特殊浸润性材料的制备及其应用研究

发布时间：2019-04-18 13:42

【摘要】：特殊浸润性材料因其特殊的表面特性而在日常生活和工农业生产中具有广阔的应用前景,也引起了研究者的极大兴趣与关注。基于特殊浸润性材料的应用前景,本文制备了具有干性粘附和自清洁特性的仿壁虎超疏水微图形,超疏水亲油油水分离网膜和表面浸润性可快速转变油水分离网膜三种不同表面特性和功能特性的特殊浸润性材料,表征和研究了三种特殊浸润性材料的表面特性和功能特性,并探索了上述材料的应用。本论文研究的主要内容和结果如下：(1)制备了具有干性粘附和自清洁特性的PDMS(聚二甲基硅氧烷,硅橡胶)仿壁虎超疏水微图形,并对微图形的粘附性能,浸润特性和自清洁性能进行了表征和研究,研究了微图形在不同粗糙度和表面能表面上的粘附特性。采用干法刻蚀和模具注塑复型相结合的方法成功制备了刚毛结构完整的仿壁虎微图形,微图形的力学研究结果表明,微图形的粘附力随预载荷的增大而增大,且减少刚毛直径,增加刚毛密度,增大刚毛长径比有利于提高微图形粘附力的提高；粘附表面的粗糙度和表面能影响微图形的粘附特性,由于“机械互锁”和有效作用面积等因素的存在,微图形的粘附性为与表面粗糙度存在匹配关系,粘附力在匹配粗糙度存在最大值,随后随粗糙度改变而降低；微图形在高表面能表面能够表现出更强的粘附力。微图形的浸润性研究结果表面,微图形表面的刚毛结构能够提高表面的超疏水性,微图形表面的浸润模型满足Cassie-Baxter模型,降低刚毛直径和占空比fs有利于提高微图形的疏水性,其中,微图形P-8-20-20的水接触角高达155.0°,滚动角为7.2°,表现出超疏水性。与壁虎脚掌类似,微图形表现出了良好的自清洁性能,定量的自清洁测试实验表明微图形P-8-20-20的自清洁效率高达91.3%。(2)以铜网网膜为基底材料,采用肉豆蔻酸乙醇溶液浸泡反应的方法成功制备了超疏水亲油油水分离网膜,并研究了网膜的油水分离特性。探讨了制备工艺参数和反应条件对网膜表面微纳结构构筑和浸润性的影响,并制备了水接触角达到156.7°,油接触0°的超疏水亲油网膜。X射线能量色散谱仪(EDS),傅里叶变换红外光谱(FTIR)和X射线衍射(XRD)结果证明,网膜表面构筑的微纳结构化学成分为Cu[CH3(CH2)12COO]2。网膜表面结构稳定,分别在pH 1.0～13.8的酸或碱溶液以及1MNaCl溶液中浸泡72 h后仍能保持较完整的微纳结构和超疏水亲油浸润特性。网膜对水和油的渗透压强分为3.18 kPa和0 kPa,对柴油、正己烷、石油醚和1,2-二氯乙烷油水混合物的油水分离效率高达98%以上,表现出良好的油水分离特性；经过100次的连续的分离测试后油水分离效率仍保持在97%以上,具有良好的结构和功能稳定性。(3)以铜网网膜为基底材料,制备了浸润性可以在超疏水亲油和水下超疏油亲水之间快速转变的油水分离网膜,并研究了网膜的油水分离特性。通过碱辅助的化学氧化的方法将铜网在2.5M NaOH,0.1 M K2S2O8溶液中室温条件下氧化反应20 min在网膜表面成功构筑了CuO纳米结构,依次对构筑了CuO纳米结构的网膜进行十八烷酸表面改性和热氧化退火处理,可以实现并控制网膜浸润性在超疏水亲油和超疏油亲水之间的快速转化。采用0.02 M的十八烷酸处理5 min后网膜表现出超疏水亲油特性,水接触角为161.6°,渗透压强达到1.2 kPa以上；继续将网膜在330℃条件下退火热氧化处理3 min,即可实现网膜浸润性由超疏水亲油向水下超疏油亲水状态的快速转变,网膜对油的渗透压强可达1.0 kPa,整个转变过程仅需8min。EDS,FTIR, XRD的结果证明,在K2S208和NaOH溶液中构筑的纳米线结构为CuO；经十八烷酸表面改性后,在CuO纳米线表面生成Cu[CH3(CH2)16COO]2;对超疏水亲油状态的网膜进行退火氧化处理,网膜表面的Cu[CH3(CH2)16COO]2发生氧化分解,表面的CuO结构重新暴露出来,从而实现网膜表面浸润性由超疏水亲油向超疏油亲水的转变。两种浸润性状态下网膜对煤油、正己烷、石油醚和1,2-二氯乙烷的油水混合物的油水分离效率在97%以上,对植物油的油水分离效率在96%以上；水下超疏油亲水浸润状态下网膜对高粘度及密度比水小的油类的分离效率优于超疏水亲油状态的网膜,对密度比水大的油类分离效果则表现相反的趋势。经过20次连续的油水分离试验后,网膜的油水分离效率基本没有降低,具有良好的稳定性和耐用性。本论文制备的三种特殊浸润性材料表现出良好的结构特性和功能特性,有望在干性粘附、自清洁和油水分离等领域得到应用。
[Abstract]:The special infiltrative material has a wide application prospect in daily life and industrial and agricultural production because of its special surface characteristics, and also aroused great interest and attention of the researchers. Based on the application prospect of special infiltrative materials, a super-hydrophobic micro-graph with dry adhesion and self-cleaning properties was prepared. The surface characteristics and functional properties of three kinds of special wettability materials are characterized and studied. The surface properties and functional properties of three kinds of special wettability materials are characterized and studied, and the application of the above materials is also explored. The main contents and results of this paper are as follows: (1) The super-hydrophobic micrographs of PDMS (polydimethylsiloxane, silicone rubber) with dry adhesion and self-cleaning properties are prepared, and the adhesion, infiltration and self-cleaning properties of the micrographs are characterized and studied. The adhesive properties of micrographs on different roughness and surface energy surface were studied. By means of the combination of dry etching and injection molding of the mould, the complete imitation gecko micrographs with the structure of the bristles are successfully prepared, and the mechanical research results of the micrographs show that the adhesion force of the micrographs is increased with the increase of the preload, the diameter of the bristles is reduced, the density of the bristles is increased, the increase of the length-to-diameter ratio of the bristles is beneficial to the improvement of the adhesion of the micro-graph, the roughness and the surface of the adhesive surface can influence the adhesion property of the micro-pattern, The adhesion force has a maximum value at the matching roughness and then decreases with the change of the roughness; the micro-pattern can exhibit a stronger adhesion force on the high surface energy surface. the surface of the infiltrative study of the micro-graph, the bristle structure of the micro-graphic surface can improve the super-hydrophobicity of the surface, the infiltration model of the micro-graphic surface can meet the Cassie-Baxter model, the diameter of the bristles and the duty ratio fs are reduced, and the hydrophobicity of the micro-graph is improved, The water contact angle of the micro-pattern P-8-20-20 was 155.0 掳, the rolling angle was 7.2 掳, and the super-hydrophobicity was exhibited. Similar to the sole of the gecko, the micrographs show good self-cleaning performance. The self-cleaning test shows that the self-cleaning efficiency of the micrographs P-8-20-20 is up to 91.3%. (2) The super-hydrophobic and oleophilic oil-water separation membrane was successfully prepared by using the copper net film as the base material, and the oil-water separation characteristic of the web was studied. The effect of preparation process parameters and reaction conditions on the structure and wettability of the micro-nano structure of the web surface was discussed, and the water contact angle reached 156.7 掳 and the oil contact was 0 掳. The X-ray energy dispersive spectrometer (EDS), the Fourier transform infrared spectroscopy (FTIR) and the X-ray diffraction (XRD) result show that the chemical composition of the micro-nano structure constructed by the surface of the web is Cu[CH3 (CH2) 12COO] 2. The surface of the omental surface is stable, and the complete micro-nano structure and the super-hydrophobic-oleophilic infiltration property can be maintained after being soaked for 72h in an acid or a base solution with a pH of 1.0 to 13.8 and a solution of 1 M NaCl, respectively. The osmotic pressure of the water and the oil is 3.18 kPa and 0 kPa, and the oil-water separation efficiency of the oil-water mixture of diesel, n-hexane, petroleum ether and 1,2-dichloroethane is up to more than 98%, and the oil-water separation characteristic is good; After 100 consecutive separation tests, the oil-water separation efficiency is still above 97%, and has good structural and functional stability. (3) The oil-water separation net film, which can change rapidly between super-hydrophobic and oleophilic and super-oleophobic and hydrophilic, is prepared by taking the copper net film as the base material, and the oil-water separation characteristic of the web is studied. The CuO nano-structure was successfully constructed on the surface of the web at room temperature in the solution of 2.5M NaOH and 0.1M K2S2O8 by the method of alkali-assisted chemical oxidation, and the surface modification of the octadecanoic acid and the thermal oxidation annealing treatment were carried out on the omentum which constructed the CuO nano-structure, The rapid transformation between the super-hydrophobic and oleophilic and super-oleophobic hydrophilic can be realized and controlled. taking the octadecane acid of 0.02M for 5 minutes, the omental film shows the super-hydrophobic and oleophilic property, the water contact angle of the water is 161.6 degrees, the osmotic pressure is strong to be more than 1.2 kPa, the net film is continuously annealed and thermally oxidized for 3 minutes under the condition of 330 DEG C, can realize the rapid transformation of the net film wettability from the super-hydrophobic and oleophilic to the underwater super-oleophobic hydrophilic state, the osmotic pressure of the net film to the oil can reach 1.0 kPa, the whole transformation process is only 8 minutes, and the results of the EDS, the FTIR and the XRD prove that the nanowire structure constructed in the K2S208 and the NaOH solution is CuO; after the surface of the octadecanoic acid is modified, Cu[CH3 (CH2) 16COO] 2 is generated on the surface of the CuO nano wire, So as to realize the transformation of the surface wettability of the omental surface from the super-hydrophobic and oleophilic to the super-oleophobic hydrophilic. the oil-water separation efficiency of the oil-water mixture of the net film on the kerosene, the n-hexane, the petroleum ether and the 1,2-dichloroethane is more than 97% under the two infiltrative states, and the oil-water separation efficiency on the vegetable oil is more than 96 percent; Under the condition of the hydrophilic infiltration of the super-oleophobic oil under water, the separation efficiency of the oil with high viscosity and density less than that of water is superior to that of the super-hydrophobic-lipophilic state, and the oil separation effect with higher density than water shows the opposite tendency. After 20 consecutive oil-water separation tests, the oil-water separation efficiency of the web was not reduced, and it had good stability and durability. The three kinds of special wettability materials prepared in this paper show good structural and functional properties, and are expected to be applied in the fields of dry adhesion, self-cleaning and oil-water separation.
【学位授予单位】：西南交通大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：R318.08

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