微纳米TiO_2和TiO_2-FPS疏水涂层上的池沸腾传热和结垢腐蚀行为
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摘要
为了应用微纳表面工程方法抑制换热表面上的污垢沉积，本文在AISI304不锈钢基底上制备和表征了微纳米TiO_2和TiO_2-FPS疏水涂层，并在自行研制的、带有污垢数据在线自动采集系统的、传热表面垂直放置的池沸腾装置中开展了CaCO_3和CaSO_4水溶液池沸腾传热和结垢研究，另外进行了TiO_2涂层的腐蚀实验研究，取得了如下研究结果：
1.微纳米TiO_2和TiO_2-FPS疏水涂层去离子水饱和池沸腾研究表明，相比TiO_2涂层，TiO_2-FPS复合疏水涂层因具有较低的表面能，较大的汽化核心密度，较小的汽泡酝酿时间和较高的汽泡脱离频率而增强传热10%以上。
2.不同涂层表面上饱和CaCO_3溶液池沸腾污垢沉积规律研究表明，与不锈钢相比，TiO_2涂层的渐近污垢热阻下降约30%，TiO_2-FPS复合疏水涂层的渐近污垢热阻下降约50%。应用渐近污垢热阻曲线方程可以较好地拟合饱和CaCO_3溶液在不同表面上的池沸腾污垢沉积数据。不同涂层表面上饱和CaSO_4溶液池沸腾污垢沉积规律研究表明，TiO_2涂层表面污垢热阻略低于不锈钢表面，而TiO_2-FPS复合涂层的污垢热阻约为不锈钢基底的0.5倍，说明TiO_2-FPS复合涂层可以显著抑制污垢沉积。不同表面上CaCO_3与CaSO_4的微观形貌研究表明，TiO_2涂层上为方解石型垢，TiO_2-FPS涂层上为霰石型垢，在TiO_2和TiO_2-FPS涂层上的CaCO_3污垢均较为蓬松，易于去除。表面上的CaSO_4垢致密，较难去除。
3.基于XDLVO和DLVO理论的CaSO_4颗粒与换热表面间的胶体相互作用分析表明，应用XDLVO理论预测不同表面的结垢趋势更为准确；欲抑制换热表面结垢，可以在换热表面涂覆低表面能非极性F-C化学键材料，以减小污垢颗粒和换热表面间的Lewis酸碱作用分量。
4.应用Tafel极化曲线、循环伏安法和电化学阻抗等电化学方法，在3.5%NaCl和0.05M NaOH混合溶液中研究了TiO_2涂层的耐腐蚀性能，结果表明，相比不锈钢，厚度为288.9±0.8nm的致密TiO_2涂层的腐蚀电势提高约0.12V，腐蚀电流约下降为0.1倍，极化电阻增大约17倍，耐腐蚀性能提高；TiO_2涂层在腐蚀介质中为多级腐蚀过程。
Both the micro-nanometer titania and hydrophobic titania-fluoroalkysilane coatingswere prepared and characterized on AISI304stainless steel with liquid phasedeposition technology. Fouling tests of CaCO_3and CaSO_4solutions were carried outon the vertical titania and titania-fluoroalkysilane coating surfaces in self-made poolboiling equipment with online acquisition system. In addition, anti-corrosion propertyof titania coating was also carried out in the mixed corrosion solution composed of3.5wt.%NaCl and0.05mol·L~(-1) NaOH. The main results obtained are as follows.
1. Pool boiling heat transfer performance of titania and hydrophobictitania-fluoroalkysilane coating surfaces were evaluated with deionized water. Theresults show that the pool boiling heat transfer coefficient on the hydrophobictitania-fluoroalkysilane coating could increase by10%or more compared with titaniacoating, which is due to the titania-fluoroalkysilane coating has very low surfaceenergy, and can provide large core density, small bubble departure diameter as well ashigh bubble departure frequency for the pool boiling.
2. CaCO_3fouling deposition performance of titania and titania-fluoroalkysilanecoatings were carried out in the pool boiling equipment. The results show that thefouling resistance curves belong to the asymptotic type. The asymptotic foulingresistance on titania and titania-fluoroalkysilane composite coating can be reducedabout30%and50%compared with polished AISI304stainless steel, respectively. Theasymptotic equation can satisfactorily predict the data of the fouling resistancesobtained on different heat transfer surfaces. The fouling tests results in saturatedCaSO_4solution indicate that the fouling resistance of titania coating is slightly lowerthan that of the polished AISI304stainless steel. The fouling resistances ontitania-fluoroalkysilane coating are approximately one-half of those on AISI304stainless steel which indicate that titania-fluoroalkysilane coating can significantlyinhibit the fouling depositions. Morphology of CaCO_3and CaSO_4crystallizationfouling was also investigated. The results show that the fouling type deposited ontitania coating is of calcite, while on titania-fluoroalkysilane coating is of aragonite.CaCO_3fouling is very fluffy, and easy to be removed both on titania andtitania-fluoroalkysilane coatings, while CaSO_4fouling is dense, and more difficult to remove than CaCO_3fouling from the heat transfer surfaces.
3. The colloidal interactions between CaSO_4fouling particles and the heat transfersurfaces were calculated and analyzed with XDLVO and DLVO theories. The resultsshow that the XDLVO theory can predict more accurately the fouling trends ofdifferent heat transfer surfaces. The key approach to reduce the tendency of CaSO_4fouling deposition is trying to reduce the Lewis acid-base interaction energycomponent and coat the non-polar and low energy materials with F-C chemical bondson the heat transfer surface.
4. The anti-corrosion performance of the titania coatings were also carried out withthe electrochemical methods, such as Tafel polarization curves, cyclic voltammetry,and electrochemical impedance techniques, in the mixed corrosion solution composedof3.5wt.%NaCl and0.05mol·L~(-1) NaOH. The results show that the anti-corrosionproperty of titania coating can be significantly improved compared with AISI304stainless steel. The titania coating with thickness of288.9±0.8nm can improve thecorrosion potential of about0.12V, decrease the corrosion current of about0.1times,and increase the polarization resistance by about17times compared with AISI304stainless steel substrate. The multistage corrosion process of titania coating mighthave happened in the corrosion solution.
1.微纳米TiO_2和TiO_2-FPS疏水涂层去离子水饱和池沸腾研究表明，相比TiO_2涂层，TiO_2-FPS复合疏水涂层因具有较低的表面能，较大的汽化核心密度，较小的汽泡酝酿时间和较高的汽泡脱离频率而增强传热10%以上。
2.不同涂层表面上饱和CaCO_3溶液池沸腾污垢沉积规律研究表明，与不锈钢相比，TiO_2涂层的渐近污垢热阻下降约30%，TiO_2-FPS复合疏水涂层的渐近污垢热阻下降约50%。应用渐近污垢热阻曲线方程可以较好地拟合饱和CaCO_3溶液在不同表面上的池沸腾污垢沉积数据。不同涂层表面上饱和CaSO_4溶液池沸腾污垢沉积规律研究表明，TiO_2涂层表面污垢热阻略低于不锈钢表面，而TiO_2-FPS复合涂层的污垢热阻约为不锈钢基底的0.5倍，说明TiO_2-FPS复合涂层可以显著抑制污垢沉积。不同表面上CaCO_3与CaSO_4的微观形貌研究表明，TiO_2涂层上为方解石型垢，TiO_2-FPS涂层上为霰石型垢，在TiO_2和TiO_2-FPS涂层上的CaCO_3污垢均较为蓬松，易于去除。表面上的CaSO_4垢致密，较难去除。
3.基于XDLVO和DLVO理论的CaSO_4颗粒与换热表面间的胶体相互作用分析表明，应用XDLVO理论预测不同表面的结垢趋势更为准确；欲抑制换热表面结垢，可以在换热表面涂覆低表面能非极性F-C化学键材料，以减小污垢颗粒和换热表面间的Lewis酸碱作用分量。
4.应用Tafel极化曲线、循环伏安法和电化学阻抗等电化学方法，在3.5%NaCl和0.05M NaOH混合溶液中研究了TiO_2涂层的耐腐蚀性能，结果表明，相比不锈钢，厚度为288.9±0.8nm的致密TiO_2涂层的腐蚀电势提高约0.12V，腐蚀电流约下降为0.1倍，极化电阻增大约17倍，耐腐蚀性能提高；TiO_2涂层在腐蚀介质中为多级腐蚀过程。
Both the micro-nanometer titania and hydrophobic titania-fluoroalkysilane coatingswere prepared and characterized on AISI304stainless steel with liquid phasedeposition technology. Fouling tests of CaCO_3and CaSO_4solutions were carried outon the vertical titania and titania-fluoroalkysilane coating surfaces in self-made poolboiling equipment with online acquisition system. In addition, anti-corrosion propertyof titania coating was also carried out in the mixed corrosion solution composed of3.5wt.%NaCl and0.05mol·L~(-1) NaOH. The main results obtained are as follows.
1. Pool boiling heat transfer performance of titania and hydrophobictitania-fluoroalkysilane coating surfaces were evaluated with deionized water. Theresults show that the pool boiling heat transfer coefficient on the hydrophobictitania-fluoroalkysilane coating could increase by10%or more compared with titaniacoating, which is due to the titania-fluoroalkysilane coating has very low surfaceenergy, and can provide large core density, small bubble departure diameter as well ashigh bubble departure frequency for the pool boiling.
2. CaCO_3fouling deposition performance of titania and titania-fluoroalkysilanecoatings were carried out in the pool boiling equipment. The results show that thefouling resistance curves belong to the asymptotic type. The asymptotic foulingresistance on titania and titania-fluoroalkysilane composite coating can be reducedabout30%and50%compared with polished AISI304stainless steel, respectively. Theasymptotic equation can satisfactorily predict the data of the fouling resistancesobtained on different heat transfer surfaces. The fouling tests results in saturatedCaSO_4solution indicate that the fouling resistance of titania coating is slightly lowerthan that of the polished AISI304stainless steel. The fouling resistances ontitania-fluoroalkysilane coating are approximately one-half of those on AISI304stainless steel which indicate that titania-fluoroalkysilane coating can significantlyinhibit the fouling depositions. Morphology of CaCO_3and CaSO_4crystallizationfouling was also investigated. The results show that the fouling type deposited ontitania coating is of calcite, while on titania-fluoroalkysilane coating is of aragonite.CaCO_3fouling is very fluffy, and easy to be removed both on titania andtitania-fluoroalkysilane coatings, while CaSO_4fouling is dense, and more difficult to remove than CaCO_3fouling from the heat transfer surfaces.
3. The colloidal interactions between CaSO_4fouling particles and the heat transfersurfaces were calculated and analyzed with XDLVO and DLVO theories. The resultsshow that the XDLVO theory can predict more accurately the fouling trends ofdifferent heat transfer surfaces. The key approach to reduce the tendency of CaSO_4fouling deposition is trying to reduce the Lewis acid-base interaction energycomponent and coat the non-polar and low energy materials with F-C chemical bondson the heat transfer surface.
4. The anti-corrosion performance of the titania coatings were also carried out withthe electrochemical methods, such as Tafel polarization curves, cyclic voltammetry,and electrochemical impedance techniques, in the mixed corrosion solution composedof3.5wt.%NaCl and0.05mol·L~(-1) NaOH. The results show that the anti-corrosionproperty of titania coating can be significantly improved compared with AISI304stainless steel. The titania coating with thickness of288.9±0.8nm can improve thecorrosion potential of about0.12V, decrease the corrosion current of about0.1times,and increase the polarization resistance by about17times compared with AISI304stainless steel substrate. The multistage corrosion process of titania coating mighthave happened in the corrosion solution.
引文
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