羟基丁腈橡胶和石墨表面的多巴胺修饰及金属化的研究
摘要
多巴胺(二羟基苯丙氨酸)是贝壳类动物分泌出蛋白质物质的主要成分。研究结果表明,多巴胺可以在各种有机或无机基体表面进行聚合,在一定条件下通过自氧化聚合形成聚多巴胺功能层,聚多巴胺功能层是一种特殊的活性功能层,聚多巴胺分子层的表面带有氨基和酚羟基等功能基团,聚多巴胺与银离子之间能够形成强的络合作用实现银的原位还原沉积。由于聚多巴胺结构上的功能基团对金属离子强的络合吸附作用,能够作为粘附层起到“桥架”作用使基体表面和银颗粒结合紧密,通过无电解沉积形成金属层以及通过大分子接枝形成的生物活性层。已有研究表明多巴胺自聚合可以作为一种有效实现材料表面功能化的手段促进金属化,并且多巴胺的聚合条件温和,对环境友好。
在本研究中,我们通过多巴胺聚合对羧基丁腈橡胶(XNBR)以及石墨粉(graphite)表面沉积多巴胺进行功能化修饰改性,并进行金属化。具体的工作如下：
(1)首先,本文主要研究了利用多巴胺的独特粘附效应和特殊的功能化层进行表面功能化修饰,继而进行化学还原金属银制备表面导电的羧基丁腈橡胶的新方法。
将超声清洁后的羧基丁腈橡胶(XNBR)浸入多巴胺的弱碱性溶液中,在氧气的作用下多巴胺进行自氧化聚合,并在XNBR上聚合并以聚多巴胺的大分子聚合物的团聚状态沉积,沉积一定能够时间后取出沉积有聚多巴胺的羧基丁腈橡胶(XNBR-PDA),继而将其浸入在无电解电镀溶液中通过化学还原进行金属银的沉积。通过X射线光电子能谱(XPS)测试XNBR表面的化学组成和元素结构及其含量的变化。研究结果表明聚多巴胺已经成功的沉积在XNBR表面。化学镀还原金属银的过程中,因为聚多巴胺的独特的多巴胺-醌基基团具有对金属的还原能力,使得聚多巴胺形成的功能层银离子的吸附点,同时可以提高银层与基体之间的结合力。本研究所制备得到的表面镀银的XNBR具有优异的导电性和反射性,其表面电阻为1.5Ω。
(2)本文研究通过多巴胺自聚合沉积在石墨粉表面对其进行表面修饰,并通过化学镀银制备石墨/银复合导电微球材料。XPS和X射线衍射对石墨粉进行了表面元素组成和结构分析,利用扫描电镜SEM对石墨粉的微观形貌与镀覆效果进行分析。结果表明,通过多巴胺修饰石墨粉表面后,实施化学镀银所得到的银颗粒连续,致密,测得复合材料的电阻率为5×10-3Ω·cm。研究结果表明,聚多巴胺不仅促进银在石墨粉表面的吸附和还原,而且能够起到“桥架”作用使石墨粉表面和银颗粒结合更加紧密。此方法简单易行,操作条件温和且对环境友好,为石墨粉表面化学镀银工艺提供了新方法。
本文提出的基于仿生技术的多巴胺自聚合方法为不同基体材料表面的功能化修饰提供了新的平台,在此基础上通过无电电镀可以实现薄膜、纤维、微/纳米粒子等各种尺寸及形状材料表面的金属化,为材料表面功能化改性提供了一个崭新的思路。
Recently, inspired by the adhesive properties of proteins in mussels, the adhesive behaviors of poly(dopamine) have been reported. The results indicated that dopamine (or 3,4-dihydroxy-phenylalanine) and other catechol compounds performed well as binding agents for coating various substrates, including inorganic or organic materials. This method is versatile because of its simple ingredients, mild reaction conditions, and applicability to various materials with complex shape. In particular, the metal binding ability of the catechol and including groups on the PDA molecular structure facilitate the immobilization of the metal ions onto the substrate. This method is versatile because of simple ingredients, mild reaction condition and non-pollution.
In this work, suface modification of XNBR and Graphite were carried out by utilizing dopamine self-polymerization and deposition. Electroless plating of silver on the as-prepared surfaces was performed to prepare conductive surfaces. The details of the work are as follows:
(1) A novel method for the preparation of electrical conductive surface silvered acrylonitrile-butadiene rubber (XNBR) was developed. Dopamine was spontaneously oxide polymerized and deposited onto the surface of NBR. Electroless plating of silver was carried out on the poly(dopamine) (PDA) functionalized NBR (XNBR-PDA) surface. The surface composition of the NBR surface was studied by X-ray photoelectron spectroscopy (XPS). XPS results showed that the PDA was successfully deposited onto the NBR surface. The surface morphology of the NBR surface was observed by scanning electron microscopy (SEM). The SEM images showed that the PDA had formed a distinctive layer ready for electroless deposition of silver. The catechol/quinone groups on the PDA molecular structure can be used as binding sites for silver ions. The silvered NBR showed high surface conductivity of 1.4Ω.
(2) Silver/graphite composite was prepared via a facile way. Graphite surface were modified by immersing into the dopamine solution, dopamine would spontaneous deposit on the surface of graphite for self-polymerization under certain circumstance, then silver plating was carried out by an electroless plating method. The structure and elements composition of the silver/graphite composite was determined by XPS and XRD, and the silver plating morphology on the surface was characterized by SEM and EDX. The results of the study indicated that, the silver particles plated on the dopamine modified graphite were compact and consecutive, the electrical resistivity of the conductive of the silver plating graphite was 5×10-3Ω·cm.
In conclusion, this paper shows that dopamine is a versatile method to functionalize the surface of substrate materials range from polymers to inorganics with various shapes, and the combination of the following electroless plating technique could prepare surface metalized composites with good adhesion between the metal with the substrate.
在本研究中,我们通过多巴胺聚合对羧基丁腈橡胶(XNBR)以及石墨粉(graphite)表面沉积多巴胺进行功能化修饰改性,并进行金属化。具体的工作如下：
(1)首先,本文主要研究了利用多巴胺的独特粘附效应和特殊的功能化层进行表面功能化修饰,继而进行化学还原金属银制备表面导电的羧基丁腈橡胶的新方法。
将超声清洁后的羧基丁腈橡胶(XNBR)浸入多巴胺的弱碱性溶液中,在氧气的作用下多巴胺进行自氧化聚合,并在XNBR上聚合并以聚多巴胺的大分子聚合物的团聚状态沉积,沉积一定能够时间后取出沉积有聚多巴胺的羧基丁腈橡胶(XNBR-PDA),继而将其浸入在无电解电镀溶液中通过化学还原进行金属银的沉积。通过X射线光电子能谱(XPS)测试XNBR表面的化学组成和元素结构及其含量的变化。研究结果表明聚多巴胺已经成功的沉积在XNBR表面。化学镀还原金属银的过程中,因为聚多巴胺的独特的多巴胺-醌基基团具有对金属的还原能力,使得聚多巴胺形成的功能层银离子的吸附点,同时可以提高银层与基体之间的结合力。本研究所制备得到的表面镀银的XNBR具有优异的导电性和反射性,其表面电阻为1.5Ω。
(2)本文研究通过多巴胺自聚合沉积在石墨粉表面对其进行表面修饰,并通过化学镀银制备石墨/银复合导电微球材料。XPS和X射线衍射对石墨粉进行了表面元素组成和结构分析,利用扫描电镜SEM对石墨粉的微观形貌与镀覆效果进行分析。结果表明,通过多巴胺修饰石墨粉表面后,实施化学镀银所得到的银颗粒连续,致密,测得复合材料的电阻率为5×10-3Ω·cm。研究结果表明,聚多巴胺不仅促进银在石墨粉表面的吸附和还原,而且能够起到“桥架”作用使石墨粉表面和银颗粒结合更加紧密。此方法简单易行,操作条件温和且对环境友好,为石墨粉表面化学镀银工艺提供了新方法。
本文提出的基于仿生技术的多巴胺自聚合方法为不同基体材料表面的功能化修饰提供了新的平台,在此基础上通过无电电镀可以实现薄膜、纤维、微/纳米粒子等各种尺寸及形状材料表面的金属化,为材料表面功能化改性提供了一个崭新的思路。
Recently, inspired by the adhesive properties of proteins in mussels, the adhesive behaviors of poly(dopamine) have been reported. The results indicated that dopamine (or 3,4-dihydroxy-phenylalanine) and other catechol compounds performed well as binding agents for coating various substrates, including inorganic or organic materials. This method is versatile because of its simple ingredients, mild reaction conditions, and applicability to various materials with complex shape. In particular, the metal binding ability of the catechol and including groups on the PDA molecular structure facilitate the immobilization of the metal ions onto the substrate. This method is versatile because of simple ingredients, mild reaction condition and non-pollution.
In this work, suface modification of XNBR and Graphite were carried out by utilizing dopamine self-polymerization and deposition. Electroless plating of silver on the as-prepared surfaces was performed to prepare conductive surfaces. The details of the work are as follows:
(1) A novel method for the preparation of electrical conductive surface silvered acrylonitrile-butadiene rubber (XNBR) was developed. Dopamine was spontaneously oxide polymerized and deposited onto the surface of NBR. Electroless plating of silver was carried out on the poly(dopamine) (PDA) functionalized NBR (XNBR-PDA) surface. The surface composition of the NBR surface was studied by X-ray photoelectron spectroscopy (XPS). XPS results showed that the PDA was successfully deposited onto the NBR surface. The surface morphology of the NBR surface was observed by scanning electron microscopy (SEM). The SEM images showed that the PDA had formed a distinctive layer ready for electroless deposition of silver. The catechol/quinone groups on the PDA molecular structure can be used as binding sites for silver ions. The silvered NBR showed high surface conductivity of 1.4Ω.
(2) Silver/graphite composite was prepared via a facile way. Graphite surface were modified by immersing into the dopamine solution, dopamine would spontaneous deposit on the surface of graphite for self-polymerization under certain circumstance, then silver plating was carried out by an electroless plating method. The structure and elements composition of the silver/graphite composite was determined by XPS and XRD, and the silver plating morphology on the surface was characterized by SEM and EDX. The results of the study indicated that, the silver particles plated on the dopamine modified graphite were compact and consecutive, the electrical resistivity of the conductive of the silver plating graphite was 5×10-3Ω·cm.
In conclusion, this paper shows that dopamine is a versatile method to functionalize the surface of substrate materials range from polymers to inorganics with various shapes, and the combination of the following electroless plating technique could prepare surface metalized composites with good adhesion between the metal with the substrate.
引文
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