材料表面仿生修饰及金属化的研究
摘要
材料表面改性的方法对材料在研究和工业应用都具有重大的意义。现有材料表面改性的方法各有优缺点。其中,通过具有优异的粘结性能和其他性能的分子和聚合物自组装在材料的表面形成功能层的方法受到大家的广泛关注。这种方法具有成本低,适用于大面积的形状复杂的三维结构基体,可在材料表面形成微米级和纳米级的功能层等优点。受到贝壳类动物分泌的粘附性蛋白质的结构的启发,有学者报道了聚多巴胺的粘附机理和性能。结果表明,多巴胺(3,4-二羟基-苯丙氨酸)以及其他具有类似儿茶酚结构的化合物可沉积在不同材料基体的表面,包括有机、无机和金属材料。通过在不同材料基体表面进行多巴胺氧化聚合以及聚多巴胺沉积可以对材料表面功能化改性。利用聚多巴胺层表面的基团进行进一步反应可以在材料表面形成其他的功能层,包括利用自组装形成单分子层、通过长链分子反应形成聚合物层,通过无电沉积形成金属层以及通过大分子接枝形成的生物活性层。
在本研究中,我们通过多巴胺聚合对聚酰亚胺膜(PI)以及玻璃微球(Glass beads)表面进行了功能化修饰改性,然后通过紫外光照或者化学镀在功能化后的基体材料表面镀覆银层。具体工作包括以下三个方面：
(1)首次研究了利用多巴胺功能化修饰及化学还原银制备高导电高反射的聚酰亚胺(PI)薄膜的新方法。在这种方法中,首先将聚酰亚胺(PI)膜浸入多巴胺水溶液中,在氧存在下多巴胺在PI表面聚合并沉积,然后在沉积有聚多巴胺的聚酰亚胺膜(PI-DOPA)表面通过化学还原(electroless plating)的方法沉积金属银层。通过X射线光电子能谱(XPS)测试PI膜表面的组成和结构的变化,结果表明PI膜的表面成功地沉积上聚多巴胺层。在银的还原过程中,由于聚多巴胺具有一定的氧化还原能力,聚多巴胺功能层不仅在化学镀银的过程中作为银离子的吸附点,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PI膜(PI/Ag)具有优异的导电性和反射性,其表面电阻为1.5Ω,反射率达95%。
(2)本文研究了通过紫外光照将银粒子还原在多巴胺功能化的PI膜表面制备抗菌薄膜的方法。研究了溶液pH、多巴胺浓度和反应时间对多巴胺聚合反应的影响。由于聚多巴胺的亲水性,经多巴胺功能化的PI膜表面的水接触角与改性前的PI膜相比有明显降低。利用X射线光电子能谱(XPS)和X射线衍射(XRD)对聚多巴胺修饰的PI膜和紫外光照还原银的PI膜的表面化学组成进行分析。通过扫描电子显微镜(SEM)观察PI表面形貌的变化。经抗菌性实验测试,此复合薄膜具有优异的抗菌性能。
(3)本文还研究了通过多巴胺功能化以及无电沉积的方法制备表面包覆有银粒子的玻璃微球(Glass beads/Ag)核壳复合微球。通过多巴胺聚合对玻璃微球表面进行功能化修饰,引入酚羟基和含氮基团。在无电沉积银的过程中,通过改变硝酸银溶液的浓度以及相应葡萄糖溶液的浓度得到表面覆盖有不同厚度和致密程度的银层的玻璃微球。通过X射线光电子能谱(XPS)和X射线衍射仪(XRD)对玻璃微球／银复合微球的表面化学组成进行分析。利用扫描电子显微镜(SEM)以及能量散射x射线能谱仪(EDX)表征玻璃微球在镀银前后的表面形貌以及元素组成的变化。在玻璃微球表面形成的多巴胺层可以起到吸附银离子的作用同时可以促进银的还原。由于聚多巴胺的“桥梁”作用,通过该方法制备的核壳结构复合微球中表面银层与玻璃微球基体之间有较强的结合力。
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。
The techniques to modify substrate surfaces are significant for many industrial and research applications. The toolbox of methods available so far covers a large number of approaches with their specific advantages and limitations. Among them, spontaneous self-assembly and organization of designed molecules and polymers incorporating adhesion and other functions, are particularly attractive as they constitute cost-effective, easy-to-unscale techniques, applicability to large areas and three-dimensional devices of complex shape, and conformity with micro and nano scale surface technologies, while requiring only minimal amounts of materials.
Recently, inspired by and studied on the composition of adhesive proteins in mussels, the adhesive mechanisms and adhesive behaviors of polydopamine have been reported. The results indicate that dopamine (or 3,4-dihydroxy-phenylalanine) and other catechol compounds perform well as binding agents for coating various substrates, including organic, inorganic and metal materials. The oxidative polymerization of dopamine and the spontaneous deposition of polydopamine on various surfaces provide a powerful route for surface modification and functionalization. Secondary reactions with the polydopamine layer can be used to create a variety of ad-layers, including self-assembled monolayers, through the deposition of long-chain molecular building blocks, metal films by electroless metallization, and bioactive surface via grafting of macromolecules.
In this work, suface modification of polyimide (PI) films and glass beads were carried out by utilizing dopamine self-polymerization and deposition. Electroless plating of silver on the as-prepared surfaces was performed to prepare conductive or antibacterial surfaces. The details of the work are as follows:
(1) A novel method was developed for the preparation of reflective and electrically conductive surfacesilvered polyimide (PI) films. Polyimide films were functionalized with poly(dopamine), simply by dipping the PI films into aqueous dopamine solution and mildly stirring at room temperature. Electroless plating of silver was readily carried out on the poly(dopamine) deposited PI (PI-DOPA) surface. The surface compositions of the modified PI films were studied by X-ray photoelectron spectroscopy (XPS). XPS results show that the PI-DOPA surfaces were successfully deposited with ploy(dopamine) and were ready for electroless deposition of silver. The poly(dopamine) layer was used not only as the chemisorption sites for silver particles during the electroless plating of silver, but also as an adhesion promotion layer for the electrolessly deposited silver. The as-prepared silvered PI films show high conductivity and reflectivity, with a surface resistance of 1.5Ωand reflectivity of 95%, respectively.
(2) Immobilization of silver nanoparticles on the dopamine functionalized polyimide (PI) films was carried out by photo-induced silver ion-reduction under atmosphere conditions. The dopamine was successfully deposited on the PI surface in mild aqueous environments. The effects of pH, dopamine concentration and reaction time on the dopamine polymerization were investigated. The water contact angles of the poly(dopamine) functionalized PI films reduced remarkably in comparison with that of the pristine PI film. The chemical composition and structure of the UV-induced deposited-silver on the modified PI films were characterized by X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). The topography of the modified PI films was investigated by scanning electron microscope (SEM). The deposited poly(dopamine) layer acted as binding sites for the silver ions. The silver-plated PI films showed good antibacterial activity due to that biofilm formation was inhibited on the polymeric surfaces in contact with bacteria.
(3) A simple method was developed to prepare silver-coated silica beads which were functionalized by dopamine. Surface modification of prisitine glass beads was carried out by dopamine polymerization and deposition followed by electroless plating. The content of ammonical AgNO3 in deionized water was varied with respective amount of glucose solution in the seeding growth process and a uniform and relative dense coverage of silver nanoparticle seeds on the surface of silica beads was achieved. The chemical composition of the Ag/silica beads core-shell composite particles were studied by X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). In addition, the morphologies of the composite particles were observed by scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDX). The poly(dopamine) layer was used as the chemi-sorption sites for silver particles and promoted the deposition of silver. The conductivity of as-prepared Ag/silver beads composite particles was tested by four-probe resistivity tester and the resistivity of the particles was 10 mQ.
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聚酰亚胺膜(PI)以及玻璃微球(Glass beads)表面进行了功能化修饰改性,然后通过紫外光照或者化学镀在功能化后的基体材料表面镀覆银层。具体工作包括以下三个方面：
(1)首次研究了利用多巴胺功能化修饰及化学还原银制备高导电高反射的聚酰亚胺(PI)薄膜的新方法。在这种方法中,首先将聚酰亚胺(PI)膜浸入多巴胺水溶液中,在氧存在下多巴胺在PI表面聚合并沉积,然后在沉积有聚多巴胺的聚酰亚胺膜(PI-DOPA)表面通过化学还原(electroless plating)的方法沉积金属银层。通过X射线光电子能谱(XPS)测试PI膜表面的组成和结构的变化,结果表明PI膜的表面成功地沉积上聚多巴胺层。在银的还原过程中,由于聚多巴胺具有一定的氧化还原能力,聚多巴胺功能层不仅在化学镀银的过程中作为银离子的吸附点,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PI膜(PI/Ag)具有优异的导电性和反射性,其表面电阻为1.5Ω,反射率达95%。
(2)本文研究了通过紫外光照将银粒子还原在多巴胺功能化的PI膜表面制备抗菌薄膜的方法。研究了溶液pH、多巴胺浓度和反应时间对多巴胺聚合反应的影响。由于聚多巴胺的亲水性,经多巴胺功能化的PI膜表面的水接触角与改性前的PI膜相比有明显降低。利用X射线光电子能谱(XPS)和X射线衍射(XRD)对聚多巴胺修饰的PI膜和紫外光照还原银的PI膜的表面化学组成进行分析。通过扫描电子显微镜(SEM)观察PI表面形貌的变化。经抗菌性实验测试,此复合薄膜具有优异的抗菌性能。
(3)本文还研究了通过多巴胺功能化以及无电沉积的方法制备表面包覆有银粒子的玻璃微球(Glass beads/Ag)核壳复合微球。通过多巴胺聚合对玻璃微球表面进行功能化修饰,引入酚羟基和含氮基团。在无电沉积银的过程中,通过改变硝酸银溶液的浓度以及相应葡萄糖溶液的浓度得到表面覆盖有不同厚度和致密程度的银层的玻璃微球。通过X射线光电子能谱(XPS)和X射线衍射仪(XRD)对玻璃微球／银复合微球的表面化学组成进行分析。利用扫描电子显微镜(SEM)以及能量散射x射线能谱仪(EDX)表征玻璃微球在镀银前后的表面形貌以及元素组成的变化。在玻璃微球表面形成的多巴胺层可以起到吸附银离子的作用同时可以促进银的还原。由于聚多巴胺的“桥梁”作用,通过该方法制备的核壳结构复合微球中表面银层与玻璃微球基体之间有较强的结合力。
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。
The techniques to modify substrate surfaces are significant for many industrial and research applications. The toolbox of methods available so far covers a large number of approaches with their specific advantages and limitations. Among them, spontaneous self-assembly and organization of designed molecules and polymers incorporating adhesion and other functions, are particularly attractive as they constitute cost-effective, easy-to-unscale techniques, applicability to large areas and three-dimensional devices of complex shape, and conformity with micro and nano scale surface technologies, while requiring only minimal amounts of materials.
Recently, inspired by and studied on the composition of adhesive proteins in mussels, the adhesive mechanisms and adhesive behaviors of polydopamine have been reported. The results indicate that dopamine (or 3,4-dihydroxy-phenylalanine) and other catechol compounds perform well as binding agents for coating various substrates, including organic, inorganic and metal materials. The oxidative polymerization of dopamine and the spontaneous deposition of polydopamine on various surfaces provide a powerful route for surface modification and functionalization. Secondary reactions with the polydopamine layer can be used to create a variety of ad-layers, including self-assembled monolayers, through the deposition of long-chain molecular building blocks, metal films by electroless metallization, and bioactive surface via grafting of macromolecules.
In this work, suface modification of polyimide (PI) films and glass beads were carried out by utilizing dopamine self-polymerization and deposition. Electroless plating of silver on the as-prepared surfaces was performed to prepare conductive or antibacterial surfaces. The details of the work are as follows:
(1) A novel method was developed for the preparation of reflective and electrically conductive surfacesilvered polyimide (PI) films. Polyimide films were functionalized with poly(dopamine), simply by dipping the PI films into aqueous dopamine solution and mildly stirring at room temperature. Electroless plating of silver was readily carried out on the poly(dopamine) deposited PI (PI-DOPA) surface. The surface compositions of the modified PI films were studied by X-ray photoelectron spectroscopy (XPS). XPS results show that the PI-DOPA surfaces were successfully deposited with ploy(dopamine) and were ready for electroless deposition of silver. The poly(dopamine) layer was used not only as the chemisorption sites for silver particles during the electroless plating of silver, but also as an adhesion promotion layer for the electrolessly deposited silver. The as-prepared silvered PI films show high conductivity and reflectivity, with a surface resistance of 1.5Ωand reflectivity of 95%, respectively.
(2) Immobilization of silver nanoparticles on the dopamine functionalized polyimide (PI) films was carried out by photo-induced silver ion-reduction under atmosphere conditions. The dopamine was successfully deposited on the PI surface in mild aqueous environments. The effects of pH, dopamine concentration and reaction time on the dopamine polymerization were investigated. The water contact angles of the poly(dopamine) functionalized PI films reduced remarkably in comparison with that of the pristine PI film. The chemical composition and structure of the UV-induced deposited-silver on the modified PI films were characterized by X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). The topography of the modified PI films was investigated by scanning electron microscope (SEM). The deposited poly(dopamine) layer acted as binding sites for the silver ions. The silver-plated PI films showed good antibacterial activity due to that biofilm formation was inhibited on the polymeric surfaces in contact with bacteria.
(3) A simple method was developed to prepare silver-coated silica beads which were functionalized by dopamine. Surface modification of prisitine glass beads was carried out by dopamine polymerization and deposition followed by electroless plating. The content of ammonical AgNO3 in deionized water was varied with respective amount of glucose solution in the seeding growth process and a uniform and relative dense coverage of silver nanoparticle seeds on the surface of silica beads was achieved. The chemical composition of the Ag/silica beads core-shell composite particles were studied by X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). In addition, the morphologies of the composite particles were observed by scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDX). The poly(dopamine) layer was used as the chemi-sorption sites for silver particles and promoted the deposition of silver. The conductivity of as-prepared Ag/silver beads composite particles was tested by four-probe resistivity tester and the resistivity of the particles was 10 mQ.
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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