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1、会计学1材料物理材料物理(wl)实用实用第一页，共33页。What is polymer solution?Why to study polymer solution?HOW to study polymer solution?3 Questions第1页/共33页第二页，共33页。WWhat is polymer solution?TraditionalCover第2页/共33页第三页，共33页。WWhy to study polymer solution?Study Best method on investigation of a single polymerApplictionsBon
2、dDopeFilaturePlastic enhancedBlend第3页/共33页第四页，共33页。HOW W to study polymer solution?Polymer solution processPolymer solution processHow to select a solventHow to select a solventSolution stateSolution state：Interaction Interaction solution and separate solution and separateSolution thermodynamicsSolu
3、tion thermodynamics第4页/共33页第五页，共33页。Josiah Willard Gibbs(1839-1903)Gibbs 方程(fngchng)G=H-TSInsluable，Phase Seperate 状态(zhungti)第5页/共33页第六页，共33页。Key points for polymer dissolvingKey points for polymer dissolvingLinear polymersSwelling to solutionCross-linked polymersOnly swellingCrystalline polymersMe
4、lting to solution第6页/共33页第七页，共33页。Solvent selectionSimilar dissolve mutually theory PolarityPolarityNon-PolarityNon-Polarity第7页/共33页第八页，共33页。(2)Similar solubility parameterSimilar solubility parameterGibbs free energy 自由(zyu)能Enthalpy 焓Entropy 熵Condition of solutionDuring solution processSolubility
5、parameter =1/2=CED Cohesive energy density第8页/共33页第九页，共33页。Therefore HM is the key(a)Polar polymer to polar solvent，HM 0,Solution is depended on the comparison of HM and T SM.HM T SM,Soluble。HM need be more little。第9页/共33页第十页，共33页。Hildebrand equation 1,2 Volume fraction of Solvent and polymer,respec
6、tively.1,2 Solubility parameter fraction of Solvent and polymer,respectively.VM Volume after blending Hildebrand J.,Scott R.L.,Solubility of Nonelectrolytes,Reinhold Publishing Corporation,New York,Chapter 7(1949)第10页/共33页第十一页，共33页。In general,Polymer is insolubleHildebrand function is good for non-o
7、r weak polar polymerFor polar polymer,Hansen公式公式(gngsh):Blend solvent：第11页/共33页第十二页，共33页。How to get How to get?=1/2=第12页/共33页第十三页，共33页。(a)Swelling methoda)Swelling methoda)Swelling methoda)Swelling method：Cross-linked polymer is dissolved in different solvents.The Cross-linked polymer is dissolved i
8、n different solvents.The of the solvent with the of the solvent with the largest swelling volume is the largest swelling volume is the of polymer.of polymer.第13页/共33页第十四页，共33页。(b)Viscoelasticity methodb)Viscoelasticity methodPolymer is dissolved in different solvents.The of the solvent with the larg
9、est solution viscoelasticity is the of polymer.第14页/共33页第十五页，共33页。聚合物各结构聚合物各结构(jigu)基团的摩基团的摩尔引力常数尔引力常数重复重复(chngf)单元的摩尔体单元的摩尔体积积(c)Calculationc)CalculationPMMA269303.465.6668.2303.4F=269+65.6+668.2+303.4*2=1609.6V=M/=(5C+2O+8H)/1.19=100/1.19第15页/共33页第十六页，共33页。statusGood solventBad solvent“Polymer-Sol
10、vent interaction factor 1 Si第19页/共33页第二十页，共33页。Flory-Hunggins Theory(Mean-field theory)Analogous to regular solution in alloysA-B alloysPolymer solution第20页/共33页第二十一页，共33页。Three Hypotheses Three Hypotheses 三点三点三点三点(sn di(sn di n)n)假设假设假设假设1.Polymer in solution is arranged like crystal.2.Polymer is f
11、lexible。3.Chains of polymer is dissolved uniformly 。第21页/共33页第二十二页，共33页。Dissolving processPolymer entityPolymer disorientationSolventPolymer SolutionSdisorientationSsolventSdisorientation第22页/共33页第二十三页，共33页。（5）-state（状态状态(zhungti)）Similar to ideal solution Condition-状态(zhungti)第23页/共33页第二十四页，共33页。（6
12、）Discussion of Hunggins parameterChemical potentialMore stableGood solvent良溶剂良溶剂(rngj)Chemical potentialNot stableBad solvent劣溶剂劣溶剂(rngj)第24页/共33页第二十五页，共33页。Phase equilibrium of polymer solutionPhase equilibrium of polymer solutionOsmotic pressure SolutionSolventSemipermeable membrane 半透膜：允许(ynx)小分子
13、通过，不允许(ynx)大分子通过。第25页/共33页第二十六页，共33页。What is the physical meaning of the second Virial coefficient A2?Molar volume of solventDensity of solute第26页/共33页第二十七页，共33页。What we can get from the following equation?(2)A2 Second Virial coefficientIntercept=Slope coefficient=Interceptslope(1)Number average mol
14、ecular weight Mn第27页/共33页第二十八页，共33页。Discussion of A2 status良溶剂良溶剂(rngj)劣溶剂劣溶剂(rngj)A2=0A20A20Huggins parameterStatusSecond Virial coefficient第28页/共33页第二十九页，共33页。Discussion of the plot(a)Add bad solvent into good solvent(b)Decrease temperature solvent temperature第29页/共33页第三十页，共33页。StableStable,metast
15、ablemetastable and and non-stablenon-stable regions regions GM can be substituted by 1 and TemperatureCritical point第30页/共33页第三十一页，共33页。Different phase equilibrium diagramsPhase separation and dissolution are controlled by three variables:temperature,pressure,and concentration.LCST-Low critical solvency temperatureUCST-Ultra critical solvency temperature第31页/共33页第三十二页，共33页。Typical polymer-solution Typical polymer-solution phase equilibrium diagramphase equilibrium diagramWeak concentrationHigh concentrationCharacteristic-Non-symmetrye.g.PVC raincoat,using plasticizer 第32页/共33页第三十三页，共33页。