目錄 目錄 ……………………………………………………………………….I 表目錄 …………………………………………………………………..III 圖目錄 …………………………………………………………………...V 一、前言…………………………………………………………………..1 二、實驗…………………………………………………………………50 2-1 實驗藥品……………………………………………………...51 2-2 實驗儀器…………………………………………………...…54 2-3超疏水薄膜材料製備………………………………………...56 2-3-1 高分子溶液之製備………………………………………...56 2-3-2 一步驟法製備超疏水薄膜材料…………………...………56 2-3-3 二步驟法製備超疏水薄膜材料……………..…….………59 2-3-4 分散聚合法製備高分子顆粒………………………….…..59 2-3-5 利用高分子顆粒以一步驟法製備超疏水薄膜材料……...62 2-4 超疏水薄膜材料之物性測試………………………………...62 2-4-1 接觸角測量……………..…………………………..……...62 2-4-2 熱重量損失測試……………..………………..…………...64 2-4-3 低溫微差掃描熱分析儀測試…………………..……..…...64 2-4-4 以SEM進行表面微結構分析……………………….……64 2-4-5 以AFM進行表面為結構分析…………………….………64 2-4-6 可視光穿透度測試………………………..……………….64 三、結果與討論…………………………………………………………68 3-1 疏水薄膜之製備與其基本物性之探討……………………...69 3-1-1 起始劑的選擇……………………………………………...69 3-1-2 高分子薄膜之接觸角……………………………………...74 3-1-3 不同乾燥溫度對薄膜接觸角之影響……………….……..79 3-1-4 高分子薄膜之熱性質………………………….….……….79 3-2 以無機粉體製備超疏水薄膜………………………………...82 3-2-1 一步驟法製備PS疏水薄膜………………………………...85 3-2-2 一步驟法製備HM33疏水薄膜…………………..………...97 3-2-3 一步驟法製備其他高分子薄膜……………………...…...111 3-2-4 二步驟法製備HM33疏水薄膜…………..………..……...118 3-3 以有機顆粒製備超疏水薄膜…………………...…………..131 3-3-1 DVB單體濃度對顆粒的影響…………………..…………131 3-3-2 共單體MMA添加對顆粒的影響…………………...……134 3-3-3 以高分子顆粒製備HM33疏水薄膜……………….……..137 四、結論………………………………………………………………145 參考文獻………………………………………………………………147 List of Tables Table 1-1: Measurements of the solid fraction φs, the advancing and receding contact angles. These contact angles are compared with the contact angles given by Cassie’s equation………..………….17 Table 1-2. Reactivities of alkanes and perfluoroalkanes…………..……38 Table 1-3. The segmental polarizabilities for various structures at optical frequencies………………………………………………….……38 Table 1-4. Critical surface tension of low-energy surface………………44 Table 2-1 The roughness from the AFM measurement…………………67 Table 3-1 The preparation conditions and contact angle of HM33 copolymer. …………………………………………………….…71 Table 3-2 The contact angle of different polymer film…………….……75 Table 3-3 The contact angle of different copolymer film………….……76 Table 3-4 The contact angle of different copolymer film under different drying temperature.…………………………………….………..80 Table 3-5 The contact angle of different A200 content added in PS solution by single step method.……………..……………….…..86 Table 3-6 The optimization for contact angel of different A200 content added in PS solution by single step method.…………..………...87 Table 3-7 The contact angel of different content of H70 added in PS solution by single step method.……………………..…………..92 Table 3-8 The optimization for contact angel of different content of H70 added in PS solution by single step method…….………………93 Table 3-9 The UV-Vis data (T%) of different film coated by different suspension by single step method………………………...……..98 Table 3-10 The contact angle of different content of A200 added in HM33 solution by single step method…………………………….……99 Table 3-11 The optimization for contact angle of different content of A200 added in HM33 solution by single step method………….100 Table 3-12 The contact angle of different content of H70 added in HM33 solution by single step method………………………………….104 Table 3-13 The optimization for contact angle of different content of H70 added in HM33 solution by single step method………….……..106 Table 3-14 The UV-Vis data (T%) of different film coated by different suspension by single step method………………………………110 Table 3-15 The contact angle of different content of H70 added in HM05 solution by single step method……………………………...…..114 Table 3-16 The contact angle of different content of H70 added in POA solution by single step method……………………………….…119 Table 3-17 The contact angle of different content of A200 or H70 added in HM33 solution by couple steps method…………...…………124 Table 3-18 The UV-Vis data (T%) of different film coated by different suspension by couple steps method………………………..……130 Table 3-19 The preparation conditions and results of polymer microspheres…………………………………………………….132 Table 3-20 The preparation conditions and results of copolymer microspheres…………………………………………..……...…135 Table 3-21 The contact angle of film preparation by different PDVB content in HM33 solution by single step method…………....….142 List of Figures Figure 1-1 Forces acting on a liquid droplet on a solid ( hydrophobic and hydrophilic solid)………………….………………………………5 Figure 1-2 The lotus and a droplet on a lotus leaf…………………….….5 Figure 1-3 SEM-image of lotus leaf. The micro structural epidermal cells are covered with nanoscopic wax crystals………………...………5 Figure 1-4 Water droplets on the lotus leaf and take up the dust covering a lotus leaf, also called “self-cleaning”……………………….……..8 Figure 1-5 Contaminating particle on a regularly sculptured wing surface of Cicada orni (a surface structure similar to lotus plant). The Lotus-effect: contaminating particles adhere to the droplet and are removed when the droplet rolls off the surface................................8 Figure 1-6 Surface roughness and self-cleaning by rinsing with water...10 Figure 1-7 Surface roughness and air cushion affect the contact angle..10 Figure 1-8 Water droplets on the wings of a butterfly and the nano structure of the wings………………………………………...…..10 Figure 1-9 (a) Drop on a rough surface in Wenzel’s model: the drop fills the grooves. (b) The apparent contact angle as predicted by Wenzel plotted against the angle according to Young’s Law……………..13 Figure 1-10 (a) Drop on a rough surface in Cassie’s model: the drop sits on the spikes. (b) The apparent contact angle as predicted by Cassie plotted against Young’s angle……………………………….……13 Figure 1-11 SEM images of the fractal AKD surface: (a, left) top view, (b, right) cross section……………………………………………….15 Figure 1-12 (a) Schematic illustration for vs heoretically predicted by Onda. (b) The apparent contact angle as predicted by Onda plotted against the angle according to Young’s Law………15 Figure 1-13 SEM images of micro-structured hydrophobic surfaces designed for quantifying the influence of the surface pattern on the contact angle. The three different surfaces (left: spikes, middle: shallow cavities and left: stripes) are crenellated on a micrometer scale……………………………………………………….……...17 Figure 1-14 (a, left) Filled-up grooves just before the liquid-solid contact is formed in the valleys. (b, right) Filled-up grooves after the liquid-solid contact is formed………………………………...…..18 Figure 1-15 The top view and side viewof one period of the roughness geometry of square pillars. The pillar cross-sectional size is a × a. A quarter of the pillar cross section is shown at each corner of the figure above………………………………………………..……..18 Figure 1-16 The scheme for the fabrication of transparent super- hydrophobic film…………………………………………………22 Figure 1-17 The SEM image of an inverse opal film with a center-to-center distance between neighboring holes of 275 nm...22 Figure 1-18 SEM images of carbon nanotube forests and an essentially spherical water droplet suspended on the PTFE-coated forest…..24 Figure 1-19 SEM pictures of film deposited with a ‘ribbon-like’ surface at two different magnifications…………………………………..24 Figure 1-20: SEM pictures of structured hydrophobic surfaces. Left: Microline pattern, Middle: Micropost pattern, and Right: Nanopost pattern…………………………………………………………….26 Figure 1-21 Schematic outline of the heat- and pressure-driven nano- imprint pattern transfer process for nanofabricating the surface of the thick polymer substrate………………………………………26 Figure 1-22 SEM images of the replication templates………………….26 Figure 1-23 Formation models of an FAS hydrophobic layer on the nano textured and hydrophilic polymer surface by low-temperature CVD……………………………………………………….……..29 Figure 1-24 SEM images of AKD surface at different magnification….29 Figure 1-25 SEM image of left the substrate and right a) as viewed from above; b) cross-sectional SEM image of the PVA nano-fibers.….31 Figure 1-26 Thermally responsive for a flat PNIPAAm-modified surface. a) Change of water drop profile when temperature was elevated from 25℃to 40℃respectively. b) Diagram of reversible formation of intermolecular hydrogen bonding……………………………..31 Figure 1-27 Scheme for fabricating metallic half-shells………………..33 Figure 1-28 SEM images of the size-reduced polystyrene beads and the water contact angle measurement on the corresponding modified surfaces……………………………………………………...……33 Figure 1-29 Concept of surface tension…………………………………40 Figure 1-30 Concept of a contact angle…………………………...…….40 Figure 1-31 Space-filling models of (A)–CH3 and (B)–CF3 groups……42 Figure 1-32 Space-filling models of (A)polyethylene and (B)PTFE chains…………………………………………………………..…42 Figure 1-33 Orientation of chains at the air/material interface…………42 Figure 34: Theoretical water (-) and hexadecane (- -) contact angles on PTFE, FAs, and nylon-6,6 surfaces…………………...………….43 Figure 1-35 Stages in the formation of random graft stabilizers in dispersion polymerization: (a)Radical formation (initiation); (b)radical transfer; (c) random grafting; (d)aggregation; (e)particle growth; (…) soluble chain; (—) insoluble chain;‧, free radical; M, monomer………………………………………………………….48 Figure 2-1 The scheme for the preparation of polymer solution.……….57 Figure 2-2 The scheme for the preparation of hydrophobic film by single step method.…………………………………………...…….…...58 Figure 2-3 The scheme for the preparation of hydrophobic film by couple steps method.……………………………………………...……..60 Figure 2-4 The scheme for the preparation of polymer microspheres by dispersion polymerization.……………………………….…...…61 Figure 2-5 The scheme for the preparation the hydrophobic film of polymer microspheres in single step method.……………………63 Figure 2-6 The schematic diagram of Atomic Force Microscopy…..….66 Figure 2-7 The specific plane of Atomic Force Microscopy…………...66 Figure 3-1 TGA diagram of HM33 copolymer prepared with different type of initiator.………………………………..……………..…..72 Figure 3-2 The DSC diagram of HM33 copolymer prepared with different type of initiator and homopolymer……………..………….…..…73 Figure 3-3 The relationship between the contact angle and HFA content of various copolymers and homopolymers.……………………....…77 Figure 3-4 The molecule model of various copolymer and homopolymers（A）PHFA（B）HM33（C）HM14（D）HM05（E）PMMA …..78 Figure 3-5 The TGA diagram of PHFA、PMMA and HM copolymers…81 Figure 3-6 The DSC diagram of PHFA、PMMA and HM copolymers…83 Figure 3-7 The plot drawn from the Onda’s equation…………......……84 Figure 3-8 The contact angle of different A200 content added in PS solution by single step method.……………………………..……88 Figure 3-9 The SEM of the film coated by suspension (A200 added in PS solution) in different ratio of A200/PS by single step method (A)0.72%、(B)7.2%、(C)28.8%、(D)50.8%、(E)75.2%、(F)150.4%.............................................................................…....89 Figure 3-10 The surface analysis of AFM:(A)A200/PS =14.4%；Ra = 160.4nm (B) A200/PS =75.2%；Ra = 229.5nm (C) A200/PS =150.4%；Ra = 171.3nm……………………………………….91 Figure 3-11 The contact angle of different content of H70 added in PS solution by single step method………………………………...…94 Figure 3-12 The SEM of the film coated by suspension (H70 added in PS solution) in different ratio of H70/PS by single step method (A)0.72%、(B)7.2%、(C)28.8%、(D)50.8%、(E)75.2%、(F)150.4%...........................................................................………95 Figure 3-13 The surface analysis of AFM: (A)H70/PS =14.4%；Ra = 173.4nm (B) H70/PS =75.2%；Ra = 194.8nm (C) H70/PS =150.4%；Ra = 180.6nm………………………………………..96 Figure 3-14 The contact angle of different content of H70 added in HM33 solution by single step method…………………..……………...101 Figure 3-15 The SEM of the film coated by suspension (A200 added in HM33 solution) in different ratio of A200/HM33 by single step method (A)0.72%、(B)14.4%、(C)28.8%、(D)37.6%、(E)75.2%、(F)150.4%.................................................................................…102 Figure 3-16 The surface analysis of AFM: (A)A200/HM33 =14.4%；Ra = 130.3nm (B)A200/ HM33 =37.6%；Ra = 287.7nm (C) A200/HM33 =75.2%；Ra = 135.3nm…………………………………………103 Figure 3-17 The contact angle of different content of H70 added in HM33 solution by single step method…………….……………………107 Figure 3-18 The SEM of the film coated by suspension (H70 added in HM33 solution) in different ratio of H70/HM33 by single step method (A)0.72%、(B)14.4%、(C)28.8%、(D)37.6%、(E)75.2%、(F)150.4%.................................................................................…108 Figure 3-19 The surface analysis of AFM: (A)H70/HM33 =14.4%；Ra = 190.6nm (B)H70/ HM33 =37.6%；Ra = 311.4nm (C)H70/HM33 =75.2%；Ra = 186.5nm…………………………………………109 Figure 3-20 The DLS diagram of A200 and H70 dispersed in MEK….112 Figure 3-21 The photographs of the water drop type on (A)glass、(B)HM33 film；(C)super-hydrophobic film by single step method, water-repellency. ……………………………………………….113 Figure 3-22 The contact angel of different content of H70 added in HM05 solution by single step method………………………………….115 Figure 3-23 The SEM of the film coated by suspension (H70 added in HM05 solution) in different ratio of H70/HM05 by single step method (A)14.4%、(B)28.8%、(C)37.6%、(D)75.2%、(E)150.4%.....................................................................................116 Figure 3-24 The surface analysis of AFM: (A)H70/HM05 =28.8%；Ra = 180.4nm (B)H70/ HM05 =75.2%；Ra = 367.7nm (C)H70/HM05 =150.4%；Ra = 119.8nm………………………………………117 Figure 3-25 The contact angel of different content of H70 added in POA solution by single step method…………………………………120 Figure 3-26 The SEM of the film coated by suspension (H70 added in POA solution) in different ratio of H70/POA by single step method (A)14.4%、(B)28.8%、(C)37.6%、 (D)75.2%、(E)150.4%……121 Figure 3-27 The photographs of the water drop type on (A)glass、(B)POA film、(C)super-hydrophilic film by single step method, complete wetting…………………………………………………………122 Figure 3-28 The contact angel of different content of A200 or H70 added in HM33 solution by two steps method…….……………….125 Figure 3-29 The SEM of the film coated by suspension (A200 added in HM33 solution) in different ratio of A200/HM33 by two steps method (A)5%、(B)20%、(C)80%；and coated by suspension (H70 added in HM33 solution) in different ratio of H70/HM33 by two steps method (D)5%、(E)20%、(F)80%.……………………....126 Figure 3-30 The surface analysis of AFM: (A)A200/HM33 =2.5%；Ra = 125.9nm (B)A200/HM33 =20%；Ra = 188nm (C) A200/HM33 =40%；Ra = 241.9nm (D) A200/HM33 =80%；Ra = 143.7nm…127 Figure 3-31The surface analysis of AFM: (A)H70/HM33 =2.5%；Ra = 121.9nm (B) H70/HM33 =20%；Ra = 180.9nm (C) H70/HM33 =40%；Ra = 193.2nm (D) H70/HM33 =80%；Ra = 152.9nm...128 Figure 3-32 The photographs of the water drop type on (A)glass、(B)HM33 film、(C)super-hydrophobic film by two steps method, water-repellency…………………………………………..…….129 Figure 3-33 The SEM of different monomer concentration in MeOH：(A)1%、(B)2%、(C)3.3%、(D)4%、(E)5%、(F)6.7%......................133 Figure 3-34 The SEM of different monomer concentration in MeOH and the MMA ratio in monomer：(A)3.3%、2%、(B)3.3%、10%、(C)5%、10%、(D)5.9%、44.1%(E)6.7%、39.5%(F)7.1%、35.7%..136 Figure 3-35 The DSL of monomer concentration =3.3% in MeOH..….138 Figure 3-36 The SEM of different rate of spin-coating：(A)4500rpm、(B)3500rpm、(C)2500rpm、(D)1500rpm、(E)1000rpm、(F)750rpm、(G)500rpm、(H)250rpm…………………………….139 Figure 3-37 The SEM of different concentration of PDVB in MeOH at 2500rpm：(A)conc.×1、(B)conc.×2、(C)conc.×3、(D)conc.×4….140 Figure 3-38 The contact angel of different content of PDVB in HM33 solution by single step method……………………………..…...143 Figure 3-39 The SEM of different ratio of PDVB/HM33 coated by single step method：(A)240%、(B)120%、(C)60%、(D)30%、(E)20%、(F)15%..........................................................................................144