超声波表征聚合物PVT性能及相关理论研究
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摘要
聚合物压力-比容-温度（P-V-T）关系直接影响着聚合物的生产、加工以及应用，掌握其基本规律并发展可工程化应用的检测技术十分重要。常规检测方法难以应用于工程实际，发展方便适用的无损在线检测方法前景广阔。本文应用超声波检测方法表征聚合物PVT，基于定量理论推导和实验数据拟合的分析建立了具体表征方法。
本文在稳态条件下同步测量聚合物PVT数据与超声波信号数据，通过分析实验数据，归纳了聚合物比容与超声波声速之间的定量关系；联系聚合物状态方程理论，应用Tait经验方程、Flory-Orwoll-Vrij自由体积模型（FOV方程）、Prigogine方阱胞腔模型（CM方程）、Dee-Walsh修正胞腔模型（MCM方程）、Sanchez-Lacombe格子流体模型（SL方程）和Hartmann-Haque模型（HH方程）等6个状态方程研究了共混组分与填充份数对状态方程参数的影响。
（1）以结晶聚合物高密度聚乙烯（HDPE）为例分析了聚合物PVT曲线与超声波信号曲线之间的关系，结果表明PVT曲线的突变与超声波振幅的极值和超声波声速的突变相对应，同时接近DSC曲线的吸热峰峰值T_m，此外，对比聚合物PVT曲线和超声波声速曲线发现二者相似，因此可由超声波声速来定量描述聚合物比容。同时，其它单组份聚合物（PP、PS）和聚合物共混体系（PP/HDPE）及聚合物填充体系（PP/CaCO_3）也具有类似的性质。
（2）对实验数据进行数值拟合，获得了三类材料体系状态方程的参数；分析了聚合物共混体系组成和聚合物填充体系填充份数对其传递超声波信号以及状态方程参数的影响，结果也显示出一定的规律性；超声波信号以及状态方程参数均可以定性描述聚合物共混体系的相容性。
（3）通过对实验数据的分析得到了5组定量描述三类材料体系超声波声速与聚合物比容的关系式。比较5个方程（组）发现方程V=c~(-1/3).F~(-7/6)很好的适用于各类材料体系，并且F值与填充份数呈现线性变化。
Pressure, volume and temperature (P-V-T) has a direct impact on theproduction, processing and application of polymers. It is very significantto understand the basic rules and to develop the on-line detection wayswhich can be used in industry. Conventional methods are difficult to beapplied to actual projects, non-destructive online detection exhibits broadprospects. In this paper, ultrasonic testing method was used tocharacterize polymer PVT. Specific characterization methods wereobtained on quantitative models and experimental data-fitted relations.
In this article, the polymer PVT data and the ultrasonic signal dataare simultaneously measured under steady state conditions. Thequantitative relationship between specific volume and ultrasonic velocityare summarized after analyzing the experimental data. Through Taitempirical equation, the Flory-Orwoll-Vrij model (FOV equation),Prigogine "square well" cell model (CM equation), Dee and Walsh modified cell model (MCM equations), Sanchez-Lacombe lattice-fluidmodel (SL equation), and the Hartmann-Haque model (HH equations),the effects of polymer structure, blend component and filler content onthe transferred ultrasonic signals and parameters’ value state equation.
(1) Crystalline high-density polyethylene (HDPE) was used as anexample to analyze the relationship between polymer PVT and ultrasonicsignals. It was shown that transition temperature of PVT curvecorresponds with the extreme values of ultrasonic amplitude and velocitywhich is close to the endothermic peak (T_m) of its DSC curve. The shapeof specific volume curve is similar to that of ultrasonic velocity curveillustrating that the latter can quantatively describe specific volume.This fact is also fitful to polymer blends (PP/HDPE) and polymer-filledsystem (PP/CaCO_3).
(2) The parameter’s values of state equation were calculated for thethree types of material systems by numerical fitting experimental data.The influences of composition for polymer blends and that of fillercontent for polymer-filled system on the ultrasonic signals and theequation of state parameters were analyzed showing certain regularity.Both of ultrasonic signal and the equation of state parameters can wellreflect the compatibility of polymer blends.
(3) Five sets of equations were developed to quantitatively describethe relations between ultrasonic velocity and specific volume for three types of complex polymer materials. Their comparison told thatV=c~(-1/3).F~(-7/6) is applicable to all materials when F-value varies linearlywith filler content.
本文在稳态条件下同步测量聚合物PVT数据与超声波信号数据，通过分析实验数据，归纳了聚合物比容与超声波声速之间的定量关系；联系聚合物状态方程理论，应用Tait经验方程、Flory-Orwoll-Vrij自由体积模型（FOV方程）、Prigogine方阱胞腔模型（CM方程）、Dee-Walsh修正胞腔模型（MCM方程）、Sanchez-Lacombe格子流体模型（SL方程）和Hartmann-Haque模型（HH方程）等6个状态方程研究了共混组分与填充份数对状态方程参数的影响。
（1）以结晶聚合物高密度聚乙烯（HDPE）为例分析了聚合物PVT曲线与超声波信号曲线之间的关系，结果表明PVT曲线的突变与超声波振幅的极值和超声波声速的突变相对应，同时接近DSC曲线的吸热峰峰值T_m，此外，对比聚合物PVT曲线和超声波声速曲线发现二者相似，因此可由超声波声速来定量描述聚合物比容。同时，其它单组份聚合物（PP、PS）和聚合物共混体系（PP/HDPE）及聚合物填充体系（PP/CaCO_3）也具有类似的性质。
（2）对实验数据进行数值拟合，获得了三类材料体系状态方程的参数；分析了聚合物共混体系组成和聚合物填充体系填充份数对其传递超声波信号以及状态方程参数的影响，结果也显示出一定的规律性；超声波信号以及状态方程参数均可以定性描述聚合物共混体系的相容性。
（3）通过对实验数据的分析得到了5组定量描述三类材料体系超声波声速与聚合物比容的关系式。比较5个方程（组）发现方程V=c~(-1/3).F~(-7/6)很好的适用于各类材料体系，并且F值与填充份数呈现线性变化。
Pressure, volume and temperature (P-V-T) has a direct impact on theproduction, processing and application of polymers. It is very significantto understand the basic rules and to develop the on-line detection wayswhich can be used in industry. Conventional methods are difficult to beapplied to actual projects, non-destructive online detection exhibits broadprospects. In this paper, ultrasonic testing method was used tocharacterize polymer PVT. Specific characterization methods wereobtained on quantitative models and experimental data-fitted relations.
In this article, the polymer PVT data and the ultrasonic signal dataare simultaneously measured under steady state conditions. Thequantitative relationship between specific volume and ultrasonic velocityare summarized after analyzing the experimental data. Through Taitempirical equation, the Flory-Orwoll-Vrij model (FOV equation),Prigogine "square well" cell model (CM equation), Dee and Walsh modified cell model (MCM equations), Sanchez-Lacombe lattice-fluidmodel (SL equation), and the Hartmann-Haque model (HH equations),the effects of polymer structure, blend component and filler content onthe transferred ultrasonic signals and parameters’ value state equation.
(1) Crystalline high-density polyethylene (HDPE) was used as anexample to analyze the relationship between polymer PVT and ultrasonicsignals. It was shown that transition temperature of PVT curvecorresponds with the extreme values of ultrasonic amplitude and velocitywhich is close to the endothermic peak (T_m) of its DSC curve. The shapeof specific volume curve is similar to that of ultrasonic velocity curveillustrating that the latter can quantatively describe specific volume.This fact is also fitful to polymer blends (PP/HDPE) and polymer-filledsystem (PP/CaCO_3).
(2) The parameter’s values of state equation were calculated for thethree types of material systems by numerical fitting experimental data.The influences of composition for polymer blends and that of fillercontent for polymer-filled system on the ultrasonic signals and theequation of state parameters were analyzed showing certain regularity.Both of ultrasonic signal and the equation of state parameters can wellreflect the compatibility of polymer blends.
(3) Five sets of equations were developed to quantitatively describethe relations between ultrasonic velocity and specific volume for three types of complex polymer materials. Their comparison told thatV=c~(-1/3).F~(-7/6) is applicable to all materials when F-value varies linearlywith filler content.
引文
[1]郭齐建,何雪涛,杨为民.注射成型CAE与聚合物P-V-T的测试[J].塑料科技,2004,4:21~23
[2]何波兵.超声技术在聚合物形态结构表征及注射成型过程在线检测中应用的基础研究[D].四川大学博士学位论文,2006,4:1~111
[3]蔡小舒,苏明旭,沈建琪.颗粒测量技术及应用[D].北京:化学工业出版社,2010,9:171~218
[4]何方成,宫兆斌.超声波声速测量技术及其在材料评价中的应用[J].材料工程,2003,8:32~34
[5] S.-S.L. Wen, C.K. Jen, K.T. Nguyen. Advances in On-line Monitoring of the InjectionMolding Process Using Ultrasonic Technique [J]. Int’l Polymer Processing,1999, vol.XIV,175~182
[6] Mingwen Jiang. Ultrasonic Monitoring of Polymer State during Injection MoldingProcessing [D]. The University of Utah.1998
[7]许菲.注射压缩精密成型原理研究[D].北京化工大学硕士研究生毕业论文,2010,4:37~60
[8]杨剑,徐婷,安立佳,董丽松,滕凤恩.高聚物及其共混物p-V-T特性的研究进展[J].高分子材料科学与工程,2001,3,17(2):10~15
[9] Michael Hess. The Use of Pressure-Volume-Temperature Measurements in PolymerScience[J]. Macromol. Symp,2004,214:361~379
[10]王建,杨为民,谢鹏程,舒晖翔.聚合物PVT关系在线测试技术[J].塑料工业,2008,10:28~30
[11]孙昭艳,杨剑,安立佳,姜振华. PE线胀系数、等温压缩率和压力系数的测定[J].工程塑料应用,1999,27(6):21~25
[12] Dan Vladimir Nichita, Perveiz Khalid, Daniel Broseta. Calculation of isentropiccompressibility and sound velocity in two-phase fluids[J]. Fluid Phase Equilibria,2010,291:95~102
[13]张巍巍,袁强,孙昭艳,安立佳,李东风.无规共聚聚丙烯的热膨胀系数和等温压缩系数的测定[J].应用化学,2004,8,21(8):757~761
[14]张颖,袁强,杨剑,孙昭艳,姜伟,安立佳.薄膜用聚丙烯树脂熔融态PVT行为的研究[J].高分子学报,2002,8,4:467~471
[15]应继儒,解孝林,孙昭艳,彭少贤. PP／POE共混物的P-V-T属性及压力对结晶温度的影响[J].高等学校化学学报,2009,2,30(2):422~426
[16] P. ZOLLER, H. H. HOEHN. Pressure-Volume-Temperature properties of Blends ofPoly(2,6-dimethyl-1,4-phenylene Ether) with Polystyrene[J]. Journal of Polymer Science:Polymer Physics Edition,1982,20:1385~1397
[17] L. A. Utrack, R. Simha. Pressure-Volume-Temperature Dependence ofPolypropylene/Organoclay Nanocomposites [J]. Macromolecules,2004,37:10123~10133
[18]陈新志,蔡振云,胡望明.化工热力学（第二版）[M].北京:化学工业出版社,2005,8:12~13
[19]吕宏凌,王保国,杨基础.用Sanchez-Lacombe状态方程改进高分子-溶剂体系扩散系数模型[J].高分子材料科学与工程,2007,5,23(3):203~206
[20]吕宏凌,王保国,杨基础.用Simha-Somcynsky状态方程改进高分子中溶剂扩散系数模型[J].化工学报,2006,7,57(7):1513~1517
[21]祝铁丽,王敏杰.用于非稳态过程计算的高聚物p-v-T状态方程[J].高分子材料科学与工程,2002,11,18(6):89~93
[22] Y. X. YI, P. ZOLLER. An Experimental and Theoretical Study of the PVT Equation ofState of Butadiene and Isoprene Elastomers to200℃and200MPa[J]. Polymer Science:Part B: Polymer Physics,1993,31:779~788
[23] V. K. SACHDEV, R. K. JAIN. Equation of State for High Density Solid and MeltPolyethylene[J]. Polymer Science: Part B: Polymer Physics,2005,43:1618–1623
[24]王建.基于注塑装备的聚合物PVT关系测控技术的研究[D].北京化工大学博士研究生学位论文,2010,5:1~120
[25]童景山,于养信,高光华.基于胞腔模型和无热溶液理论推导超额热力学函数和液相活度系数方程[J].天然气化工,1994,19(6):50~53
[26] B.Rudolf, J.Kressler, K.Shimomai, T.Ougizawa, T.Ittotie. Evaluation of equation-of-stateparameters from PVT data[J]. Acta Polymer,1995,46:312-318
[27]唐萍,李光宪. Flory状态方程理论研究PS/PMMA/SAN相行为[J].高等学校化学学报,2000,1:136~139
[28] PATRICK A. RODCERS. Pressure-Volume-Temperature Relationships for Polymericliquids: A Review of Equations of State and Their Characteristic Parameters for56Polymers[J]. Journal of Applied Polymer Science,1993,48:1061~1080
[29]Hiroshi Machida, Ryosuke Taguchi, Yoshiyuki Sato, Richard L. Smith Jr. Analysis ofionic liquid PVT behavior with a Modified Cell Model[J]. Fluid Phase Equilibria,2009,281:127~132
[30]徐婷,杨剑,安立佳,姬相玲,姜炳政.利用pVT分析仪测定交联PEG的热膨胀系数、等温压缩系数和热压系数[J].高分子材料科学与工程,2001,1,17(1):117~120
[31] Ryan A. Krenz, Torben Laursen, Robert A. Heidemann. The Modified Sanchez-LacombeEquation of State Applied to Polydisperse Polyethylene Solutions[J]. General Research,2009,48:10664~10681
[32] Qingping Guo, Chul B. Park, Xiang Xu and Jin Wang. Relationship of Fractional FreeVolumes Derived from the Equations of State (EOS) and the Doolittle Equation[J]. Journalof Cellular Plastics,2007,1,43:69~82
[33]应继儒. PP/POE共混体系的微结构与性能[D].华中科技大学博士学位论文,2008,8:82~108
[34] Khashayar Nasrifar. Comparative study of eleven equations of state in predicting thethermodynamic properties of hydrogen[J]. International Journal of Hydrogen Energy,2010,35:3802~3811
[35] Bruce Hartmann, Mustafa A. Haque. Equation of state for polymer solids[J]. J. Appl.Phys.,1985,11,58(8):2831~2836
[36]仲崇立,汪文川,卢焕章,陈效宁.基团贡献法确定简化空穴理论状态方程的分子参数[J].高校化工工程学报,1995,9,9(3):209~214
[37] L.A. Utracki. PVT of amorphous and crystalline polymers and their nanocomposites [J].Polymer Degradation and Stability,2010,95:411~421
[38]肖国军,史济斌,刘国杰.液态聚合物的内压与状态方程[J].化工学报,2004,4,55(4):526~530
[39] B.Rudolf, J.Kressler, K.Shimomai, T.Ougizawa, T.Ittotie. Evaluation of equation-of-stateparameters from PVT data[J]. Acta Polymer,1995,46:312~318
[40]李宏飞,蒙延峰,霍红,蒋世春,安丽佳.压力对高分子液-液相转变行为的影响[J].科学通报,2005,4,50(7):613~622
[41] V.S. Parekh, R.P. Danner. J. Polym. Sci.[J]1995,33(B):395~402
[42] Yoshiyuki Sato, Hajime Hashiguchi, Shigeki Takishima, Hirokatsu Masuoka. Predictionof PVT properties of polymer melts with a new group-contribution equation of state[J].Fluid Phase Equilibria,1998,144:427–440
[43]杨为民,丁玉梅,谢鹏程.注射成型新技术[M].北京:化学工业出版社,2008:420~456
[44] Thomas C.L., Adebo A.O., Bur A.J.. Ultrasonic measurement of polymer materialproperties during injection molding[J]. ANTEC Conference Proceedings, SPE,1994:2236~2237
[45] Thomas C.L., Jiang Mingwen, Chen Chichang, etc. Ultrasonic instrument for PVTcharacterization of Polymer[J]. ANTEC Conference Proceedings, SPE,1995:2707~2714
[46] J.G. Kim, H. Kim, H.S. Kim, etc. Investigation of pressure-volume-temperatuer relationby ultrasonic techinque and its application for the quality prediction of injection moldedprats[J]. Korea-Australia Rheology Journal.2004,16(4):163~168
[2]何波兵.超声技术在聚合物形态结构表征及注射成型过程在线检测中应用的基础研究[D].四川大学博士学位论文,2006,4:1~111
[3]蔡小舒,苏明旭,沈建琪.颗粒测量技术及应用[D].北京:化学工业出版社,2010,9:171~218
[4]何方成,宫兆斌.超声波声速测量技术及其在材料评价中的应用[J].材料工程,2003,8:32~34
[5] S.-S.L. Wen, C.K. Jen, K.T. Nguyen. Advances in On-line Monitoring of the InjectionMolding Process Using Ultrasonic Technique [J]. Int’l Polymer Processing,1999, vol.XIV,175~182
[6] Mingwen Jiang. Ultrasonic Monitoring of Polymer State during Injection MoldingProcessing [D]. The University of Utah.1998
[7]许菲.注射压缩精密成型原理研究[D].北京化工大学硕士研究生毕业论文,2010,4:37~60
[8]杨剑,徐婷,安立佳,董丽松,滕凤恩.高聚物及其共混物p-V-T特性的研究进展[J].高分子材料科学与工程,2001,3,17(2):10~15
[9] Michael Hess. The Use of Pressure-Volume-Temperature Measurements in PolymerScience[J]. Macromol. Symp,2004,214:361~379
[10]王建,杨为民,谢鹏程,舒晖翔.聚合物PVT关系在线测试技术[J].塑料工业,2008,10:28~30
[11]孙昭艳,杨剑,安立佳,姜振华. PE线胀系数、等温压缩率和压力系数的测定[J].工程塑料应用,1999,27(6):21~25
[12] Dan Vladimir Nichita, Perveiz Khalid, Daniel Broseta. Calculation of isentropiccompressibility and sound velocity in two-phase fluids[J]. Fluid Phase Equilibria,2010,291:95~102
[13]张巍巍,袁强,孙昭艳,安立佳,李东风.无规共聚聚丙烯的热膨胀系数和等温压缩系数的测定[J].应用化学,2004,8,21(8):757~761
[14]张颖,袁强,杨剑,孙昭艳,姜伟,安立佳.薄膜用聚丙烯树脂熔融态PVT行为的研究[J].高分子学报,2002,8,4:467~471
[15]应继儒,解孝林,孙昭艳,彭少贤. PP／POE共混物的P-V-T属性及压力对结晶温度的影响[J].高等学校化学学报,2009,2,30(2):422~426
[16] P. ZOLLER, H. H. HOEHN. Pressure-Volume-Temperature properties of Blends ofPoly(2,6-dimethyl-1,4-phenylene Ether) with Polystyrene[J]. Journal of Polymer Science:Polymer Physics Edition,1982,20:1385~1397
[17] L. A. Utrack, R. Simha. Pressure-Volume-Temperature Dependence ofPolypropylene/Organoclay Nanocomposites [J]. Macromolecules,2004,37:10123~10133
[18]陈新志,蔡振云,胡望明.化工热力学（第二版）[M].北京:化学工业出版社,2005,8:12~13
[19]吕宏凌,王保国,杨基础.用Sanchez-Lacombe状态方程改进高分子-溶剂体系扩散系数模型[J].高分子材料科学与工程,2007,5,23(3):203~206
[20]吕宏凌,王保国,杨基础.用Simha-Somcynsky状态方程改进高分子中溶剂扩散系数模型[J].化工学报,2006,7,57(7):1513~1517
[21]祝铁丽,王敏杰.用于非稳态过程计算的高聚物p-v-T状态方程[J].高分子材料科学与工程,2002,11,18(6):89~93
[22] Y. X. YI, P. ZOLLER. An Experimental and Theoretical Study of the PVT Equation ofState of Butadiene and Isoprene Elastomers to200℃and200MPa[J]. Polymer Science:Part B: Polymer Physics,1993,31:779~788
[23] V. K. SACHDEV, R. K. JAIN. Equation of State for High Density Solid and MeltPolyethylene[J]. Polymer Science: Part B: Polymer Physics,2005,43:1618–1623
[24]王建.基于注塑装备的聚合物PVT关系测控技术的研究[D].北京化工大学博士研究生学位论文,2010,5:1~120
[25]童景山,于养信,高光华.基于胞腔模型和无热溶液理论推导超额热力学函数和液相活度系数方程[J].天然气化工,1994,19(6):50~53
[26] B.Rudolf, J.Kressler, K.Shimomai, T.Ougizawa, T.Ittotie. Evaluation of equation-of-stateparameters from PVT data[J]. Acta Polymer,1995,46:312-318
[27]唐萍,李光宪. Flory状态方程理论研究PS/PMMA/SAN相行为[J].高等学校化学学报,2000,1:136~139
[28] PATRICK A. RODCERS. Pressure-Volume-Temperature Relationships for Polymericliquids: A Review of Equations of State and Their Characteristic Parameters for56Polymers[J]. Journal of Applied Polymer Science,1993,48:1061~1080
[29]Hiroshi Machida, Ryosuke Taguchi, Yoshiyuki Sato, Richard L. Smith Jr. Analysis ofionic liquid PVT behavior with a Modified Cell Model[J]. Fluid Phase Equilibria,2009,281:127~132
[30]徐婷,杨剑,安立佳,姬相玲,姜炳政.利用pVT分析仪测定交联PEG的热膨胀系数、等温压缩系数和热压系数[J].高分子材料科学与工程,2001,1,17(1):117~120
[31] Ryan A. Krenz, Torben Laursen, Robert A. Heidemann. The Modified Sanchez-LacombeEquation of State Applied to Polydisperse Polyethylene Solutions[J]. General Research,2009,48:10664~10681
[32] Qingping Guo, Chul B. Park, Xiang Xu and Jin Wang. Relationship of Fractional FreeVolumes Derived from the Equations of State (EOS) and the Doolittle Equation[J]. Journalof Cellular Plastics,2007,1,43:69~82
[33]应继儒. PP/POE共混体系的微结构与性能[D].华中科技大学博士学位论文,2008,8:82~108
[34] Khashayar Nasrifar. Comparative study of eleven equations of state in predicting thethermodynamic properties of hydrogen[J]. International Journal of Hydrogen Energy,2010,35:3802~3811
[35] Bruce Hartmann, Mustafa A. Haque. Equation of state for polymer solids[J]. J. Appl.Phys.,1985,11,58(8):2831~2836
[36]仲崇立,汪文川,卢焕章,陈效宁.基团贡献法确定简化空穴理论状态方程的分子参数[J].高校化工工程学报,1995,9,9(3):209~214
[37] L.A. Utracki. PVT of amorphous and crystalline polymers and their nanocomposites [J].Polymer Degradation and Stability,2010,95:411~421
[38]肖国军,史济斌,刘国杰.液态聚合物的内压与状态方程[J].化工学报,2004,4,55(4):526~530
[39] B.Rudolf, J.Kressler, K.Shimomai, T.Ougizawa, T.Ittotie. Evaluation of equation-of-stateparameters from PVT data[J]. Acta Polymer,1995,46:312~318
[40]李宏飞,蒙延峰,霍红,蒋世春,安丽佳.压力对高分子液-液相转变行为的影响[J].科学通报,2005,4,50(7):613~622
[41] V.S. Parekh, R.P. Danner. J. Polym. Sci.[J]1995,33(B):395~402
[42] Yoshiyuki Sato, Hajime Hashiguchi, Shigeki Takishima, Hirokatsu Masuoka. Predictionof PVT properties of polymer melts with a new group-contribution equation of state[J].Fluid Phase Equilibria,1998,144:427–440
[43]杨为民,丁玉梅,谢鹏程.注射成型新技术[M].北京:化学工业出版社,2008:420~456
[44] Thomas C.L., Adebo A.O., Bur A.J.. Ultrasonic measurement of polymer materialproperties during injection molding[J]. ANTEC Conference Proceedings, SPE,1994:2236~2237
[45] Thomas C.L., Jiang Mingwen, Chen Chichang, etc. Ultrasonic instrument for PVTcharacterization of Polymer[J]. ANTEC Conference Proceedings, SPE,1995:2707~2714
[46] J.G. Kim, H. Kim, H.S. Kim, etc. Investigation of pressure-volume-temperatuer relationby ultrasonic techinque and its application for the quality prediction of injection moldedprats[J]. Korea-Australia Rheology Journal.2004,16(4):163~168