Neutron spin echo spectroscopy of entangled polymer melts [M. Zamponi, et al. J. Phys. Chem. B2008,112, 16220], and of tracer diffusion of short polymer chains in highly entangled polymer melt [M. Zamponi et al. Phys. Rev. Lett. 2021, 126, 187801.] and [M. Kruteva et al. Macromolecules2021, 54, 11384] found the center-of-mass mean-square displacements at shorter times are subdiffusive, heterogeneous, non-Gaussian, and cooperative. These properties contradict the assumption of reptation within the tube in the tube-reptation (TR) model, but are in accord with the predictions from the many-chain cooperative dynamics in the theory of Guenza. The inadequacy of the TR model revealed by the microscopic experiments and theory motivates the author to reexamine previously published data of diffusion of entangled polymer chains from experiments and simulations used to test the TR model. The results reported in this study lead to the conclusion that the key predictions of the TR model are at variance with experimental and simulation data. The cause lies in the reptation hypothesis contradicting the cooperative nature of entangled chain diffusion proven by its dynamics being isomorphic to cooperative diffusion in other materials. The Coupling Model has predictions consistent with the cooperative diffusion properties in interacting materials [Prog. Mater. Sci., 2023,139, 101130.]. Applied to the entangled polymers, the predictions successfully explain the data, especially those contradicting the TR model. Thus, diffusion of entangled polymer chains is a cooperative many-chain process in having the universal properties of many-body cooperative diffusion established in many other interacting materials, and the reptation hypothesis is unwarranted.
{"title":"Do Entangled Polymer Chains Reptate?","authors":"Kia L. Ngai","doi":"10.1002/mats.202400024","DOIUrl":"10.1002/mats.202400024","url":null,"abstract":"<p>Neutron spin echo spectroscopy of entangled polymer melts [M. Zamponi, et al. <i>J. Phys. Chem. B</i> <b>2008,</b> <i>112</i>, 16220], and of tracer diffusion of short polymer chains in highly entangled polymer melt [M. Zamponi et al. <i>Phys. Rev. Lett</i>. <b>2021</b>, <i>126</i>, 187801.] and [M. Kruteva et al. <i>Macromolecules</i> <b>2021</b>, <i>54</i>, 11384] found the center-of-mass mean-square displacements at shorter times are subdiffusive, heterogeneous, non-Gaussian, and cooperative. These properties contradict the assumption of reptation within the tube in the tube-reptation (TR) model, but are in accord with the predictions from the many-chain cooperative dynamics in the theory of Guenza. The inadequacy of the TR model revealed by the microscopic experiments and theory motivates the author to reexamine previously published data of diffusion of entangled polymer chains from experiments and simulations used to test the TR model. The results reported in this study lead to the conclusion that the key predictions of the TR model are at variance with experimental and simulation data. The cause lies in the reptation hypothesis contradicting the cooperative nature of entangled chain diffusion proven by its dynamics being isomorphic to cooperative diffusion in other materials. The Coupling Model has predictions consistent with the cooperative diffusion properties in interacting materials [<i>Prog. Mater. Sci</i>., <b>2023,</b> <i>139</i>, 101130.]. Applied to the entangled polymers, the predictions successfully explain the data, especially those contradicting the TR model. Thus, diffusion of entangled polymer chains is a cooperative many-chain process in having the universal properties of many-body cooperative diffusion established in many other interacting materials, and the reptation hypothesis is unwarranted.</p>","PeriodicalId":18157,"journal":{"name":"Macromolecular Theory and Simulations","volume":null,"pages":null},"PeriodicalIF":1.8,"publicationDate":"2024-05-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140830706","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The double quench phase separation is a simplified type of continuous cooling process that is widely seen in industrial processes for polymeric membrane formation. Uncommon quenching conditions can lead to the creation of novel membrane microstructures. This study aims to theoretically investigate the impact of nonisothermality on the morphology formation during the double-quench thermally-induced phase separation process. First, quench is employed during different stages of phase separation to observe the possibility of secondary morphology formation. Next, two initial quench temperatures are selected, one shallow and the other deep. The initial solution temperature and the secondary quench temperature are kept constant to inspect the impact of the initial quench temperature on the structure formation. Lastly, the results of the secondary quench are compared with and without employing the enthalpy of demixing. Results verified that the stage of phase separation, the initial and secondary quench temperatures, cooling rate, and the secondary quench composition are the most important parameters in the the nonisothermal double quench phase separation process. The morphology should be well-developed in order for the secondary structure formation. In addition, it is shown that heat generation during demixing in the primary and secondary quenches significantly influences the secondary morphology formation.
{"title":"Numerical Modeling and Simulation of the Nonisothermal Double Quench Phase Separation Process for the Production of Polymeric Membranes Using Polystyrene-Cyclohexanol Polymer Solution","authors":"Samira Ranjbarrad, Philip K. Chan","doi":"10.1002/mats.202400022","DOIUrl":"10.1002/mats.202400022","url":null,"abstract":"<p>The double quench phase separation is a simplified type of continuous cooling process that is widely seen in industrial processes for polymeric membrane formation. Uncommon quenching conditions can lead to the creation of novel membrane microstructures. This study aims to theoretically investigate the impact of nonisothermality on the morphology formation during the double-quench thermally-induced phase separation process. First, quench is employed during different stages of phase separation to observe the possibility of secondary morphology formation. Next, two initial quench temperatures are selected, one shallow and the other deep. The initial solution temperature and the secondary quench temperature are kept constant to inspect the impact of the initial quench temperature on the structure formation. Lastly, the results of the secondary quench are compared with and without employing the enthalpy of demixing. Results verified that the stage of phase separation, the initial and secondary quench temperatures, cooling rate, and the secondary quench composition are the most important parameters in the the nonisothermal double quench phase separation process. The morphology should be well-developed in order for the secondary structure formation. In addition, it is shown that heat generation during demixing in the primary and secondary quenches significantly influences the secondary morphology formation.</p>","PeriodicalId":18157,"journal":{"name":"Macromolecular Theory and Simulations","volume":null,"pages":null},"PeriodicalIF":1.8,"publicationDate":"2024-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/mats.202400022","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140830704","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Sung Jin Pai, Eung Jun Kang, Won Min Ahn, Jae Sung Kim, Young Chan Bae, Ji Won Kwon, Jeong Seok Oh
Swelling experiments are conducted on nonfiller natural rubber using four solvents (toluene, cyclohexane, tetrahydrofuran (THF), and methylethylketone (MEK)) over temperatures from 10 to 70 °C. Toluene, cyclohexane, and THF, classified as effective solvents, show swelling ratios between 3 and 7, influenced by the crosslink density of the rubber. MEK, however, has a lower ratio of 1.5 to 2. Temperature has a minor impact on swelling compared to the crosslink density. The study evaluates the Extended Modified Double Lattice (EMDL) model for its mixing contribution in polymer network swelling, aiming to improve the Flory–Hüggins (FH) model. The superiority of EMDL above FH is in the boundary condition at the unvulcanized state, the former aligning its interaction energy with values from solvent activities in primary linear polymer/solvent solutions, unlike the FH model. The EMDL model also accounts for oriented interactions in polar solvents through a secondary lattice, linking specific interaction energy with solvent dipole moments. The study observes a nonlinear correlation between crosslinking density and sulfur amount, proposing a nonrandom mixing at lower sulfur concentrations. This model shows strong alignment with experimental data, suggesting that replacing the FH model's mixing contribution with the EMDL model could improve results with minimal additional complexity.
{"title":"Swelling Behaviors of Natural Rubber/Solvent Systems Based on the Extended Modified Double Lattice Model","authors":"Sung Jin Pai, Eung Jun Kang, Won Min Ahn, Jae Sung Kim, Young Chan Bae, Ji Won Kwon, Jeong Seok Oh","doi":"10.1002/mats.202400015","DOIUrl":"10.1002/mats.202400015","url":null,"abstract":"<p>Swelling experiments are conducted on nonfiller natural rubber using four solvents (toluene, cyclohexane, tetrahydrofuran (THF), and methylethylketone (MEK)) over temperatures from 10 to 70 °C. Toluene, cyclohexane, and THF, classified as effective solvents, show swelling ratios between 3 and 7, influenced by the crosslink density of the rubber. MEK, however, has a lower ratio of 1.5 to 2. Temperature has a minor impact on swelling compared to the crosslink density. The study evaluates the Extended Modified Double Lattice (EMDL) model for its mixing contribution in polymer network swelling, aiming to improve the Flory–Hüggins (FH) model. The superiority of EMDL above FH is in the boundary condition at the unvulcanized state, the former aligning its interaction energy with values from solvent activities in primary linear polymer/solvent solutions, unlike the FH model. The EMDL model also accounts for oriented interactions in polar solvents through a secondary lattice, linking specific interaction energy with solvent dipole moments. The study observes a nonlinear correlation between crosslinking density and sulfur amount, proposing a nonrandom mixing at lower sulfur concentrations. This model shows strong alignment with experimental data, suggesting that replacing the FH model's mixing contribution with the EMDL model could improve results with minimal additional complexity.</p>","PeriodicalId":18157,"journal":{"name":"Macromolecular Theory and Simulations","volume":null,"pages":null},"PeriodicalIF":1.8,"publicationDate":"2024-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/mats.202400015","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140625072","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Muhammad Asif Javed, Abuzar Ghaffari, Sami Ullah Khan, Ehab Elattar
The coating process is widely used in various industries to enhance the production quality and efficiency. This study gives a comprehensive analysis of non-isothermal blade coating of non-Newtonian nanofluid incorporating magnetic, thermophoresis, and Brownian effects. The mathematical equations derived from mass, momentum, and energy conservation laws are initially streamlined by means of lubrication approximation theory (LAT). Subsequently, these dimensionless equations are solved in dimensionless form numerically using fourth order Runge–Kutta and Newton–Raphson methods. This study includes the effects of the slip parameter, magnetohydrodynamic (MHD) and other material parameters on the coating thickness (