高黏附性超疏水表面的制备

高黏附性超疏水表面的制备Preparationofsuperhydrophobicsurfacewithhighadhesion摘要润湿性和黏附性是固体表面的重要特性。近些年来，高黏附性超疏水表面的制备技术和相关理论研究不断被报道。本文提出了一种化学腐蚀与热压剥离相结合的高黏附性超疏水表面制备方法，实验过程绿色环保，操作简单，耗时短。主要研究内容如下：1、首先，利用化学腐蚀的方法制得超亲水的金属表面；其次，利用热压机，通过控制温度来制得高密度聚乙烯板；最后，利用热压机将腐蚀后的金属模板与高密度聚乙烯板压合，采用热压剥离的方法，获得超疏水金属板及聚乙烯表面。2、探究热压温度对样品表面浸润性及黏附性的影响，确定制备高黏附性超疏水表面的最佳热压温度。3、探究高黏附超疏水样品表面在微反应器及液滴无损转移方面的应用。关键词超疏水高黏附性化学腐蚀热压剥离AbstractWettabilityandadhesionareimportantpropertiesofsolidsurface.Inrecentyears,thepreparationtechnologyandrelatedtheoreticalresearchofhighadhesionsuperhydrophobicsurfacehavebeenreported.Inthispaper,apreparationmethodofhighadhesionsuperhydrophobicsurface,whichcombineschemicalcorrosionwithhotpressstripping,isproposed.Themainresearchcontentsareasfollows:1.Firstly,thesuperhydrophobicmetalsurfaceismadebychemicalcorrosionmethod;secondly,thehigh-densitypolyethyleneplateismadebycontrollingthetemperaturewiththehotpress;finally,themetaltemplateaftercorrosionispressedwiththehigh-densitypolyethyleneplatebythehotpress,andthesuperhydrophobicmetalplateandthepolyethylenesurfaceareobtainedbythehotpressstrippingmethod.2.Toexploretheinfluenceofhot-pressingtemperatureonthewettabilityandadhesionofthesamplesurface,andtodeterminethebesthot-pressingtemperatureforthepreparationofhighadhesionsuperhydrophobicsurface.3.ToexploretheapplicationofhighadhesionsuperhydrophobicsamplesurfaceinMicroreactoranddropletnondestructivetransfer.Keywordssuper-hydrophobichighadhesionchemicalcorrosionhotpressstripping目录第1章绪论 第1章绪论1.1引言润湿是指固体表面固气界面逐渐被固液界面替换的过程。表面润湿性是固体最重要的性质之一，它代表了液体（通常为水）在固体材料表面的铺展能力及倾向性ADDINEN.CITE<EndNote><Cite><Author>Barthlott</Author><Year>1997</Year><RecNum>145</RecNum><DisplayText><styleface="superscript">[1]</style></DisplayText><record><rec-number>145</rec-number><foreign-keys><keyapp="EN"db-id="xts9zv5252fsxkewd9b5tvr4rt2t2vevwefx"timestamp="1540100586">145</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>W.Barthlott</author><author>C.Neinhuis</author></authors></contributors><titles><title>Purityofthesacredlotus,orescapefromcontaminationinbiologicalsurfaces</title><secondary-title>Planta</secondary-title></titles><periodical><full-title>Planta</full-title></periodical><pages>1-8</pages><volume>202</volume><number>1</number><dates><year>1997</year></dates><urls></urls></record></Cite></EndNote>[1]。根据固体表面的润湿性（又称浸润性）的不同，一般可分为非润湿、部分润湿、完全润湿表面。目前，固体表面润湿性通常使用接触角测定仪测定静态接触角进行表征。，称固体表面完全润湿；，固体表面能被液体部分润湿，呈疏水性，其中，，称为超亲水表面；，固体表面不被液体所润湿，液滴呈圆球状，呈疏水性，其中，，称为超疏水表面。表面的润湿性与表面的吸附、粘合、分散、摩擦等物理化学过程密切相关，.不论是在自然界中还是在人们的日常生活以及工农业生产中都发挥着十分重要的作用。在工业催化、原油开采、矿物浮选、机械润滑、装修涂料和生物医药等领域，材料表面的润湿性都有着广泛的应用ADDINEN.CITE<EndNote><Cite><Author>林龙翔</Author><Year>2013</Year><RecNum>162</RecNum><DisplayText><styleface="superscript">[2,3]</style></DisplayText><record><rec-number>162</rec-number><foreign-keys><keyapp="EN"db-id="xts9zv5252fsxkewd9b5tvr4rt2t2vevwefx"timestamp="1540104274">162</key></foreign-keys><ref-typename="Thesis">32</ref-type><contributors><authors><author>林龙翔</author></authors></contributors><titles><title>微图案化透明超亲/超疏水模板及细胞与生物材料相互作用的原位/高能量研究</title></titles><dates><year>2013</year></dates><publisher>厦门大学</publisher><urls></urls></record></Cite><Cite><Author>李杰</Author><Year>2012</Year><RecNum>175</RecNum><record><rec-number>175</rec-number><foreign-keys><keyapp="EN"db-id="xts9zv5252fsxkewd9b5tvr4rt2t2vevwefx"timestamp="1540106382">175</key></foreign-keys><ref-typename="Thesis">32</ref-type><contributors><authors><author>李杰</author></authors></contributors><titles><title>镁合金及硅基底超疏水表面的制备与性能研究</title></titles><dates><year>2012</year></dates><publisher>大连海事大学</publisher><urls></urls></record></Cite></EndNote>[2,3]。自然界中具有特殊润湿性的动植物表面引起了人们的关注与研究。如以荷叶表面为代表的超疏水低黏附现象，水滴在其表面呈球形，且极易滚落，以此带走表面的灰尘，实现荷叶表面的自清洁功能。以玫瑰花瓣表面为代表的超疏水高黏附现象，在接触角大于150°的情况下，将表面竖直或翻转180°，水滴仍能够黏附在表面上，不滴落。超疏水表面因其特殊的浸润性不仅引起了研究者们的科学兴趣，更因其特殊的黏附性在工业生产和日常生活中引起了广泛关注与应用。例如，超疏水低黏附性表面在自清洁ADDINEN.CITE<EndNote><Cite><Author>Nakajima</Author><Year>2000</Year><RecNum>224</RecNum><DisplayText><styleface="superscript">[4,5]</style></DisplayText><record><rec-number>224</rec-number><foreign-keys><keyapp="EN"db-id="xts9zv5252fsxkewd9b5tvr4rt2t2vevwefx"timestamp="1587475778">224</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Nakajima,A</author><author>Watanabe,T</author><author>Takai,K</author><author>Yamauchi,G</author><author>Fujishima,A</author><author>Hashimoto,K</author></authors></contributors><titles><title>TransparentSuperhydrophobicThinFilmswithSelf-CleaningProperties</title><secondary-title>Langmuir</secondary-title></titles><periodical><full-title>Langmuir</full-title><abbr-1>Langmuir:theACSjournalofsurfacesandcolloids</abbr-1></periodical><pages>7044-7047</pages><volume>16</volume><number>17</number><dates><year>2000</year></dates><urls></urls></record></Cite><Cite><Author>Bhushan</Author><Year>2009</Year><RecNum>203</RecNum><record><rec-number>203</rec-number><foreign-keys><keyapp="EN"db-id="xts9zv5252fsxkewd9b5tvr4rt2t2vevwefx"timestamp="1540114270">203</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Bhushan,Bharat</author><author>Yong,ChaeJung</author><author>Koch,Kerstin</author></authors></contributors><titles><title>Self-CleaningEfficiencyofArtificialSuperhydrophobicSurfaces</title><secondary-title>Langmuir</secondary-title></titles><periodical><full-title>Langmuir</full-title><abbr-1>Langmuir:theACSjournalofsurfacesandcolloids</abbr-1></periodical><pages>3240-3248</pages><volume>25</volume><number>5</number><dates><year>2009</year></dates><urls></urls></record></Cite></EndNote>[4,5]、防雾防雪防冰ADDINEN.CITE<EndNote><Cite><Author>Kulinich</Author><Year>2011</Year><RecNum>140</RecNum><DisplayText><styleface="superscript">[6,7]</style></DisplayText><record><rec-number>140</rec-number><foreign-keys><keyapp="EN"db-id="xts9zv5252fsxkewd9b5tvr4rt2t2vevwefx"timestamp="1540099896">140</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Kulinich,S.A.</author><author>Farhadi,S</author><author>Nose,K</author><author>Du,X.W.</author></authors></contributors><titles><title>Superhydrophobicsurfaces:aretheyreallyice-repellent?</title><secondary-title>Langmuir</secondary-title></titles><periodical><full-title>Langmuir</full-title><abbr-1>Langmuir:theACSjournalofsurfacesandcolloids</abbr-1></periodical><pages>25-29</pages><volume>27</volume><number>1</number><dates><year>2011</year></dates><urls></urls></record></Cite><Cite><Author>Mishchenko</Author><Year>2010</Year><RecNum>142</RecNum><record><rec-number>142</rec-number><foreign-keys><keyapp="EN"db-id="xts9zv5252fsxkewd9b5tvr4rt2t2vevwefx"timestamp="1540100169">142</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Mishchenko,L</author><author>Hatton,B</author><author>Bahadur,V</author><author>Taylor,J.A.</author><author>Krupenkin,T</author><author>Aizenberg,J</author></authors></contributors><titles><title>Designofice-freenanostructuredsurfacesbasedonrepulsionofimpactingwaterdroplets</title><secondary-title>AcsNano</secondary-title></titles><periodical><full-title>AcsNano</full-title></periodical><pages>7699-7707</pages><volume>4</volume><number>12</number><dates><year>2010</year></dates><urls></urls></record></Cite></EndNote>[6,7]、防腐抗抗阻ADDINEN.CITEADDINEN.CITE.DATA[8,9]、油水分离ADDINEN.CITE<EndNote><Cite><Author>Li</Author><Year>2015</Year><RecNum>26</RecNum><DisplayText><styleface="superscript">[10]</style></DisplayText><record><rec-number>26</rec-number><foreign-keys><keyapp="EN"db-id="xts9zv5252fsxkewd9b5tvr4rt2t2vevwefx"timestamp="1540086732">26</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Li,Hui</author><author>Zhao,Xiaoyun</author><author>Wu,Pengfei</author><author>Zhang,Shuxiang</author><author>Geng,Bing</author></authors></contributors><titles><title>Facilepreparationofsuperhydrophobicandsuperoleophilicporouspolymermembranesforoil/waterseparationfromapolyarylesterpolydimethylsiloxaneblockcopolymer</title><secondary-title>JournalofMaterialsScience</secondary-title></titles><periodical><full-title>JournalofMaterialsScience</full-title></periodical><pages>3211-3218</pages><volume>51</volume><number>6</number><dates><year>2015</year></dates><isbn>0022-2461 1573-4803</isbn><urls></urls><electronic-resource-num>10.1007/s10853-015-9632-6</electronic-resource-num></record></Cite></EndNote>[10]等方面良好的应用前景，而超疏水高黏附性表面在微流体系统ADDINEN.CITE<EndNote><Cite><Author>Bormashenko</Author><Year>2008</Year><RecNum>161</RecNum><DisplayText><styleface="superscript">[11]</style></DisplayText><record><rec-number>161</rec-number><foreign-keys><keyapp="EN"db-id="xts9zv5252fsxkewd9b5tvr4rt2t2vevwefx"timestamp="1540103830">161</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Bormashenko,E</author><author>Pogreb,R</author><author>Bormashenko,Y</author><author>Musin,A</author><author>Stein,T</author></authors></contributors><titles><title>Newinvestigationsonferrofluidics:ferrofluidicmarblesandmagnetic-field-drivendropsonsuperhydrophobicsurfaces</title><secondary-title>LangmuirtheAcsJournalofSurfaces&Colloids</secondary-title></titles><periodical><full-title>LangmuirtheAcsJournalofSurfaces&Colloids</full-title></periodical><pages>12119-22</pages><volume>24</volume><number>21</number><dates><year>2008</year></dates><urls></urls></record></Cite></EndNote>[11]，液体无损转移ADDINEN.CITE<EndNote><Cite><Author>Hong</Author><Year>2007</Year><RecNum>157</RecNum><DisplayText><styleface="superscript">[12]</style></DisplayText><record><rec-number>157</rec-number><foreign-keys><keyapp="EN"db-id="xts9zv5252fsxkewd9b5tvr4rt2t2vevwefx"timestamp="1540103424">157</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Hong,X.</author><author>Gao,X.</author><author>Jiang,L.</author></authors></contributors><titles><title>Applicationofsuperhydrophobicsurfacewithhighadhesiveforceinnolosttransportofsuperparamagneticmicrodroplet</title><secondary-title>JournaloftheAmericanChemicalSociety</secondary-title></titles><periodical><full-title>JournaloftheAmericanChemicalSociety</full-title></periodical><pages>1478-9</pages><volume>129</volume><number>6</number><dates><year>2007</year></dates><urls></urls></record></Cite></EndNote>[12]和生物技术等方面发挥着重大作用。影响固体表面浸润性的因素主要有（1）表面粗糙度（2）表面自由能。目前制备超疏水表面的方法主要有两类ADDINEN.CITE<EndNote><Cite><Author>Ma</Author><Year>2006</Year><RecNum>213</RecNum><DisplayText><styleface="superscript">[13]</style></DisplayText><record><rec-number>213</rec-number><foreign-keys><keyapp="EN"db-id="xts9zv5252fsxkewd9b5tvr4rt2t2vevwefx"timestamp="1541207684">213</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>MinglinMa</author><author>RandalM.Hill</author></authors></contributors><titles><title>Superhydrophobicsurfaces</title><secondary-title>CurrentOpinioninColloid&InterfaceScience</secondary-title></titles><periodical><full-title>CurrentOpinioninColloid&InterfaceScience</full-title></periodical><pages>193-202</pages><volume>11</volume><number>4</number><dates><year>2006</year></dates><urls></urls></record></Cite></EndNote>[13]：一、在粗糙表面上修饰低表面能物质；二、在低表面能物质上构造粗糙结构。并且，表面微观结构与化学成分的非均匀性同时影响表面的黏附性。而如何通过改变表面的微观结构或化学成分来制备不同黏附性的超疏水表面，是研究者主要解决的问题。本文基于超疏水表面研究的理论基础，采用一种化学腐蚀与热压剥离相结合的高黏附性超疏水表面制备方法，来获得绿色可控的高黏附超疏水金属表面及聚乙烯表面，进而探究其在微反应器及无损转移方面的具体应用。1.2表面润湿性理论基础1.2.1接触角目前，固体表面润湿性通常使用静态接触角进行表征。所谓静态接触角是指将液体滴在固体表面上，液滴在固体表面上形成热力学平衡时所持有的角，具体是指从固-液-气三相交叉点作气液界面的切线，此切线与固液交界线之间的夹角，它反应了固、液、气界面间表面张力平衡的结果。当液滴处于平衡状态时，三相接触线上存在着固、气、液界面间表面张力的平衡，通过对液滴在固体表面的受力分析，英国科学家T.YoungADDINEN.CITE<EndNote><Cite><Author>Young</Author><RecNum>136</RecNum><DisplayText><styleface="superscript">[14]</style></DisplayText><record><rec-number>136</rec-number><foreign-keys><keyapp="EN"db-id="xts9zv5252fsxkewd9b5tvr4rt2t2vevwefx"timestamp="1540099365">136</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Young,Thomas</author></authors></contributors><titles><title>AnEssayontheCohesionofFluids</title><secondary-title>PhilosophicalTransactionsoftheRoyalSocietyofLondon</secondary-title></titles><periodical><full-title>PhilosophicalTransactionsoftheRoyalSocietyofLondon</full-title></periodical><pages>65-87</pages><volume>95</volume><dates></dates><urls></urls></record></Cite></EndNote>[14]提出了Young’s方程（杨氏方程）：(1)其中，、、分别代表固-气、固-液、液-气界面的界面张力，为本征接触角。Young’s方程所对应的模型是理想化模型，要求固体表面是平滑、不变形，其组成均匀、各向同性的。当固体表面的静态接触角时，称为超亲水表面；静态接触角时称为超疏水表面。Young’s方程仅适用于固、液、气三相平衡接触的情况，根据公式（1），三个界面张力之间必须满足下列不等式：（2）否则，如果，则无法求出满足公式（1）的值，因此公式(1)也就不适用。图1固体表面上液滴的形状和接触角ADDINEN.CITE<EndNote><Cite><Author>景治娇</Author><Year>2015</Year><RecNum>194</RecNum><DisplayText><styleface="superscript">[15]</style></DisplayText><record><rec-number>194</rec-number><foreign-keys><keyapp="EN"db-id="xts9zv5252fsxkewd9b5tvr4rt2t2vevwefx"timestamp="1540108522">194</key></foreign-keys><ref-typename="Thesis">32</ref-type><contributors><authors><author>景治娇</author></authors></contributors><titles><title>黏附性可控超疏水表面的制备及其性能研究</title></titles><dates><year>2015</year></dates><publisher>西北师范大学</publisher><urls></urls></record></Cite></EndNote>[15]1.2.2接触角滞后静态接触角是衡量固体表面润湿性最常用的标准，但通过静态接触角去准确衡量具有实际应用价值的固体表面的润湿性是不确切的，还应该考虑水滴在固体表面的动态行为特征。因此，必须考虑液滴在微小力作用下的运动情况ADDINEN.CITE<EndNote><Cite><Author>And</Author><Year>2000</Year><RecNum>144</RecNum><DisplayText><styleface="superscript">[16,17]</style></DisplayText><record><rec-number>144</rec-number><foreign-keys><keyapp="EN"db-id="xts9zv5252fsxkewd9b5tvr4rt2t2vevwefx"timestamp="1540100363">144</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>And,DidemÖner</author><author>Mccarthy,ThomasJ.</author></authors></contributors><titles><title>UltrahydrophobicSurfaces.EffectsofTopographyLengthScalesonWettability</title><secondary-title>Langmuir</secondary-title></titles><periodical><full-title>Langmuir</full-title><abbr-1>Langmuir:theACSjournalofsurfacesandcolloids</abbr-1></periodical><pages>7777-7782</pages><volume>16</volume><number>20</number><dates><year>2000</year></dates><urls></urls></record></Cite><Cite><Author>And</Author><Year>2002</Year><RecNum>147</RecNum><record><rec-number>147</rec-number><foreign-keys><keyapp="EN"db-id="xts9zv5252fsxkewd9b5tvr4rt2t2vevwefx"timestamp="1540100922">147</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>And,P.Roura</author><author>Fort,J.</author></authors></contributors><titles><title>Commenton“EffectsoftheSurfaceRoughnessonSlidingAnglesofWaterDropletsonSuperhydrophobicSurfaces”</title><secondary-title>Langmuir</secondary-title></titles><periodical><full-title>Langmuir</full-title><abbr-1>Langmuir:theACSjournalofsurfacesandcolloids</abbr-1></periodical><pages>566-569</pages><volume>18</volume><number>2</number><dates><year>2002</year></dates><urls></urls></record></Cite></EndNote>[16,17]。所以，研究固体表面动态过程中的接触角：前进角、后退角和接触角滞后（又称迟滞角)就显得十分必要。由于实际固体表面是不均匀的，液体在表面上展开时需要克服一系列由于表面起伏而造成的自由能势垒ADDINEN.CITE<EndNote><Cite><Author>崔晓松</Author><Year>2010</Year><RecNum>167</RecNum><DisplayText><styleface="superscript">[15,18]</style></DisplayText><record><rec-number>167</rec-number><foreign-keys><keyapp="EN"db-id="xts9zv5252fsxkewd9b5tvr4rt2t2vevwefx"timestamp="1540105547">167</key></foreign-keys><ref-typename="Thesis">32</ref-type><contributors><authors><author>崔晓松</author></authors></contributors><titles><title>基于热力学分析的超疏水表面几何优化设计</title></titles><dates><year>2010</year></dates><publisher>湘潭大学</publisher><urls></urls></record></Cite><Cite><Author>景治娇</Author><Year>2015</Year><RecNum>194</RecNum><record><rec-number>194</rec-number><foreign-keys><keyapp="EN"db-id="xts9zv5252fsxkewd9b5tvr4rt2t2vevwefx"timestamp="1540108522">194</key></foreign-keys><ref-typename="Thesis">32</ref-type><contributors><authors><author>景治娇</author></authors></contributors><titles><title>黏附性可控超疏水表面的制备及其性能研究</title></titles><dates><year>2015</year></dates><publisher>西北师范大学</publisher><urls></urls></record></Cite></EndNote>[15,18]。当某一水滴静置于粗糙的固体表面上时，将少量的水填充到该液滴中，液滴变高，在固-液-气三相接触线不变的前提下，接触角会随着水滴体积的增加而变大，到达某一时刻时，三相接触线开始前进，此时的接触角称为前进角。相反，如果液滴被抽回时，液滴趋于平坦，在三相接触线不发生变化的时候，接触角会不断减小，某一时刻时三相接触线开始后退，此时的接触角称为后退角ADDINEN.CITE<EndNote><Cite><Author>景治娇</Author><Year>2015</Year><RecNum>194</RecNum><DisplayText><styleface="superscript">[15]</style></DisplayText><record><rec-number>194</rec-number><foreign-keys><keyapp="EN"db-id="xts9zv5252fsxkewd9b5tvr4rt2t2vevwefx"timestamp="1540108522">194</key></foreign-keys><ref-typename="Thesis">32</ref-type><contributors><authors><author>景治娇</author></authors></contributors><titles><title>黏附性可控超疏水表面的制备及其性能研究</title></titles><dates><year>2015</year></dates><publisher>西北师范大学</publisher><urls></urls></record></Cite></EndNote>[15]。接触角滞后定义为前进角与后退角的差值，表达式如下：（3）接触角滞后的程度代表了液体从固体表面脱离的难易程度。接触角滞后越大表明液体越难从固体表面脱离，而接触角滞后越小表明液体很容易从表面脱离ADDINEN.CITE<EndNote><Cite><Author>Wei</Author><Year>1999</Year><RecNum>159</RecNum><DisplayText><styleface="superscript">[19]</style></DisplayText><record><rec-number>159</rec-number><foreign-keys><keyapp="EN"db-id="xts9zv5252fsxkewd9b5tvr4rt2t2vevwefx"timestamp="1540103620">159</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Wei,Chen</author><author>Fadeev,AlexanderY.</author><author>Meng,CheHsieh</author><author>Öner,Didem</author><author>JeffreyYoungblood,And</author><author>Mccarthy,ThomasJ.</author></authors></contributors><titles><title>UltrahydrophobicandUltralyophobicSurfaces:SomeCommentsandExamples</title><secondary-title>Langmuir</secondary-title></titles><periodical><full-title>Langmuir</full-title><abbr-1>Langmuir:theACSjournalofsurfacesandcolloids</abbr-1></periodical><pages>3395</pages><volume>15</volume><number>10</number><dates><year>1999</year></dates><urls></urls></record></Cite></EndNote>[19]。影响接触角滞后的主要因素包括ADDINEN.CITE<EndNote><Cite><Author>章莉娟</Author><Year>2006</Year><RecNum>207</RecNum><DisplayText><styleface="superscript">[20]</style></DisplayText><record><rec-number>207</rec-number><foreign-keys><keyapp="EN"db-id="xts9zv5252fsxkewd9b5tvr4rt2t2vevwefx"timestamp="1540124777">207</key></foreign-keys><ref-typename="Book">6</ref-type><contributors><authors><author>章莉娟</author><author>郑忠</author></authors></contributors><titles><title>胶体与界面化学(第2版)</title></titles><dates><year>2006</year></dates><publisher>华南理工大学出版社</publisher><urls></urls></record></Cite></EndNote>[20]：(1)固体表面的粗糙形貌和粗糙度对接触角滞后有着很大的影响；(2)固体表面的不均匀性或测试体系多向性的滞后会影响接触角滞后的大小，液体前沿倾向于停止在相边界上，而相的交界处存在着能垒，前进角反应的是低表面能物质区，具有较大的本征接触角，后退角趋向于反应高表面能区，具有较小的本征接触角；(3)固体或液体表面的吸附使其表面受到污染，接触角发生显著地变化，从而引起接触角滞后现象。图2（a）前进角（b）后退角ADDINEN.CITE<EndNote><Cite><Author>Tian</Author><Year>2012</Year><RecNum>228</RecNum><DisplayText><styleface="superscript">[21]</style></DisplayText><record><rec-number>228</rec-number><foreign-keys><keyapp="EN"db-id="xts9zv5252fsxkewd9b5tvr4rt2t2vevwefx"timestamp="1588239553">228</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Tian,Shibing</author><author>Li,Lin</author><author>Sun,Wangning</author><author>Xia,Xiaoxiang</author><author>Han,Dong</author><author>Li,Junjie</author><author>Gu,Changzhi%JSciRep</author></authors></contributors><titles><title>Robustadhesionofflower-likefew-layergraphenenanoclusters</title></titles><pages>511</pages><volume>2</volume><dates><year>2012</year></dates><urls></urls></record></Cite></EndNote>[21]（c）滚动角ADDINEN.CITE<EndNote><Cite><Author>景治娇</Author><Year>2015</Year><RecNum>194</RecNum><DisplayText><styleface="superscript">[15]</style></DisplayText><record><rec-number>194</rec-number><foreign-keys><keyapp="EN"db-id="xts9zv5252fsxkewd9b5tvr4rt2t2vevwefx"timestamp="1540108522">194</key></foreign-keys><ref-typename="Thesis">32</ref-type><contributors><authors><author>景治娇</author></authors></contributors><titles><title>黏附性可控超疏水表面的制备及其性能研究</title></titles><dates><year>2015</year></dates><publisher>西北师范大学</publisher><urls></urls></record></Cite></EndNote>[15]1.2.3滚动角滚动角也是衡量固体表面润湿性的一个重要物理量。滚动角是指一定质量的水滴在倾斜表面受重力作用开始滚动时的临界角度。滚动角不仅和前进角、后退角有关，而且与液滴所受的重力也有一定的关系。1950年，BikermanADDINEN.CITE<EndNote><Cite><Author>Bikerman</Author><Year>1950</Year><RecNum>208</RecNum><DisplayText><styleface="superscript">[22]</style></DisplayText><record><rec-number>208</rec-number><foreign-keys><keyapp="EN"db-id="xts9zv5252fsxkewd9b5tvr4rt2t2vevwefx"timestamp="1540125064">208</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Bikerman,J.J.</author></authors></contributors><titles><title>Slidingofdropsfromsurfacesofdifferentroughnesses</title><secondary-title>JournalofColloidScience</secondary-title></titles><periodical><full-title>JOURNALoFCOLLOIDSCIENCE</full-title></periodical><pages>349-359</pages><volume>5</volume><number>4</number><dates><year>1950</year></dates><urls></urls></record></Cite></EndNote>[22]提出(4)其中是液滴所受的重力，是滚动角，是液滴的宽度，是水滴与固体接触的的表面张力，是一个常数，它取决于固体的润湿性和粗糙度。1960年，由KawasakiADDINEN.CITE<EndNote><Cite><Author>Kawasaki</Author><Year>1960</Year><RecNum>191</RecNum><DisplayText><styleface="superscript">[23]</style></DisplayText><record><rec-number>191</rec-number><foreign-keys><keyapp="EN"db-id="xts9zv5252fsxkewd9b5tvr4rt2t2vevwefx"timestamp="1540108264">191</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Kawasaki,Koji</author></authors></contributors><titles><title>Studyofwettabilityofpolymersbyslidingofwaterdrop</title><secondary-title>JournalofColloidScience</secondary-title></titles><periodical><full-title>JOURNALoFCOLLOIDSCIENCE</full-title></periodical><pages>402-407</pages><volume>15</volume><number>5</number><dates><year>1960</year></dates><urls></urls></record></Cite></EndNote>[23]导出（5）其中，为前进角，为后退角。1962年FurmidgeADDINEN.CITE<EndNote><Cite><Author>Furmidge</Author><Year>1962</Year><RecNum>196</RecNum><DisplayText><styleface="superscript">[24]</style></DisplayText><record><rec-number>196</rec-number><foreign-keys><keyapp="EN"db-id="xts9zv5252fsxkewd9b5tvr4rt2t2vevwefx"timestamp="1540109739">196</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Furmidge,C.G.L</author></authors></contributors><titles><title>Studiesatphaseinterfaces.I.Theslidingofliquiddropsonsolidsurfacesandatheoryforsprayretention</title><secondary-title>JournalofColloidScience</secondary-title></titles><periodical><full-title>JOURNALoFCOLLOIDSCIENCE</full-title></periodical><pages>309-324</pages><volume>17</volume><number>4</number><dates><year>1962</year></dates><urls></urls></record></Cite></EndNote>[24]重申这一方程，此后式（4）被通称为Furmidge方程。由式（4）中可知，液滴由于重力在与斜面水平的方向上的分力作用而滚落。实际情况下，不同的液滴的值不同，导致前进角、后退角及滚动角各自大小关系不同。所以仅通过接触角滞后来判断固体表面的超疏水性是不够的，滚动角更能准确评价出固体表面上液滴的滚动特征。通常，滚动角越大，说明固体表面对水滴的黏附性就越大，且常称滚动角大于的表面为高黏附性表面。1.2.4Wenzel状态Young’s方程的适用范围是平滑、组成均匀的理想表面，对于存在一定粗糙度的实际固体表面，考虑到粗糙度对表面浸润性的影响，需要对已有的接触模型进行改变。1936年，WenzelADDINEN.CITE<EndNote><Cite><Author>Wenzel</Author><Year>1949</Year><RecNum>152</RecNum><DisplayText><styleface="superscript">[25,26]</style></DisplayText><record><rec-number>152</rec-number><foreign-keys><keyapp="EN"db-id="xts9zv5252fsxkewd9b5tvr4rt2t2vevwefx"timestamp="1540102597">152</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Wenzel,RobertN.</author></authors></contributors><titles><title>SurfaceRoughnessandContactAngle</title><secondary-title>JournalofPhysical&ColloidChemistry</secondary-title></titles><periodical><full-title>JournalofPhysical&ColloidChemistry</full-title></periodical><pages>1466-1467</pages><volume>53</volume><number>9</number><dates><year>1949</year></dates><urls></urls></record></Cite><Cite><Author>Wenzel</Author><Year>1936</Year><RecNum>198</RecNum><record><rec-number>198</rec-number><foreign-keys><keyapp="EN"db-id="xts9zv5252fsxkewd9b5tvr4rt2t2vevwefx"timestamp="1540110211">198</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Wenzel,RobertN.</author></authors></contributors><titles><title>RESISTANCEOFSOLIDSURFACESTOWETTINGBYWATER</title><secondary-title>Ind.eng.chem</secondary-title></titles><periodical><full-title>Ind.eng.chem</full-title></periodical><pages>988-994</pages><volume>28</volume><number>8</number><dates><year>1936</year></dates><urls></urls></record></Cite></EndNote>[25,26]首次提出在进行表面润湿性评估时应该考虑表面粗糙度这一重要参数的影响。他由此建立了Wenzel模型，如图3（a），并提出当液体与固体表面接触时，液体能够填充满粗糙表面上的凹陷部分，形成湿接触。此外，Wenzel对Young’s方程进行了进一步的修正，如下：(6)该方程也可简化为：(7)（7）式中，代表粗糙表面的平衡接触角（即表观接触角），代表理想表面的本征接触角。为实际的固-液界面接触面积与表观固-液界面接触面积之比（即粗糙度）。式(7)的成立必须满足两个基本假设：(1)材料的表面粗糙程度与液滴的尺寸相比可忽略不计：(2)材料表面的几何形状不影响其表面积的大小。由于粗糙因子总大于1，从Wenzel方程式中可以看出：（1）时，随着表面粗糙度的增加而降低，表面变的更亲液；（2）时，随着表面粗糙度的增加而增大，表面变的更疏液。图3液体与粗糙表面的理论接触模型（a）Wenzel态（b）过渡态（c）Cassie态ADDINEN.CITE<EndNote><Cite><Author>景治娇</Author><Year>2015</Year><RecNum>194</RecNum><DisplayText><styleface="superscript">[15]</style></DisplayText><record><rec-number>194</rec-number><foreign-keys><keyapp="EN"db-id="xts9zv5252fsxkewd9b5tvr4rt2t2vevwefx"timestamp="1540108522">194</key></foreign-keys><ref-typename="Thesis">32</ref-type><contributors><authors><author>景治娇</author></authors></contributors><titles><title>黏附性可控超疏水表面的制备及其性能研究</title></titles><dates><year>2015</year></dates><publisher>西北师范大学</publisher><urls></urls></record></Cite></EndNote>[15]1.2.5Cassie状态Cassie和BaxterADDINEN.CITE<EndNote><Cite><Author>Cassie</Author><Year>1944</Year><RecNum>214</RecNum><DisplayText><styleface="superscript">[27]</style></DisplayText><record><rec-number>214</rec-number><foreign-keys><keyapp="EN"db-id="xts9zv5252fsxkewd9b5tvr4rt2t2vevwefx"timestamp="1541208101">214</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Cassie,A.B.D.</author><author>Baxter,S.</author></authors></contributors><titles><title>Wettabilityofporoussurfaces</title><secondary-title>Tra