铜表面均三嗪二硫醇硅烷纳米薄膜的制备及性能研究

发布时间：2018-03-06 07:25

本文选题：均三嗪二硫醇硅烷　切入点：自组装　出处：《哈尔滨工业大学》2017年博士论文　论文类型：学位论文

【摘要】：金属铜及其合金的腐蚀防护在日常生活和工业生产中十分重要。对铜而言,含有单防腐蚀官能团的有机防腐剂几乎被研究完全。本文针对上述发展局限问题,提出了一种合成新型有机防腐剂的路线。简言之,组装多种防腐蚀官能团于一种分子中,通过不同技术制备相应的防腐蚀结构。针对铜及其合金,合成出均三嗪二硫醇硅烷这一新型防腐剂,其由均三嗪二硫醇和硅烷防腐蚀官能团结合而成。本博士论文以均三嗪二硫醇硅烷的一个典型化合物,6-(3-三乙氧基硅基丙基氨)-1,3,5-三嗪-2,4-二硫醇单钠盐(简称TESPA)为基础。一方面,通过自组装技术和电化学沉积方法,在金属铜表面制备了TESPA的不同类型纳米薄膜,研究了它们对铜的保护性能(防腐蚀性能)。另一方面,在粗糙化的金属铜网和铜泡沫表面引入了TESPA和长链硅烷的复合纳米薄膜,制备了超湿润界面。研究了复合纳米薄膜的重复使用稳定性和酸碱耐蚀性,拓展了该类纳米薄膜的应用领域。需要指出一点,TESPA类化合物并非首次出现,日本科学家于2006年已经合成。但是,本文在于提出“组装多种防腐蚀官能团于一种分子中”这样一种防腐蚀路线,TESPA是其中之一。博士工作具体内容如下:采用自组装技术,在铜表面制备了TESPA自组装纳米薄膜,120°C加热自组装纳米薄膜后得到了TESPA热聚合纳米薄膜。TESPA自组装薄膜一定程度保护了铜(76.73%),而热聚合纳米薄膜以最大程度保护铜(95.59%)。前者的等效电路为R(Q(R(Q(RG)))),出现了特征的Gerischer阻抗;后者的等效电路为R(Q(R(RQ))),Gerischer阻抗消失。TESPA水解衍生物单体通过巯基和铜/铜氧化物之间的强化学作用,自组装在铜表面形成纳米薄膜。加热使得TESPA自组装纳米薄膜发生两部分官能团的聚合,硅羟基脱水缩合形成-SiOSi-交联的网状结构,未和铜键合的巯基热聚合生成二硫键(-SS-)。依据均三嗪二硫醇类化合物电化学聚合原理,在铜表面恒电流制备了TESPA聚合纳米薄膜,此时巯基电聚合生成交联的二硫键结构。水解TESPA电聚合纳米薄膜,烷氧基(-SiOCH_2CH_3)水解为硅羟基(-SiOH),继续120°C加热使得硅羟基脱水缩合交联形成网状的-SiOSi-结构。水解后的电聚合薄膜(不论加热与否)具有多功能性,既可以有效的保护铜又能提供活性位点(-SiOH),为继续化学改性提供活性平台。加热水解的TESPA电聚合纳米薄膜较未加热的电聚合纳米薄膜防腐蚀能力强,这是-SiOSi-结构发挥保护作用。直接电聚合TESPA纳米薄膜只存在传荷控制,存在硅羟基的电聚合纳米薄膜出现了Warburg扩散。基于TESPA自组装纳米薄膜和热聚合纳米薄膜在铜表面排列特性(即巯基和铜基底化学键合,提供保护铜基底的结构;硅羟基位于TESPA纳米薄膜顶层,提供了活性反应位点),通过层层自组装方法在铜表面制备了两大类型的复合纳米薄膜。一类是对金属绿色无害的正辛基三乙氧基硅烷(OTES)和TESPA形成的复合纳米薄膜。另一类是对金属具有腐蚀破坏作用的十八烷基三氯硅烷(OTS)和TESPA形成的复合纳米薄膜。尽管OTES烷基链长度小于OTS烷基链,但OTES-TESPA复合纳米薄膜对铜基底的保护效率大于OTS-TESPA复合纳米薄膜。原因在于OTES与TESPA反应产生无腐蚀性的醇类副产物,OTS与TESPA反应产生腐蚀性副产物HCl,并且生成氯含量很高的杂质颗粒。采用组合刻蚀法,得到粗糙度优越的铜网。将TESPA热聚合纳米薄膜引入,得到亲水性铜网,其具有制备超亲水表面的潜力。制备OTS-TESPA双层复合纳米薄膜后,转变为超疏水铜网。超疏水铜网对四氯化碳、二氯甲烷、甲苯、正己烷及辛烷/水混合物能够有效分离,50次分离后,各油水混合体系的循环效率依旧在95%以上,对应的铜网依旧体现超疏水性能(151°)。采用水热氧化法,在铜泡沫表面引入“花蕾”状的微米纳米级结构。将含有表面能低的全氟癸基三氯硅烷(PFDTCS)引入TESPA热聚合纳米薄膜修饰的铜泡沫表面,得到PFDTCS-TESPA修饰的超疏水铜泡沫。超疏水铜泡沫对甲苯、辛烷、正己烷、二氯甲烷和四氯化碳/水混合物能够有效分离,50次分离后,各油水混合体系的循环效率依旧在98.3%以上,对应的铜泡沫依旧体系超疏水性能(160°)。超疏水泡沫性能相对超疏水铜网有很大提升,具有更加优越的化学稳定性和耐用性,主要原因在于PFDTCS中存在大量低表面能的氟原子。
[Abstract]:Corrosion protection of metal copper and its alloy is very important in our daily life and industrial production. For copper, containing organic functional groups of single corrosion preservative was almost completely. According to the above research development limitations, presents a synthesis of novel organic preservatives route. In short, assembly of various anti-corrosion in a group in the molecule, through different preparation technology of corresponding anti-corrosion structure for copper and its alloys, were synthesized in three of the new two thiol silane preservatives, by three in two groups with thiols and anti-corrosion silane together. This thesis takes a typical three triazine compounds were two thiol silane. 6- (3- triethoxysilyl propyl ammonia) -1,3,5- three in -2,4- two thiols monosodium salt (TESPA) as the foundation. On the one hand, through self-assembly technique and electrochemical deposition method on the surface of metal copper prepared by TESPA The different types of nano thin film, studied the protection performance of the copper (corrosion). On the other hand, the nano composite films TESPA and long chain silane introduced on the roughened copper mesh and a copper foam surface, super wet interface were prepared on composite nano film stability and reuse acid and alkali corrosion resistance, expand the application field of the nano thin film. It should be noted that the TESPA compound is not the first time, Japanese scientists in 2006 has been synthesized. However, this paper is to put forward "the assembly of various functional groups in a molecule of corrosion in such a corrosion resistant line, TESPA is one of the specific content. Dr. work is as follows: using the self-assembly technology, were prepared on copper surface TESPA self-assembled nano film, 120 DEG C heating self assembled nano film obtained TESPA nano film thermal polymerization of.TESPA self assembled films The degree of protection of copper (76.73%), while the thermal polymerization of nano thin film with the greatest degree of protection of copper (95.59%). The equivalent circuit of the former is R (Q (R (Q (RG)))), the Gerischer impedance characteristics; equivalent circuit of the latter is R (Q (R (RQ))). The impedance of the Gerischer lost the hydrolysis of.TESPA derivative monomer through the strong chemical effect of thiol and copper / copper oxide between the self-assembled nano film on the copper surface formation. Heating makes the TESPA self assembling nano film two part polymerization of functional groups, silicon hydroxyl dehydration condensation formation of -SiOSi- crosslinked network structure, and thermal thiol copper bonding the polymerization of two disulfide bonds (-SS-). On the basis of three triazine thiols were two electrochemical polymerization principle on copper surface was prepared by constant current polymerization of TESPA nanometer thin films, the thiol electro polymerization to form a crosslinked structure. Two disulfide bond hydrolysis polymerization TESPA nano film, alkoxy (-SiOCH_2CH_3) hydrolysis Silicon hydroxyl (-SiOH), -SiOSi- to 120 DEG C heating structure makes the silicon hydroxyl dehydration condensation cross-linked to form a mesh. The electrical polymeric film after hydrolysis (whether it is heated or not) has multiple functions, can effectively protect the copper and can provide the active site (-SiOH), in order to provide chemical modification activity platform. TESPA electro polymerization nano film is heated and hydrolyzed with electrical heating polymerization of nano thin film anti corrosion ability, this is the -SiOSi- structure play a protective role. The direct electrochemical polymerization of TESPA nano films are only controlled by charge transfer, there are silicon hydroxyl polymerization nano thin film appeared Warburg diffusion. TESPA self-assembled nano films and nano thermal polymerization the film on the copper surface are arranged based on the characteristic (offer active reaction sites that thiol and copper substrates by chemical bond, provide protection structure; the base copper silicon hydroxyl groups located on the top floor, TESPA nano film), through layer by layer self-assembly The method of preparing nano composite film of two types on the copper surface system. One is n-octyltriethoxysilane on metal green harmless (OTES) nano composite film and the formation of TESPA. Another is a destructive effect on metal corrosion eighteen three alkyl chlorosilane (OTS) nano composite films and TESPA the formation of OTES. Although the alkyl chain length of alkyl chain is less than OTS, but the protection efficiency of OTES-TESPA nano composite films on copper substrates than OTS-TESPA nanocomposite thin films. The reason is that OTES and TESPA produced by the reaction of alcohols by-products non corrosive, anti OTS and TESPA should produce corrosive by-products HCl, and generate chlorine impurity particles content high. The combination of etching, copper mesh roughness is superior. The TESPA thermal polymerization of nano thin film is introduced, by hydrophilic copper network, its preparation of super hydrophilic surface potential. The preparation of OTS-TESPA nano composite M film, into a super hydrophobic copper mesh. The superhydrophobic copper mesh on carbon tetrachloride, toluene, dichloromethane, n-hexane and isooctane / water mixture can be separated effectively, 50 times after the separation, the circulation efficiency of oil-water mixtures is still above 95%, the copper net still reflect the super hydrophobic properties (151 degrees). By hydrothermal oxidation on copper foam surface into "bud" shaped micro and nano structure. The surface can contain perfluorodecyl low three chloro silane (PFDTCS) copper foam surface using TESPA nano film thermal polymerization modification, PFDTCS-TESPA modification of superhydrophobic copper foam. Superhydrophobic copper foam of toluene, octane, n-hexane, dichloromethane and carbon tetrachloride / water mixture can be separated effectively, 50 times after the separation, the circulation efficiency of oil-water mixtures is still above 98.3%, the corresponding copper foam system still super hydrophobic properties (160 DEG) super hydrophobic foam. The performance of the super hydrophobic copper network has been greatly improved, and it has more superior chemical stability and durability. The main reason is that there exist lots of fluorine atoms with low surface energy in PFDTCS.

【学位授予单位】：哈尔滨工业大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：TB383.2;TG174.4

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