生物表面海洋防污性能研究
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摘要
海洋污损生物给社会生产和军事装备造成极大的危害和巨大的经济损失,传统毒物释放型防污涂料在有效防止污损生物附着的同时,也给海洋环境带来了严重污染,随着国际社会对环境问题的日益关注,开发高效、广谱、环境友好型的海洋防污涂料势在必行。许多海洋生物通过非常“友好”的方法来防止污损,这些方式非常巧妙,具有广谱性和高效性,符合防污技术的发展方向。
本文基于生物具有很强防污能力的现象,从研究生物的防污方式出发,探寻生物防污的基本规律,以此为依据,选择合适的方法构建及调控材料表面特性,建立防污效果评估方法并结合附着点理论、破坏力学、粘结模型等理论方法分析表面特性对防污性能的影响,研究其防污机制。本文主要研究内容如下:
(1)通过SEM、EDS、GC-MS等测试手段以及实地调查、观测等方式,较全面地分析了陆地及淡水生植物(荷叶、洋紫荆、樟树)、硬骨鱼系、软骨鱼系(如鲨鱼)、红树科植物、大型藻类、贝螺类等典型生物表面的防污方式,归纳提取了对仿生设计有益的因素。
(2)以生物防污为依据,利用聚二甲基硅氧烷(PDMS)为涂层基体仿生设计了5种表面特性不同的涂层样板并对其进行表征:①通过在涂层中添加5%、10%、15%的改性纳米SiO2制备不同模量的涂层;②采用不同型号的金相砂纸复制其表面结构制备具有不同微观尺度表面的涂层;③通过在不同色漆表面刷涂PDMS制备了不同颜色的涂层;④通过在涂层中添加与基体结构相近、低表面能、不相容的硅油制备润滑剂渗出的涂层;⑤选择PTFE、PMMA、PDMS三种材质作为不同表面能样板。
(3)采用实验室内微生物(小新月菱形藻)粘附实验、大型污损生物(东方小藤壶)幼虫粘附实验和青岛实海挂板试验建立防污效果评估方法,并对上述涂层表面各因素对防污效果的影响进行评价。结果表明,模量影响污损生物脱落方式和粘附强度,降低涂层模量可降低污损程度;微结构表面相对光滑表面防污效果不明显;润滑剂渗出涂层能明显抑制污损,是一种行之有效的防污方式;颜色对污损生物附着有一定影响;表面能对防污效果影响较复杂,理论上存在一定范围表面能数值使得涂层表面生物粘附强度较低。
通过本项目研究,进一步在理论上揭示海洋生物防污的规律,为新型防污涂料的表面工程优化设计拓展思路、提供依据。
Any marine structures such as ship hulls, jetties and platforms are subject to diverse and severe biofouling, which restricts their applications and results in tremendous expense. Traditional toxic antifouling coating can prevent marine organisms fouling effectively, but it also causes serious pollution to the marine environment. As more attention is payed to protecting the marine environment, the research and development of high efficient, broad-spectrum, non-toxic antifouling paint is imperative. Many marine foliages and animals have environmental friendly and ingenious antifouling properties, which accord with the trend of antifouling technology.
Inspired from nature, different antifouling quomodos of representative biologic surfaces were studied firstly. Then, biomimetic coatings were prepared and modified based on nature antifouling quomodos. Finally, efficient evaluation methods of testing the antifouling performances were established and the antifouling performances of different man-made coatings were analyzed by academic methods, such as attachment point theory, fracture mechanics, adhesion model, etc. The major work of this dissertation is summarized as follows:
Firstly, some testing methods of scan electron microscope (SEM), energy dispersive X-ray spectroscopy (EDS), gas chromatography (GC)-mass spectrum (MS), etc and investigation method were used to study representative biologic surfaces, including land foliages (lotus leaves, Cinnamoum camphora (Linn.) leaves, Bauhinia blakeana Dunn leaves), chondrichthyes, osteichthyes, mangrove plants, macroalgae, etc. Beneficial biomimetic factors were aslo summarized based on these reseach.
Secondly, polydimethyl siloxane (PDMS) was chosen as matrix material and five different types of biomimetic PDMS surfaces were prepared and charactered.①Coatings of different elastic modulus were prepared by doping 5%, 10%, 15% weight percent silicon dioxide nanoparticles into the PDMS matrix.②Based on the soft lithography and casting, PDMS surfaces with different microtopographies were obtained by using five different types of metallographic abrasive paper as templates and replicating them.③Different coloured PDMS coatings were prepared by coating PDMS liquid on different coloured paint surfaces.④Coatings with diffuse lubricant surfaces were prepared by adding silicone oil with similar structure and low surface energy into PDMS matrix.⑤Three kinds of materials of polytetrafluroethene (PTFE), polymethyl methacrylate (PMMA) and PDMS were chosen as different surface energy coatings.
Thirdly, diatom (Nitzschia closterium f. minutissima) attachment experiment, macrofouler (Chthamalusc hallengeri Hoek) attachment experiment and marine immersion experiment in sea area of Qingtao were used as evaluation methods of testing the antifouling performances, the influence of elastic modulus, sueface microtopography, colour, diffuse lubricant and surface energy on antifouling performances was studied by these evaluation methods. The results show that elastic modulus has influence on adhesive strength and fracture types of fouling organisms, low elastic modulus coating is advisable. Microtextured surface does not have obvious antifouling performances compare to slippery surface. Silicone oil can diffuse to the surface of the coating and improve the antifouling performances remarkably. Colour has influence on antifouling performances, antifouling paints with excellent colour could be prepared based on the main fouling organisms in corresponding sea area. Effect of surface energy on attachment of fouling organisms is complicated, no linear relationship is found, a certain surface energy numerical value range in which the surface has the least adhesive strength is existent in theory.
This dissertation makes chear antifouling mechanisms of biologic surfaces theoretically, the work makes theoretical preparations for the development of novel non-toxic antifouling coatings.
本文基于生物具有很强防污能力的现象,从研究生物的防污方式出发,探寻生物防污的基本规律,以此为依据,选择合适的方法构建及调控材料表面特性,建立防污效果评估方法并结合附着点理论、破坏力学、粘结模型等理论方法分析表面特性对防污性能的影响,研究其防污机制。本文主要研究内容如下:
(1)通过SEM、EDS、GC-MS等测试手段以及实地调查、观测等方式,较全面地分析了陆地及淡水生植物(荷叶、洋紫荆、樟树)、硬骨鱼系、软骨鱼系(如鲨鱼)、红树科植物、大型藻类、贝螺类等典型生物表面的防污方式,归纳提取了对仿生设计有益的因素。
(2)以生物防污为依据,利用聚二甲基硅氧烷(PDMS)为涂层基体仿生设计了5种表面特性不同的涂层样板并对其进行表征:①通过在涂层中添加5%、10%、15%的改性纳米SiO2制备不同模量的涂层;②采用不同型号的金相砂纸复制其表面结构制备具有不同微观尺度表面的涂层;③通过在不同色漆表面刷涂PDMS制备了不同颜色的涂层;④通过在涂层中添加与基体结构相近、低表面能、不相容的硅油制备润滑剂渗出的涂层;⑤选择PTFE、PMMA、PDMS三种材质作为不同表面能样板。
(3)采用实验室内微生物(小新月菱形藻)粘附实验、大型污损生物(东方小藤壶)幼虫粘附实验和青岛实海挂板试验建立防污效果评估方法,并对上述涂层表面各因素对防污效果的影响进行评价。结果表明,模量影响污损生物脱落方式和粘附强度,降低涂层模量可降低污损程度;微结构表面相对光滑表面防污效果不明显;润滑剂渗出涂层能明显抑制污损,是一种行之有效的防污方式;颜色对污损生物附着有一定影响;表面能对防污效果影响较复杂,理论上存在一定范围表面能数值使得涂层表面生物粘附强度较低。
通过本项目研究,进一步在理论上揭示海洋生物防污的规律,为新型防污涂料的表面工程优化设计拓展思路、提供依据。
Any marine structures such as ship hulls, jetties and platforms are subject to diverse and severe biofouling, which restricts their applications and results in tremendous expense. Traditional toxic antifouling coating can prevent marine organisms fouling effectively, but it also causes serious pollution to the marine environment. As more attention is payed to protecting the marine environment, the research and development of high efficient, broad-spectrum, non-toxic antifouling paint is imperative. Many marine foliages and animals have environmental friendly and ingenious antifouling properties, which accord with the trend of antifouling technology.
Inspired from nature, different antifouling quomodos of representative biologic surfaces were studied firstly. Then, biomimetic coatings were prepared and modified based on nature antifouling quomodos. Finally, efficient evaluation methods of testing the antifouling performances were established and the antifouling performances of different man-made coatings were analyzed by academic methods, such as attachment point theory, fracture mechanics, adhesion model, etc. The major work of this dissertation is summarized as follows:
Firstly, some testing methods of scan electron microscope (SEM), energy dispersive X-ray spectroscopy (EDS), gas chromatography (GC)-mass spectrum (MS), etc and investigation method were used to study representative biologic surfaces, including land foliages (lotus leaves, Cinnamoum camphora (Linn.) leaves, Bauhinia blakeana Dunn leaves), chondrichthyes, osteichthyes, mangrove plants, macroalgae, etc. Beneficial biomimetic factors were aslo summarized based on these reseach.
Secondly, polydimethyl siloxane (PDMS) was chosen as matrix material and five different types of biomimetic PDMS surfaces were prepared and charactered.①Coatings of different elastic modulus were prepared by doping 5%, 10%, 15% weight percent silicon dioxide nanoparticles into the PDMS matrix.②Based on the soft lithography and casting, PDMS surfaces with different microtopographies were obtained by using five different types of metallographic abrasive paper as templates and replicating them.③Different coloured PDMS coatings were prepared by coating PDMS liquid on different coloured paint surfaces.④Coatings with diffuse lubricant surfaces were prepared by adding silicone oil with similar structure and low surface energy into PDMS matrix.⑤Three kinds of materials of polytetrafluroethene (PTFE), polymethyl methacrylate (PMMA) and PDMS were chosen as different surface energy coatings.
Thirdly, diatom (Nitzschia closterium f. minutissima) attachment experiment, macrofouler (Chthamalusc hallengeri Hoek) attachment experiment and marine immersion experiment in sea area of Qingtao were used as evaluation methods of testing the antifouling performances, the influence of elastic modulus, sueface microtopography, colour, diffuse lubricant and surface energy on antifouling performances was studied by these evaluation methods. The results show that elastic modulus has influence on adhesive strength and fracture types of fouling organisms, low elastic modulus coating is advisable. Microtextured surface does not have obvious antifouling performances compare to slippery surface. Silicone oil can diffuse to the surface of the coating and improve the antifouling performances remarkably. Colour has influence on antifouling performances, antifouling paints with excellent colour could be prepared based on the main fouling organisms in corresponding sea area. Effect of surface energy on attachment of fouling organisms is complicated, no linear relationship is found, a certain surface energy numerical value range in which the surface has the least adhesive strength is existent in theory.
This dissertation makes chear antifouling mechanisms of biologic surfaces theoretically, the work makes theoretical preparations for the development of novel non-toxic antifouling coatings.
引文
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