‐initiated atom‐transfer radical polymerization (ATRP) of 4‐vinylpyridine (4VP) on a pretreated Si(100) surface was carried out. The composition and topography of the Si(100) surface modified by poly(4‐vinylpyridine) (P4VP) were characterized by XPS and atomic force microscopy (AFM), respectively. The P4VP layer on the Si(100) surface was used not only as chemisorption sites for the palladium complexes without prior sensitization by SnCl₂ solution during the electroless plating, but also as an adhesion promotion layer for the electrolessly deposited copper. The electrolessly deposited copper on the Si–P4VP surface exhibited a 180° peel adhesion strength above 6 N/cm. The adhesion strength was much higher than that of the electrolessly deposited copper to the pristine silicon surface. Copyright © 2008 John Wiley & Sons, Ltd.     

空心微珠表面化学镀Ni-Co-P合金

以无机非金属粉煤灰空心微珠为芯材, 利用化学镀工艺对其表面进行金属化改性, 可以得到表面完整包覆的导电粉体, 该粉体具有中空, 质轻, 粒度细, 高强度, 耐高温, 导电性能好等多种优异性能, 可部分代替金属和铁氧体微粉作为电磁波吸收剂. 采用SnCl2和PdCl2进行敏化-活化处理后, 在空心微珠表面化学包覆Ni-Co-P合金层, 利用XRD、EDS、SEM和镶嵌金相等方法对样品进行形貌观察和分析表征, 结果表明, 使用PdCl2作活化剂可以得到优质均匀的Ni-Co-P合金镀层, 镀层光亮, 均匀, 包覆完整. 化学镀后镀层呈非晶态, 450 ℃氢气气氛下热处理后出现结晶相Ni3P和六方晶系的α-Co单质.     

Electrochemically deposited palladium as a substrate for self-assembled monolayers

The vast majority of reports of self-assembled monolayers (SAMs) on metals focus on the use of gold. However, other metals, such as palladium, platinum, and silver offer advantages over gold as a substrate. In this work, palladium is electrochemically deposited from PdCl2 solutions on glassy carbon electrodes to form a substrate for alkanethiol SAMs. The conditions for deposition are optimized with respect to the electrolyte, pH, and electrochemical parameters. The palladium surfaces have been characterized by scanning electron microscopy (SEM) and the surface roughness has been estimated by chronocoulometry. SAMs of alkane thiols have been formed on the palladium surfaces, and their ability to suppress a Faradaic process is used as an indication for palladium coverage on the glassy carbon. The morphology of the Pd deposit as characterized by SEM and the blocking behavior of the SAM formed on deposited Pd delivers a consistent picture of the Pd surface. It has been clearly demonstrated that, via selection of experimental conditions for the electrochemical deposition, the morphology of the palladium surface and its ability to support SAMs can be controlled. The work will be applied to create a mixed monolayer of metals, which can subsequently be used to create a mixed SAM of a biocomponent and an alkanethiol for biosensing applications.