十六硫醇自组装膜对Ag的防变色作用研究

针对Ag制品的变色问题,在Ag表面制备十六硫醇(HDT)自组装分子膜(SAMs),用H2S加速变色实验评价防变色效果,通过正交试验法得到最佳成膜工艺为:温度60℃,浓度0.1 mol/L,自组装时间为2 h。采用接触角测定和极化曲线、电化学阻抗、循环伏安曲线等电化学方法对膜的性能进行表征。结果表明:乙醇溶液中HDT在Ag表面形成了一层致密的自组装分子膜,具有良好的防变色效果。HDT SAMs对Ag腐蚀的阳极氧化和阴极还原均有抑制作用,膜的覆盖率为94.8%,缓蚀率达到95.9%。     

水溶液中银表面自组装膜工艺

采用银在水溶液表面形成C18SH自组装膜(SAMs)的工艺,在银表面得到致密、平整,表现出明显疏水性的SAMs。EMPA和XPS测试表明,表面活性剂分别作为C18SH的分散剂,自组装过程中起到传输作用,本身不参与成膜,但影响SAMs的厚度和倾斜角。银试样表面的Ag2O在成膜过程中被硫醇中的H-S键还原为Ag,同时有Ag-S-C18H37键的形态形成。     

OTS自组装单分子膜在玻璃表面功能化的研究

采用分子自组装技术在羟基化的玻璃基片表面成功制备了十八烷基三氯硅烷单层膜 (OTS-SAMs).运用接触角测试仪测定了水在自组装薄膜表面的接触角;用原子力显微镜(AFM)分析了OTS-SAMs的表面形貌,并对经过紫外线照射改性的OTS-SAMs薄膜表面进行分析.结果表明:该组装膜具有很好的疏水性,其对水的接触角高达105°;在组装初期2 min内,十八烷基三氯硅烷水解产物主要是与基体表面的羟基发生聚合反应,表现为岛状物结构团簇,随着组装时间的增加,基体表面的有机硅烷分子之间发生聚合反应,当组装15 min后,成膜过程趋于稳定,可以在基体表面形成平整致密的自组装薄膜;经过紫外线照射改性后的薄膜表面亲水性明显提高,在2 h时达到了很好的羟基化效果.     

《电镀与精饰》2011年第3期

<正>L半胱氨酸自组装膜对间苯二酚氧化的电催化作用电沉积ZnO薄膜超声处理后结构和缺陷的研究-研究了pH对L-半胱氨酸自组装膜修饰电极的影响,发现该膜对间苯二酚的电化学氧化具有明显的催化作用。在pH=6.86的L-半胱氨酸溶液中制得的膜最致密。在pH=5的醋酸钠-醋酸缓冲溶液中,间苯二酚在L-半胱氨酸自组装膜修饰电极上产生一灵敏的氧化峰,且峰电流与间苯二酚浓度在0.1～0.6mmol/L范围内呈良好的线性关系     

MPTS/Mg分子膜的制备及摩擦学性能的研究

目的通过在金属镁表面自组装MPTs分子膜,改善金属镁的耐摩擦性。方法采用自组装成膜技术,以MPTS为自组装溶质,使其浸入到溶剂中制备成自组装分子膜溶液,然后吸附于镁基体表面。通过扫描电子显微镜(SEM)和自动椭圆偏振测厚仪测试了在金属镁片形成的MPTS分子膜的形貌及膜厚范围,并进行了详细的分析。结果随着自组装时间的延长,膜的致密性逐渐增强,力学性能得到很大的改善。当反应时间为5 min时,MPTS组装处于初期膜生长阶段,膜层比较疏松、多孔,此时的自组装膜还没有起到缓释作用;当反应时间延长到60~80 min时,反应逐步趋于完全;当成膜时间达到80 min时,已在金属镁表面形成了比较致密有序且质地均匀的MPTS自组装分子膜。结论通过自组装成膜技术,在金属镁表面形成性能优良的膜层,随着自组装时间的延长,膜的致密性逐渐增强,其耐摩擦性能得到进一步的完善,且其受力均匀。     

不同链长烷基硫醇自组装膜对银的防变色作用

将不同链长的烷基硫醇溶于乙醇,在银表面制备自组装膜。采用接触角测试、电化学试验、加速变色试验和X射线光电子能谱(XPS)等方法来表征自组装膜的性能。结果表明:十二烷基硫醇(DT)、十六烷基硫醇(HDT)和十八烷基硫醇(ODT)都可以在银表面形成疏水性的自组装膜,对基体腐蚀起到良好的保护作用;ODT自组装膜的致密性最好,而HDT自组装膜的防变色效果最好。     

430 不锈钢表面月桂酸自组装膜的探究

采用浸泡法在430不锈钢表面制备了月桂酸自组装膜,通过电化学方法、接触角测试及微观形貌分析,研究了该自组装膜在430不锈钢表面的吸附行为及缓蚀作用。研究结果表明:经过简单的浸泡,月桂酸分子能够稳定地吸附在不锈钢表面,自组装时间、组装液浓度以及基底表面前处理对组装膜的缓蚀效率有较大影响,自组装时间4 h、月桂酸浓度5 mmol/L、组装温度35℃为最佳自组装条件;基底在组装之前进行钝化处理,有利于形成致密的自组装分子膜,提高不锈钢的耐蚀性能。     

表面膜对点阵结构Ti6Al4V表面超疏水特性的影响

采用激光加工在Ti6Al4V试样表面加工不同间距的点阵结构,采用自组装技术制备4种自组装分子膜。通过表面形貌和接触角的测量表征试样的表面特性。结果表明:通过激光点阵加工和沉积自组装分子膜,可显著增加Ti6Al4V试样的水接触角。长链分子FDTS、FOTS和OTS制备的自组装分子膜,使Ti6Al4V试样的接触角均大于150?,形成超疏水表面,其中沉积FDTS自组装分子膜时,试样的接触角最大,可达164.5?。沉积短链分子MPS自组装分子膜时,只有当激光加工间距为50μm时,试样方可形成超疏水表面;间距增大后,试样表面变成疏水表面。沉积4种自组装分子膜时,试样的接触角均随激光点阵加工间距的增大而减小。     

采用配体交换法制备贵金属纳米粒子修饰电极的研究

选择8个碳链长度的烷基双硫醇分子在电极表面自组装构筑Au-SHSAM模板,然后将由弱保护剂四辛基溴化铵(TOAB)稳定的小尺寸Au、Ag、Pd和Pt纳米粒子通过纳米粒子与电极上巯基之间的强相互作用(M-S)将其表面的弱保护剂TOAB替换的方式,成功实现了贵金属纳米粒子在巯基模板电极表面的自组装,利用循环伏安法(CV)和扫描隧道显微镜(STM)对纳米粒子修饰电极在H2SO4溶液中的电化学行为以及纳米粒子在电极表面的形貌进行了表征,发现可以通过调节浸泡时间控制纳米粒子在电极表面的覆盖度。该方法新颖、简单而且具有一定的普适性。     

咪唑啉自组装单分子膜在镁合金AZ91D表面的防腐蚀研究

用咪唑啉水溶液在镁合金(AZ91D)电极表面制备了自组装单分子膜，研究了该组装膜在0.2 mol/L NaCl中对AZ91D的缓蚀作用.通过接触角、FT-IR、EIS和线性极化等方法对自组装膜的形成过程和保护效率进行了研究，得出最佳的咪唑啉组装液浓度为5×10-4mol/L和最佳组装时间为72 h下的缓蚀效率.     

Growth of self-assembled monolayer on tetrahedral amorphous carbon film coated magnetic head

The magnetic heads overcoated by tetrahedral amorphous carbon (ta-C) films have been immersed in the 1H, 1H, 2H, 2H-perfluorodecyltrichlorosilane (FDTS) solvent at different predetermined dipping time. The growth of FDTS self-assembled monolayer (SAM) on the ta-C surface has been confirmed by time-of-flight secondary ion mass spectrometry. Four distinct stages were observed in the growing process: (1) low coverage (nucleation), (2) growing up (3) coalescence and (4) complete monolayer, similar to the theoretical models of epitaxial film growth at low temperatures. Contact angle measurement using de-ionized water is carried out to study the time dependence of contact angle during the growth process of FDTS monolayer. The surface morphology, profiles and roughness (rms) of FDTS monolayer were determined by atomic force microscopy (AFM). Furthermore, the variation of monolayer thickness and distribution was revealed by transmission electron microscopy, which is in agreement with the AFM and contact angle results.     

Studies on corrosion inhibition of copper by alkanethiol SAMs prepared in aqueous micellar solution

The character of 1‐dodecanethiol (DT) self‐assembled monolayers (SAMs) formed on copper surface in aqueous micellar solution is investigated by means of contact angle measurement, electrochemical impedance spectroscopy (EIS), and polarization curves. The contact angle measurement shows that the SAMs formed in aqueous micellar solution are oriented and compact. According to the electrochemical measurements, it is found that both the concentration of DT and temperature can significantly affect the property of SAMs. The DT SAMs can prevent the corrosion of copper in chloride‐containing solution effectively because the inhibition efficiency can reach 99.59% at the DT concentration of 10^?2 M . The adsorption of DT in aqueous micellar solution obeys to the Langmuir adsorption isotherm, and the value of the free energy of adsorption calculated indicates that the adsorption of DT molecule is a spontaneous process and a typical of chemical adsorption.     

Prevention of passive film breakdown on iron in a borate buffer solution containing chloride ion by coverage with a self-assembled monolayer of hexadecanoate ion

Breakdown of a passive film on iron in a borate buffer solution (pH 8.49) containing 0.1 M of Cl⁻ was suppressed by coverage of the passive film surface with a self-assembled monolayer (SAM) of hexadecanoate ion C₁₅H₃₁CO₂⁻ (C₁₆A⁻). The pitting potential of an iron electrode previously passivated in the borate buffer at 0.50 V/SCE increased by treatment in an aqueous solution of sodium hexadecanoate for many hours, indicating protection of the passive film from breakdown caused by an attack on defects of the film with Cl⁻. No breakdown occurred over the potential range of the passive region by coverage with the SAM of C₁₆A⁻ in some cases. Structures of the passive film and the monolayer were characterized by X-ray photoelectron and Fourier transform infrared reflection spectroscopies and contact angle measurement with a drop of water.     

玻璃OTS自组装膜的构建及钛表面图案化

采用自组装技术在玻璃表面接枝了疏水的十八烷基三氯硅烷(OTS)膜,通过原子力显微镜(AFM)和接触角对OTS膜进行了表征和成膜机理探讨。结果表明:OTS膜层的疏水性好,且OTS自组装分子膜在玻璃表面呈"岛式"形貌;该功能化玻璃的OTS膜层可应用于钛表面图案化,通过紫外辐照技术并借助OTS玻璃成功地在钛基体表面构建了图案化的明胶涂层,OTS膜层的疏水性随着图案化过程中紫外辐射时间的增长而减弱,具有一定的时效性。     

Corrosion inhibition of copper by 2,5-dimercapto-1,3,4-thiadiazole monolayer in acidic solution

2,5-Dimercapto-1,3,4-thiadiazole (DMTD) monolayer was self-assembled on the fresh copper surface to form protective monolayer against copper corrosion in acidic solution. Its corrosion inhibition was investigated in 0.5 M HCl by cyclic voltammetry, potentiodynamic polarization and electrochemical impedance spectroscopy methods. The results revealed that the DMTD monolayer inhibited the copper corrosion effectively with the optimum self-assembly time of 10 h and the optimum self-assembly concentration of 7.5 mM. Surface observation was performed using scanning electron microscope, contact angle goniometer and Fourier transform infrared spectrometer. The molecular simulation has been used to simulate the adsorption model of DMTD molecule on Cu(1 1 1) surface.     

植酸在 316 L 不锈钢表面的自组装及缓蚀性能研究

以浸泡法在化学氧化处理前后的316L不锈钢表面制备了植酸自组装膜,通过动电位扫描、SEM观察及FT-IR测试,研究了组装液pH与组装时间对植酸自组装膜吸附行为及耐蚀性能的影响。结果表明:植酸被成功地组装到316L不锈钢表面,并使其耐腐蚀性能大大提高。相比而言,化学氧化处理有利于形成更致密、更耐腐蚀的自组装膜。不经化学氧化处理时,植酸组装的最佳pH为6.90,最佳时间为12 h;而经化学氧化处理时,植酸组装的最佳pH也为6.90,但最佳时间缩短为4 h。     

Lubrication for Micro Forming of Ultra Thin Metal Foil

The objective of the present investigation is to establish lubrication technique in micro forming operation. Conventional lubricant, in general, cannot be applied directly to micro forming process, since the lubricant thickness is similar to the dimensions of feature size in micro forming operations. In present investigation, the Octadecyltrichlorosilane (OTS) self-assembled monolayer (SAM) was chosen as a potential lubricant because it sticks to Si wafer die and can be applied to surface with uniform thickness of several nanometer thick. Friction coefficient and adhesion force were measured for OTS SAM coated wafer. It is shown that OTS SAM coated Si wafer offers substantially lower friction and lower adhesion than bare Si wafer. Micro channel wafer die was coated with OTS SAM and channel forming operation with 1μm thick copper foil was carried out. Experimental results show that OTS SAM coated wafer die improves forming characteristic of ultra thin copper foil substantially. These results show that SAM coating can be used as a lubricant in micro forming successfully.     

Improvement of the film thickness by modification of the hydroxymethylbenzene SAM with tetraethoxysilane and octanediol for protection of iron from corrosion in 0.5 M NaCl

For enhancing the protective efficiency, P of a film prepared by modification of a p-hydroxymethylbenzene HOC₆H₄ (HOMB) self-assembled monolayer (SAM) adsorbed on iron by the formation of a covalent bond, an increase in the film thickness, d was attempted. The HOMB SAM was modified with tetraethoxysilane (C₂H₅O)₄Si (TES), 1,8-octanediol HO(CH₂)₈OH (C₈DO), 1,2-bis(triethoxysilyl)ethane (C₂H₅O)₃Si(CH₂)₂Si(OC₂H₅)₃ (BTESE) and alkyltriethoxysilane C_nH_2n+1Si(OC₂H₅)₃ (C_nTES, n = 8 or 18). The P value of the film was determined by polarization measurement of a covered iron electrode in an aerated 0.5 M NaCl solution after immersion in the solution for 1.5–72 h of the immersion time, t. High values of P, more than 82% were obtained for the films of HOMB SAM modified with TES, C₈DO and C_nTES and with TES, C₈DO, BTESE and C_nTES in the range of t up to 72 h. The highest value was 93.2%, for the film of HOMB SAM modified with TES, C₈DO, BTESE and C₁₈TES, of which d was 4.7 nm. The film of HOMB SAM modified with TES, C₈DO and C₈TES was characterized by contact angle measurement, X-ray photoelectron spectroscopy and FTIR reflection spectroscopy.     

Preparation of a one-dimensional polymer film on passivated iron by modification of a carboxylate ion self-assembled monolayer with octyltriethoxysilane for preventing passive film breakdown

A self-assembled monolayer (SAM) of 16-hydroxyhexadecanoate ion HO(CH₂)₁₅CO₂⁻(HOC₁₆A⁻) has been prepared on an iron electrode passivated in a borate buffer solution (pH 8.49) in the preceding paper. In this work, the HOC₁₆A⁻ SAM on the passivated electrode was modified with octyltriethoxysilane C₈H₁₇Si(OC₂H₅)₃ to form a film composed of one-dimensional polymer. Prevention of passive film breakdown was examined by anodic polarization measurements of the electrodes uncoated and coated with the modified SAM in the borate buffer containing 0.1 M of Cl⁻. The pitting potential, E_pit of the coated electrode shifted from that of the uncoated electrode in the positive direction, indicating prevention of passive film breakdown. The anodic current density was decreased in the passive and transpassive regions by coverage with the modified SAM. Neither current spikes nor E_pit was observed in the curve of the passive region in some cases, demonstrating complete protection of the passive film against breakdown in the Cl⁻ solution. The modified SAM on the electrode was characterized by X-ray photoelectron and FTIR reflection spectroscopies and contact angle measurement.     

Prevention of zinc corrosion in oxygenated 0.5 M NaCl by treatment in a cerium(III) nitrate solution and modification with sodium hexadecanoate

A self-assembled monolayer (SAM) of hexadecanoate ion (C₁₆A⁻) was prepared on a zinc electrode covered with a layer of hydrated cerium(III) oxide Ce₂O₃. The protection of zinc against corrosion was examined for the electrode coated with the Ce₂O₃ layer and the C₁₆A⁻ SAM in an oxygenated 0.5 M NaCl solution. A more positive open-circuit potential of the coated electrode was maintained during immersion in the solution for 4 h than that of the uncoated one and polarization curves showed marked suppression of the anodic process, implying that the layer modified with the SAM acted as a passive film. The protective efficiency of the modified layer was extremely high, more than 99%. The zinc surface coated with the Ce₂O₃ layer and the C₁₆A⁻ SAM was characterized by X-ray photoelectron and FTIR reflection spectroscopies and contact angle measurement with a drop of water.