長(zhǎng)效流體—固體復(fù)合表面的制備及耐蝕性研究
發(fā)布時(shí)間：2018-10-24 22:25
【摘要】：腐蝕是材料在海洋環(huán)境應(yīng)用中面臨的重要問題。近年來(lái),基于超疏水材料的防腐蝕引起了人們的關(guān)注。氣-固復(fù)合結(jié)構(gòu)的超疏水表面能夠利用微納米級(jí)粗糙結(jié)構(gòu)駐留的空氣墊隔絕基體金屬與腐蝕性介質(zhì)的直接接觸,從而保護(hù)金屬免遭腐蝕。然而,空氣的溶解以及水蒸氣的凝結(jié)作用使得超疏水表面在水下壽命短,難以實(shí)現(xiàn)對(duì)基體金屬的長(zhǎng)效保護(hù),限制了此類材料在水下環(huán)境中的應(yīng)用。本文針對(duì)超疏水材料水下環(huán)境壽命短的難題進(jìn)行了兩方面的探索:(1)在粗糙疏水結(jié)構(gòu)中浸注不溶于水的全氟潤(rùn)滑油,構(gòu)筑長(zhǎng)效液-固復(fù)相疏水表面。(2)采用外加通氣法規(guī)避傳統(tǒng)超疏水層的有限量空氣的溶解問題,實(shí)現(xiàn)超疏水層的長(zhǎng)效化。兩種疏水結(jié)構(gòu)均用于低合金鋼的防腐蝕,并在海水環(huán)境中表現(xiàn)出良好耐蝕性能,可作為特殊保護(hù)層用于海洋環(huán)境中材料的腐蝕防護(hù)。由于油不溶于水,在水壓的作用下不會(huì)逸出,可與微納米級(jí)粗糙結(jié)構(gòu)形成水下穩(wěn)定的液-固復(fù)合體系。本文采用溶解-沉積法在低合金鋼表面構(gòu)建了具有微米級(jí)粗糙結(jié)構(gòu)的十四酸鐵金屬配合物,并在其表面浸潤(rùn)全氟聚醚油構(gòu)成金屬配合物-全氟聚醚油復(fù)合體系(SLIPS涂層)。利用掃描電子顯微鏡、能譜儀、接觸角測(cè)試儀以及共聚焦顯微鏡分析了金屬配合物的表面形貌、元素組成,濕潤(rùn)性以及表面粗糙度,并分析了復(fù)合體系的成膜機(jī)理和防腐機(jī)理。研究結(jié)果表明,制備的十四酸鐵金屬配合物與水滴的接觸角高達(dá)152.45°。涂層表面形貌與電解時(shí)間以及電解質(zhì)導(dǎo)電性有關(guān),電解時(shí)間越長(zhǎng),高氯酸鋰濃度越高,涂層表面越粗糙�；w金屬表面不斷溶解的鐵離子與溶液中的十四酸反應(yīng)構(gòu)成金屬配合物,該金屬配合物主要為不連續(xù)的乳突和殼體。電化學(xué)實(shí)驗(yàn)表明經(jīng)20μL全氟聚醚油覆蓋的SLIPS涂層的腐蝕電流密度Icorr為低合金鋼以及疏水性涂層的十分之一,且隨著浸沒時(shí)間延長(zhǎng)而增大。由于油膜不能完全覆蓋金屬表面,表面發(fā)生腐蝕。當(dāng)油膜含量為40μL,60μL和80μL時(shí),其腐蝕電流密度Icorr相比20μL降低了6個(gè)數(shù)量級(jí),且隨著浸沒時(shí)間的延長(zhǎng),試樣表面不再發(fā)生腐蝕。完全覆蓋基體表面的油膜的能夠有效阻止腐蝕性介質(zhì)與疏水涂層的接觸,達(dá)到長(zhǎng)效防腐蝕的目的。將傳統(tǒng)立體網(wǎng)狀結(jié)構(gòu)的海綿采用一步浸泡法制備了整體具有疏水性的超疏水海綿,其與水滴接觸角為163.6°,并可通過向其內(nèi)部不斷充入干燥空氣得到長(zhǎng)效超疏水效果。借助于濕敏電阻監(jiān)測(cè)通入不同氣體流量時(shí)海綿內(nèi)部濕度變化,通氣量越高,內(nèi)部濕度越低,疏水性越好。電化學(xué)實(shí)驗(yàn)表明,當(dāng)超疏水海綿浸沒在水中46 h之后,海綿內(nèi)部鋼針的腐蝕電流密度Icorr提高了10倍,這是由于隨著浸沒時(shí)間延長(zhǎng),海綿內(nèi)空氣逸出,超疏水性能消失;但當(dāng)有干燥空氣不斷充入時(shí),鋼針的腐蝕電流密度Icorr變化不大。不斷通入的干燥氣體能夠有效的隔絕外界腐蝕介質(zhì)與鋼針的接觸,保護(hù)鋼針免于腐蝕。
[Abstract]:Corrosion is an important problem in marine environment application. In recent years, the anti-corrosion based on super-hydrophobic materials has attracted people's attention. the super-hydrophobic surface of the gas-solid composite structure can isolate the direct contact between the base metal and the corrosive medium by using the air cushion which resides on the micro-scale coarse structure so as to protect the metal from corrosion. However, the dissolution of air and the condensation of water vapor make the super-hydrophobic surface short in water and difficult to realize long-acting protection of matrix metal, which limits the application of such materials in underwater environment. In order to solve the problem of short life of super-hydrophobic material under water environment, this paper explores two aspects: (1) soaking water-insoluble perfluorolubricating oil in a rough hydrophobic structure, and constructing a long-acting liquid-solid complex-phase hydrophobic surface. and (2) adopting the external ventilation regulations to avoid the problem of limited air dissolution of the traditional super-hydrophobic layer and realizing the long-acting of the super-hydrophobic layer. Both hydrophobic structures are used for corrosion protection of low alloy steel and show good corrosion resistance in seawater environment, and can be used as special protection layer for corrosion protection of materials in the marine environment. As the oil is insoluble in water, the water does not escape under the action of water pressure, and the underwater stable liquid-solid composite system can be formed with the micro-scale coarse structure. In this paper, a tetradecanoic acid metal complex with micron-sized roughness structure was constructed on low alloy steel surface by dissolution-deposition method, and perfluoropolyether oil was soaked in the surface of low alloy steel to form a metal complex-perfluoropolyether oil composite system (SLIPS coating). Surface morphology, element composition, wettability and surface roughness of metal complex were analyzed by scanning electron microscope, energy spectrometer, contact angle tester and confocal microscope, and the film forming mechanism and anti-corrosion mechanism of the composite system were analyzed. The results showed that the contact angle of tetradecanoic acid metal complex with water drops reached 152. 45 擄. the surface morphology of the coating is related to the electrolysis time and the electrolyte conductivity, the longer the electrolysis time, the higher the lithium perchlorate concentration, and the more rough the coating surface. the continuously dissolving iron ions on the metal surface of the matrix form a metal complex with the tetradecanoic acid in the solution, and the metal complex is mainly discontinuous mastoid and shell. Electrochemical experiments show that the corrosion current density Icorr of the SLIPS coating covered with 20. m u.L of perfluoropolyether oil is one tenth of the low alloy steel and the hydrophobic coating, and increases as the immersion time is prolonged. Corrosion occurs on the surface because the oil film cannot completely cover the metal surface. When the oil film content is 40 & mu; L, 60 & mu; L, and 80 & mu; L, the corrosion current density Icorr is reduced by 6 orders of magnitude as compared to 20 & mu; L, and corrosion is no longer occurring on the surface of the sample as the immersion time is prolonged. the contact between the corrosive medium and the hydrophobic coating can be effectively prevented by completely covering the oil film on the surface of the substrate, so that the purpose of long-acting corrosion prevention is achieved. A super-hydrophobic sponge with hydrophobic property is prepared by one-step soaking method, and the contact angle of water drops is 163. 6 擄, and the long-acting super-hydrophobic effect can be obtained by continuously charging dry air into the sponge. By using the wet-sensitive resistor to monitor the change of humidity inside the sponge, the higher the volume of aeration, the lower the internal humidity and the better the hydrophobicity. The electrochemical experiments show that the corrosion current density Icorr of the steel needle inside the sponge is increased by 10 times when the super-hydrophobic sponge is immersed in water for 46 hours, which is due to the prolonged immersion time, the escape of air in the sponge, and the disappearance of the super-hydrophobic property; however, when the dry air is continuously filled, The corrosion current density Icorr of the steel needle is not large. the continuously communicated drying gas can effectively isolate the contact between the external corrosion medium and the steel needle and protect the steel needle from corrosion.
【學(xué)位授予單位】：中國(guó)石油大學(xué)(華東)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類號(hào)】：TG174.4
本文編號(hào)：2292742
[Abstract]:Corrosion is an important problem in marine environment application. In recent years, the anti-corrosion based on super-hydrophobic materials has attracted people's attention. the super-hydrophobic surface of the gas-solid composite structure can isolate the direct contact between the base metal and the corrosive medium by using the air cushion which resides on the micro-scale coarse structure so as to protect the metal from corrosion. However, the dissolution of air and the condensation of water vapor make the super-hydrophobic surface short in water and difficult to realize long-acting protection of matrix metal, which limits the application of such materials in underwater environment. In order to solve the problem of short life of super-hydrophobic material under water environment, this paper explores two aspects: (1) soaking water-insoluble perfluorolubricating oil in a rough hydrophobic structure, and constructing a long-acting liquid-solid complex-phase hydrophobic surface. and (2) adopting the external ventilation regulations to avoid the problem of limited air dissolution of the traditional super-hydrophobic layer and realizing the long-acting of the super-hydrophobic layer. Both hydrophobic structures are used for corrosion protection of low alloy steel and show good corrosion resistance in seawater environment, and can be used as special protection layer for corrosion protection of materials in the marine environment. As the oil is insoluble in water, the water does not escape under the action of water pressure, and the underwater stable liquid-solid composite system can be formed with the micro-scale coarse structure. In this paper, a tetradecanoic acid metal complex with micron-sized roughness structure was constructed on low alloy steel surface by dissolution-deposition method, and perfluoropolyether oil was soaked in the surface of low alloy steel to form a metal complex-perfluoropolyether oil composite system (SLIPS coating). Surface morphology, element composition, wettability and surface roughness of metal complex were analyzed by scanning electron microscope, energy spectrometer, contact angle tester and confocal microscope, and the film forming mechanism and anti-corrosion mechanism of the composite system were analyzed. The results showed that the contact angle of tetradecanoic acid metal complex with water drops reached 152. 45 擄. the surface morphology of the coating is related to the electrolysis time and the electrolyte conductivity, the longer the electrolysis time, the higher the lithium perchlorate concentration, and the more rough the coating surface. the continuously dissolving iron ions on the metal surface of the matrix form a metal complex with the tetradecanoic acid in the solution, and the metal complex is mainly discontinuous mastoid and shell. Electrochemical experiments show that the corrosion current density Icorr of the SLIPS coating covered with 20. m u.L of perfluoropolyether oil is one tenth of the low alloy steel and the hydrophobic coating, and increases as the immersion time is prolonged. Corrosion occurs on the surface because the oil film cannot completely cover the metal surface. When the oil film content is 40 & mu; L, 60 & mu; L, and 80 & mu; L, the corrosion current density Icorr is reduced by 6 orders of magnitude as compared to 20 & mu; L, and corrosion is no longer occurring on the surface of the sample as the immersion time is prolonged. the contact between the corrosive medium and the hydrophobic coating can be effectively prevented by completely covering the oil film on the surface of the substrate, so that the purpose of long-acting corrosion prevention is achieved. A super-hydrophobic sponge with hydrophobic property is prepared by one-step soaking method, and the contact angle of water drops is 163. 6 擄, and the long-acting super-hydrophobic effect can be obtained by continuously charging dry air into the sponge. By using the wet-sensitive resistor to monitor the change of humidity inside the sponge, the higher the volume of aeration, the lower the internal humidity and the better the hydrophobicity. The electrochemical experiments show that the corrosion current density Icorr of the steel needle inside the sponge is increased by 10 times when the super-hydrophobic sponge is immersed in water for 46 hours, which is due to the prolonged immersion time, the escape of air in the sponge, and the disappearance of the super-hydrophobic property; however, when the dry air is continuously filled, The corrosion current density Icorr of the steel needle is not large. the continuously communicated drying gas can effectively isolate the contact between the external corrosion medium and the steel needle and protect the steel needle from corrosion.
【學(xué)位授予單位】：中國(guó)石油大學(xué)(華東)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類號(hào)】：TG174.4
【參考文獻(xiàn)】
相關(guān)期刊論文 前2條
1 李楊;王立達(dá);劉貴昌;;鋁基超疏水表面的制備及其耐蝕性[J];電鍍與涂飾;2012年05期
2 劉通;劉濤;陳守剛;程莎;尹衍升;;超疏水表面改善鋁基材料的抗海水腐蝕性能[J];無(wú)機(jī)化學(xué)學(xué)報(bào);2008年11期
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