Shear banding in entangled polymer melts remains a fundamental yet unresolved phenomenon in nonlinear polymer rheology.Here,we perform molecular dynamics simulations of bidisperse entangled melts—comprising equal num...Shear banding in entangled polymer melts remains a fundamental yet unresolved phenomenon in nonlinear polymer rheology.Here,we perform molecular dynamics simulations of bidisperse entangled melts—comprising equal numbers of chains with lengths N=200 and N=400—to uncover the structural origins and dynamic evolution of shear banding.This bidisperse system amplifies spatial heterogeneities in the entanglement network and facilitates direct comparison with monodisperse melts of N=300,revealing quantitatively consistent steady-state shear stress versus shear rate responses.Notably,a pronounced stress plateau spanning over an order of magnitude in shear rate is observed,within which shear banding emerges reproducibly across independent simulations,as confirmed by systematic velocity profile and interface position analyses.Our findings challenge the prevailing notion that shear banding arises solely from dynamic flow instabilities.Instead,we establish a microstructure-driven framework,demonstrating that shear band nucleation is governed by pre-existing structural heterogeneities—specifically,localized weakening of the entanglement network at short-chain-enriched“soft spots”,indicative of a robust microstructural memory effect.During shear start-up,short chains preferentially disentangle and migrate along the shear direction;beyond a critical strain,long chains retract and redistribute away from the fast shear band center to minimize elastic energy.This chain-length-dependent migration dynamically enriches the shear band in short chains,stabilizing its structure and revealing a molecular mechanism that links entanglement heterogeneity to macroscopic flow localization.By bridging molecular-scale structural features with nonlinear rheological responses,this work offers a complementary perspective to classical tube and convective constraint release(CCR)models,highlighting the critical interplay between microstructural heterogeneity and chain migration in the onset and persistence of shear banding.展开更多
The practical applications of crystalline porous materials toward industrial separations require shaping them into robust monoliths(e.g., foams). The current methods are often complicated, environmentally unfriendly, ...The practical applications of crystalline porous materials toward industrial separations require shaping them into robust monoliths(e.g., foams). The current methods are often complicated, environmentally unfriendly, and unscalable, significantly hampering their practical application. Herein, we report a scalable, facile “one-step thermomolding” method to fabricate a class of hierarchically olefin-linked covalent organic framework(COF) foams via melt polymerization. The obtained pure COF foams possess higher crystallinity and porosity than literature, good moldability, and processability, greatly benefiting their practical applications(e.g., efficient oil-water separation with 99% removal efficiency and >100 cycle reusability). Moreover, a COF exhibiting the smallest(0.58 nm) eclipsed stacking pore among all 2-dimensional COFs with neutral skeletons is first fabricated via this protocol, demonstrating good C2 H2 purification performance and recyclability, surpassing the current benchmark materials. We believe that this facile fabrication strategy can promote access to a broad diversity of new COF foams and enlighten further avenues for green routes to large-scale synthesis and usage of COFs.展开更多
This paper presents developing soft sensors for polymer melt index in an industrial polymerization process by using deep belief network(DBN).The important quality variable melt index of polypropylene is hard to measur...This paper presents developing soft sensors for polymer melt index in an industrial polymerization process by using deep belief network(DBN).The important quality variable melt index of polypropylene is hard to measure in industrial processes.Lack of online measurement instruments becomes a problem in polymer quality control.One effective solution is to use soft sensors to estimate the quality variables from process data.In recent years,deep learning has achieved many successful applications in image classification and speech recognition.DBN as one novel technique has strong generalization capability to model complex dynamic processes due to its deep architecture.It can meet the demand of modelling accuracy when applied to actual processes.Compared to the conventional neural networks,the training of DBN contains a supervised training phase and an unsupervised training phase.To mine the valuable information from process data,DBN can be trained by the process data without existing labels in an unsupervised training phase to improve the performance of estimation.Selection of DBN structure is investigated in the paper.The modelling results achieved by DBN and feedforward neural networks are compared in this paper.It is shown that the DBN models give very accurate estimations of the polymer melt index.展开更多
This study utilizes molecular dynamics simulation to investigate the complex dynamics of entangled semi-flexible polymer melts.The investigation reveals a significant stress overshoot phenomenon in the systems,demonst...This study utilizes molecular dynamics simulation to investigate the complex dynamics of entangled semi-flexible polymer melts.The investigation reveals a significant stress overshoot phenomenon in the systems,demonstrating the intricate interplay between shear rates,chain orientation,and chain stretching dynamics.Additionally,the identification of metastable states,characterized by a dual-plateau phenomenon in the shear stress-strain curve at specific Rouse-Weissenberg number Wi_(R),showcases the system’s responsiveness to external perturbations and its transition to stable shear banding states.Moreover,the analysis of flow field deviations uncovers a progression of shear bands with increasing Wi_(R),displaying distinct behaviors in the system’s dynamics under different shear rates and chain lengths.These findings challenge established theoretical frameworks and advocate for refined modelling approaches in polymer rheology research.展开更多
Using molecular dynamics(MD)simulations,this study explores the fluid properties of three polymer melts with the same number of entanglements,Z,achieved by adjusting the entanglement length Ne,while investigating the ...Using molecular dynamics(MD)simulations,this study explores the fluid properties of three polymer melts with the same number of entanglements,Z,achieved by adjusting the entanglement length Ne,while investigating the evolution of polymer melt conformation and entanglement under high-rate elongational flow.The identification of a master curve indicates consistent normalized linear viscoelastic behavior.Surprising findings regarding the steady-state viscosity at various elongational rates(Wi_(R)>4.7)for polymer melts with the same Z have been uncovered,challenging existing tube models.Nevertheless,the study demonstrates the potential for normalizing the steady-state elongational viscosity at high rates(Wi_(R)>4.7)by scaling with the square of the chain contour length.Additionally,the observed independence of viscosity on the elongational rate at high rates suggests that higher rates lead to a more significant alignment of polymer chains,a decrease in entanglement,and a stretching in contour length of polymer chains.Molecular-level tracking of tagged chains further supports the assumption of no entanglement under rapid elongation,emphasizing the need for further research on disentanglement in polymer melts subjected to high-rate elongational flow.These results carry significant implications for understanding and predicting the behavior of polymer melts under high-rate elongational flow conditions.展开更多
A two steps direct copolymerisation process was developed. The first step is to produce oligomer and then the oligomer of lactic acid/glycolic acid (90/10) is polymerized with binary catalyst tin chloride dihydrate/p-...A two steps direct copolymerisation process was developed. The first step is to produce oligomer and then the oligomer of lactic acid/glycolic acid (90/10) is polymerized with binary catalyst tin chloride dihydrate/p-toluenesulfonic acid. In this way, the direct synthesis of copoly (lactic acid/glycolic acid) without any organic solvent was investigated. The properties and structures of products were characterized by nuclear magnetic resonance (NMR), differential scanning calorimetry (DSC), X-ray diffraction and so on. The results show that comparatively high molecular weight copolymer of lactic acid and glycolic acid can be prepared by direct processing under appropriate technological conditions.展开更多
Based on the molecular theory of non-linear viscoelasticity with constrained entanglements in polymer melts, the material functions in simple shear flow were formulated, the theoretical relations between. eta((gamma) ...Based on the molecular theory of non-linear viscoelasticity with constrained entanglements in polymer melts, the material functions in simple shear flow were formulated, the theoretical relations between. eta((gamma) over dot), psi (10)((gamma) over dot) and shear rate ((gamma) over dot), and topologically constrained dimension number n ' and a were derived. Linear viscoelastic parameters (eta (0) and G(N)(0)) and topologically constrained dimension number (n ' a and <(<upsilon>)over bar>) as a function of the primary molecular weight (M-n), molecular weight between entanglements (M-C) and the entanglement sites sequence distribution in polymer chain were determined. A new method for determination of viscoelastic parameters (eta (0), psi (10), G(N)(0) and J(e)(0)), topologically constrained dimension number (n ', a and v) and molecular weight (M-n, M-c and M-e) from the shear flow measurements was proposed. It was used to determine those parameters and structures of HDPE, making a good agreement between these values and those obtained by other methods. The agreement affords a quantitative verification for the molecular theory of nonlinear viscoelasticity with constrained entanglement in polymer melts.展开更多
An integral constitutive equation and a set of material functions for describing the strain history of polymer melts were formulated in terms of the Cauchy-Green and Finger tensors. A simple memory function and the de...An integral constitutive equation and a set of material functions for describing the strain history of polymer melts were formulated in terms of the Cauchy-Green and Finger tensors. A simple memory function and the dependence of ηo and τt on M3.4 were derived from the theory of non-linear viscoelasticity with constraints of entanglements for polymer melts and substituted into the Oldroye-Walters-Fredickson constitutive equation. An integral constitutive equation for polymer melts was consequently obtained. Some material functions of the constitutive equation related to certain 'test flow' are examined as follows : (1) simple steady shear flow; (2) steady elongation flow; (3) small-amplitude oscillatory shear flow; (4) stress growth upon the inception of steady shear elongation flow; (5) stress relaxation (modulus and compllance). These theoretical relations for simple steady shear flow were compared with experimental data from our laboratory and references for various polymer melts and concentrated solutions. A good agreement between the theory and experiment was achieved.展开更多
Conceptually, an imagined conformation ellipsoid is supposed to represent the shape of a polymer chain for polymer melts in flow fields and to be equivalent to the volume element in a mathematical sense in continuum m...Conceptually, an imagined conformation ellipsoid is supposed to represent the shape of a polymer chain for polymer melts in flow fields and to be equivalent to the volume element in a mathematical sense in continuum mechanics. A power law dependence of shear modulus of polymer melts on detC, referred to as envelope volume, is proposed. Based on those assumptions and the non-linear relation of shear modulus, a phenomenological viscoelastic model is derived. The model is tested in simple shear flow, simple elongational flow, oscillatory shear flow, and relaxation process after flow suddenly stopped. The results show that the model works well to predict the change of internal structure and viscoelastic performance of polymer melts in flow fields.展开更多
An approach of stochastically statistical mechanics and a unified molecular theory of nonlinear viscoelasticity with constraints of Nagai chain entanglement for polymer melts have been proposed. A multimode model stru...An approach of stochastically statistical mechanics and a unified molecular theory of nonlinear viscoelasticity with constraints of Nagai chain entanglement for polymer melts have been proposed. A multimode model structure for a single polymer chain with n tail segments and N reversible entanglement sites on the test polymer chain is developed. Based on the above model structure and the mechanism of molecular flow by the dynamical reorganization of entanglement sites, the probability distribution function of the end-to-end vectr for a single polymer chain at entangled state and the viscoelastic free energy of deformation for polymer melts are calculated by using the method of the stochastically statistical mechanics. The four types of stress-strain relation and the memory function are derived from this thery. The above theoretical relations are verified by the experimentaf data for various polymer melts. These relations are found to be in good agreement with the experimental results展开更多
A constitutive model of quasi-Newtonian fluid based on the type of flow is used in abrupt planar contraction now.The numerical results from finite element analysis are consistent with experimental data for stress patt...A constitutive model of quasi-Newtonian fluid based on the type of flow is used in abrupt planar contraction now.The numerical results from finite element analysis are consistent with experimental data for stress patterns and velocityprofiles in the flow field. The chain conformations of polymer melts are then investigated in such a planar contraction byusing the phenomenological model with internal parameters proposed by the author. That is, the shape and orientation ofpolymer chain coils are predicted and discussed in different flow regions of the contraction flow field that possess simpleshear flow, extensional flow, vortical flow, and mixed flow respectively.展开更多
Dissipative particle dynamics(DPD)with bond uncrossability shows a great potential in studying entangled polymers,however relatively little is known of applicability range of entangled DPD model to be use as a model f...Dissipative particle dynamics(DPD)with bond uncrossability shows a great potential in studying entangled polymers,however relatively little is known of applicability range of entangled DPD model to be use as a model for ideal chains and properly describe the full dynamics of entangled melts.Therefore,we perform a comprehensive study on structure,dynamics and linear viscoelasticity of a typical DPD entangled model system,semiflexible linear polymer melt.These polymers obey Flory's ideality hypothesis in chain dimensions,but their local structure exhibits nonideal behavior due to weak correlated hole effect.Both monomer motion and viscoelasticity relaxation reproduce the full pictures as predicted by reptation theory.The stronger chain length dependent diffusion coefficient and relaxation time as well as dynamic moduli are in close agreement with predictions of modern tube model that accounts for additional relaxation mechanisms besides chain reptation.However,an anomalous sub-diffusive center of mass motion is observed both before and after the intermediate reptation regime and the cross-correlation between chains is not negligible even these polymers obey stress-optical law,indicating limitations of the reptation theory.Hence semiflexible linear entangled DPD model can correctly describe statics and dynamics of entangled polymer melts.展开更多
The dynamic properties of polymer melts are investigated in the range of normal liquid regime to the supercooled liquid regime. The polymer is modeled as a coarse-grained bead-spring model with chain length ranging fr...The dynamic properties of polymer melts are investigated in the range of normal liquid regime to the supercooled liquid regime. The polymer is modeled as a coarse-grained bead-spring model with chain length ranging from 5 to 160. The mean squared displacement and non-Gaussian parameter are used to describe the self diffusion of polymer beads. We find slow dynamics with decreasing temperature and increasing chain length. The time evolution of non-Gaussian parameters shows two peaks （or one peak one shoulder） in the a-relaxation time, τa, regime and sub-diffusion time regime, respectively, where the first primary peak indicates the dynamic heterogeneity stemmed from the motion of beads, and the secondary peak is the result of correlated motion along a polymer chain. Moreover, the relaxation of polymer beads shows clear two-step decay in supercooled melts and the dynamics shows growing heterogeneity with decreasing temperature. As chain length is increased, a peak of the dynamic susceptibility occurs, and the peak height, x＊4, increases and then reaches a plateau. The curves of the height of the first peak of a2, a2＊, versus τa and the curves of x＊4 versus τa follow two master curves for different chain lengths. Our results indicate the similarity of dynamic heterogeneity dominated by the motion of single bead even the chain length is different. It is interesting to find that the Stokes-Einstein （SE） relation between ra and diffusion coefficient D, D-rq 1, is highly length-scale dependent. The SE relation breaks down in both normal melts regime and supercooled regime at large magnitude of wave vectors, attributed to the non-Brownian motion arising from the chain connectivity and growing heterogeneity due to supercooling. However, the SE relation is reconstructed when the probing length scale is large （at small magnitude of wave vectors）. Our results show a hierarchical physical picture of the supercooled polymeric dynamics.展开更多
By introducing a vibrating force field into the extrusion process of polymer melt, an experimental equipment of constant velocity type dynamic rheometer of capillary (CVDRC) was designed. A set of experimental procedu...By introducing a vibrating force field into the extrusion process of polymer melt, an experimental equipment of constant velocity type dynamic rheometer of capillary (CVDRC) was designed. A set of experimental procedures was established, by which the dynamic rheological parameters of polymer can be acquired, and a set of data management methods to undergo time-domain or frequency-domain analysis was set up for dynamic rheological data of polymer melt. Meantime, the characterization formula of polymer melt's rheological behavior in a vibrating force field was set up. The instantaneous value of capillary entry pressure, capillary volume flow rate and their phase difference were measured and analyzed, and the melt apparent viscosity, which describes the rheological behavior of polymer melt in a vibrating force field, was obtained.展开更多
The influence of fluorine on the structure of CaO Si（）e-Al2Oa Na2O-CaF2 continuous-casting-type slag was measured by Raman spectroscopy, and the degree of polymerization of mould flux and the structural behavior of ...The influence of fluorine on the structure of CaO Si（）e-Al2Oa Na2O-CaF2 continuous-casting-type slag was measured by Raman spectroscopy, and the degree of polymerization of mould flux and the structural behavior of F- in the melt were investigated by classifying and quantifying the structural species of F ions. The results exhibit that the main structural units of Si O tetrahedra are Q1, Q1 and Q2, and the actual measured number of non bridging oxygen ions in the [SiO4 ]-tetrahedra （denoted by NBO/T） in creases from 2. 73 to 3.44 with increasing the molar ratio of F to （F＋O） （denoted by XF/X（F-O ） from 0.06 to 0. 19. It means that the degree of polymerization o1 meh structure decreases with an increase in XE/X（F＋O）. In addition, most of F- ions were distributed in Si-O tetrahedra and Al-O tetrahedra. With increasing XF/X（F＋O）, the complex structural units Al-Otetrahedra are gradually replaced hy discrete structural units A1F4 because of the breakage of Al-O bonds in Al-Otetrahedra by F ions, and the SiO （bridging oxygen） bonds of SiO tetrahedra are broken to form [SiOnF1-n]-tetrahedra by F ions coordinating with Si4 ＋ .展开更多
Nylon 10 T and Nylon 10T/1010 samples were synthesized by direct melt polymerization. The non-isothermal crystallization kinetics of Nylon 10 T and Nylon 10T/1010 was investigated by means of differential scanning cal...Nylon 10 T and Nylon 10T/1010 samples were synthesized by direct melt polymerization. The non-isothermal crystallization kinetics of Nylon 10 T and Nylon 10T/1010 was investigated by means of differential scanning calorimetry(DSC). Jeziorny equation and Mo equation were applied to describe the non-isothermal crystallization kinetics of the Nylon 10 T and the Nylon 10T/1010. The activation energies for non-isothermal crystallization were obtained by Vyazovkin's method and Friedman's method, respectively. These results showed that Jeziorny equation and Mo equation well described the non-isothermal crystallization kinetics of the Nylon 10 T and the Nylon 10T/1010. It was found that the values of the activation energy for non-isothermal crystallization of the Nylon 10T/1010 were lower than those of the Nylon 10 T at a given temperature or relative crystallinity degree,which revealed that crystallization ability of the Nylon 10T/1010 was higher. The crystal morphology was observed by means of a polarized optical microscope(POM) and X-ray diffraction(XRD). It was found that the addition of sebacic acid comonomer not only did not change the crystal form of the Nylon 10 T, but also significantly increased the number and decreased the size of spherulites. Comparing with the Nylon 10 T, the crystallization rate was increased with the addition of the sebacic acid comonomer.展开更多
The morphology and crytal structure of poly(p-phenylene terephthalate) (PPT), prepared by confined thin filmmelt (CTFMP) and solution (CTFSP) and bulk solution polymerization, were characterized by transmission electr...The morphology and crytal structure of poly(p-phenylene terephthalate) (PPT), prepared by confined thin filmmelt (CTFMP) and solution (CTFSP) and bulk solution polymerization, were characterized by transmission electronmicroscopy, electron dimaction and molecular modeling. The unit cell is monoclinic (P2_1/a space group) with parameters a =7.89, b = 5.49, c = 12.65 A, α=γ= 90°, β=100.33°, density = 1.48 g/cm^3, the a, b and β values differing slightly from thosereported previously in the literature. A degree of variation in relative intensities of hk0 reflections in, apparently, untilted[001] ED patterns was observed from a given sample, suggesting some variation in molecular packing. ED evidence wasfound for a second phase, with [001] appearing the same as for phase Ⅱ of the related poly(p-oxybenzoate) (PpOBA)polymer. CTFMP crystals polymerized above 220℃ (up to 370℃) and CTFSP crystals polymerized at 300℃ consisted oflamellae 100-200 A thick.展开更多
Terephthalic acid,2,5-furandicarboxylic acid and 1,8-octanediol were adopted as monomers and antimony trioxide as catalyst,and poly(terephthalic acid-2,5-furandicarboxylic acid-1,8-octanediol) copolyesters identified ...Terephthalic acid,2,5-furandicarboxylic acid and 1,8-octanediol were adopted as monomers and antimony trioxide as catalyst,and poly(terephthalic acid-2,5-furandicarboxylic acid-1,8-octanediol) copolyesters identified as PEOT-x,where x is the mole fraction of furandicarboxylic acid in the samples,were synthesized by direct esterification.The molecular structure of the copolyesters was characterized by FTIR and 1H NMR spectroscopy.Gel permeation chromatography (GPC),differential scanning calorimetry (DSC),and thermogravimetric analysis (TGA) were used to characterize the molecular weight,molar mass dispersity,glass transition temperature,and thermal stability of the copolyesters,respectively.The mechanical properties of the samples were also investigated.The number-average molecular weight (M_(n)) of the samples varies from 9 700-18 800 g/mol,and molar mass dispersity (■=M_(w)/M_(n)) from 2.15-3.34.The initial decomposition temperature of the copolyesters is in the 332-356 ℃ range,with maximum decomposition rates at 390-410 ℃,while the glass transition temperature (Tg) varies from 0-33 ℃.Mechanical test shows that PEOT-10 has the highest tensile strength,while PEOT-90 has the largest tensile modulus and elongation at break.The experimental results show that these copolyesters can be synthesized with relatively high molecular weights,good thermal stability,and fair mechanical properties,which makes them excellent replacements for commercial polyesters,such as PET,and these properties can be tuned through the relative amounts of biomass monomer 2,5-furandicarboxylic acid used in the reactions.展开更多
Nylon 10T and nylon 10T/1010 samples were synthesized by direct melt polymerization.The isothermal crystallization kinetics of nylon 10T and nylon 10T/1010 was investigated by means of differential scanning calorimetr...Nylon 10T and nylon 10T/1010 samples were synthesized by direct melt polymerization.The isothermal crystallization kinetics of nylon 10T and nylon 10T/1010 was investigated by means of differential scanning calorimetry（DSC）.The crystallization kinetics under isothermal condition has been analyzed by the Avrami equation.It was found that the Avrami equation was well-suited to describe the isothermal crystallization kinetics,combined with the results of the Turnbull-Fisher equation.The values of Tm^0 and Kg were obtained by Hoffman-Weeks and Lauritzen-Hoffman equations,respectively.The activation energies for isothermal crystallization of nylon 10T and nylon 10T/1010 were determined using the Arrhenius equation and found to be-123.24 and-81.86 kJ·mol^（-1）,respectively,which reveals that the crystallization ability of nylon 10T/1010was lower than that of nylon 10T during the isothermal crystallization process.The crystal morphology was observed by means of polarized optical microscopy（POM）and X-ray diffraction（XRD）.It was found that the addition of sebacic acid comonomer did not change the crystal form of nylon 10T,but significantly increased the number and decreased the size of spherulites.展开更多
A wholly-aromatic thermotropic liquid crystalline polymer (WATLCP) composed of p-hydroxybenzoic acid (HBA), 4,4'-dihydroxy bisphenyl (BP), terephthalic acid (TPA), m-phthalic acid (MPA) was synthesized. It was sym...A wholly-aromatic thermotropic liquid crystalline polymer (WATLCP) composed of p-hydroxybenzoic acid (HBA), 4,4'-dihydroxy bisphenyl (BP), terephthalic acid (TPA), m-phthalic acid (MPA) was synthesized. It was symbolized by BP-LCP. Using a similar method, a new copolymer BP-PSF was prepared. BP-PSF has a semi-flexible chain polysulfone and a rigid-rod chain like BP-LCP. By FT-IR, polarizing microscope and DSC technique, the structures and properties of BP-LCP and BP-PSF were studied.展开更多
基金financially supported by the National Natural Science Foundation of China(Nos.22341304,22341303 and 22103079)National Key R&D Program of China(Nos.2020YFA0713601 and 2023YFA1008800)+1 种基金Strategic Priority Research Program of the Chinese Academy of Sciences(XDC0180303)Fundamental Enhancement Program(No.2024-JCJQ-JJ-0247)。
文摘Shear banding in entangled polymer melts remains a fundamental yet unresolved phenomenon in nonlinear polymer rheology.Here,we perform molecular dynamics simulations of bidisperse entangled melts—comprising equal numbers of chains with lengths N=200 and N=400—to uncover the structural origins and dynamic evolution of shear banding.This bidisperse system amplifies spatial heterogeneities in the entanglement network and facilitates direct comparison with monodisperse melts of N=300,revealing quantitatively consistent steady-state shear stress versus shear rate responses.Notably,a pronounced stress plateau spanning over an order of magnitude in shear rate is observed,within which shear banding emerges reproducibly across independent simulations,as confirmed by systematic velocity profile and interface position analyses.Our findings challenge the prevailing notion that shear banding arises solely from dynamic flow instabilities.Instead,we establish a microstructure-driven framework,demonstrating that shear band nucleation is governed by pre-existing structural heterogeneities—specifically,localized weakening of the entanglement network at short-chain-enriched“soft spots”,indicative of a robust microstructural memory effect.During shear start-up,short chains preferentially disentangle and migrate along the shear direction;beyond a critical strain,long chains retract and redistribute away from the fast shear band center to minimize elastic energy.This chain-length-dependent migration dynamically enriches the shear band in short chains,stabilizing its structure and revealing a molecular mechanism that links entanglement heterogeneity to macroscopic flow localization.By bridging molecular-scale structural features with nonlinear rheological responses,this work offers a complementary perspective to classical tube and convective constraint release(CCR)models,highlighting the critical interplay between microstructural heterogeneity and chain migration in the onset and persistence of shear banding.
基金supported by the National Natural Science Foundation of China (22175099)111 Projects (B12015)Frontiers Science Center for New Organic Matter (63181206)。
文摘The practical applications of crystalline porous materials toward industrial separations require shaping them into robust monoliths(e.g., foams). The current methods are often complicated, environmentally unfriendly, and unscalable, significantly hampering their practical application. Herein, we report a scalable, facile “one-step thermomolding” method to fabricate a class of hierarchically olefin-linked covalent organic framework(COF) foams via melt polymerization. The obtained pure COF foams possess higher crystallinity and porosity than literature, good moldability, and processability, greatly benefiting their practical applications(e.g., efficient oil-water separation with 99% removal efficiency and >100 cycle reusability). Moreover, a COF exhibiting the smallest(0.58 nm) eclipsed stacking pore among all 2-dimensional COFs with neutral skeletons is first fabricated via this protocol, demonstrating good C2 H2 purification performance and recyclability, surpassing the current benchmark materials. We believe that this facile fabrication strategy can promote access to a broad diversity of new COF foams and enlighten further avenues for green routes to large-scale synthesis and usage of COFs.
基金supported by National Natural Science Foundation of China (No. 61673236)the European Union (No. PIRSES-GA-2013-612230)
文摘This paper presents developing soft sensors for polymer melt index in an industrial polymerization process by using deep belief network(DBN).The important quality variable melt index of polypropylene is hard to measure in industrial processes.Lack of online measurement instruments becomes a problem in polymer quality control.One effective solution is to use soft sensors to estimate the quality variables from process data.In recent years,deep learning has achieved many successful applications in image classification and speech recognition.DBN as one novel technique has strong generalization capability to model complex dynamic processes due to its deep architecture.It can meet the demand of modelling accuracy when applied to actual processes.Compared to the conventional neural networks,the training of DBN contains a supervised training phase and an unsupervised training phase.To mine the valuable information from process data,DBN can be trained by the process data without existing labels in an unsupervised training phase to improve the performance of estimation.Selection of DBN structure is investigated in the paper.The modelling results achieved by DBN and feedforward neural networks are compared in this paper.It is shown that the DBN models give very accurate estimations of the polymer melt index.
基金financially supported by the National Key R&D Program of China(Nos.2020YFA0713601 and 2023YFA1008800)the National Natural Science Foundation of China(Nos.22341304,22341303,22103079,22073092 and 22303100)+1 种基金the Cooperation Project between Jilin Province and CAS(No.2023SYHZ0003)Additional support for Y.Lu was provided by the Youth Innovation Promotion Association of CAS(No.Y202054)。
文摘This study utilizes molecular dynamics simulation to investigate the complex dynamics of entangled semi-flexible polymer melts.The investigation reveals a significant stress overshoot phenomenon in the systems,demonstrating the intricate interplay between shear rates,chain orientation,and chain stretching dynamics.Additionally,the identification of metastable states,characterized by a dual-plateau phenomenon in the shear stress-strain curve at specific Rouse-Weissenberg number Wi_(R),showcases the system’s responsiveness to external perturbations and its transition to stable shear banding states.Moreover,the analysis of flow field deviations uncovers a progression of shear bands with increasing Wi_(R),displaying distinct behaviors in the system’s dynamics under different shear rates and chain lengths.These findings challenge established theoretical frameworks and advocate for refined modelling approaches in polymer rheology research.
基金supported by the National Key R&D Program of China(Nos.2020YFA0713601 and 2023YFA1008800)the National Natural Science Foundation of China(Nos.22341304,22341303,22103079 and 22073092)the Cooperation Project between Jilin Province and CAS(No.2023SYHZ0003).
文摘Using molecular dynamics(MD)simulations,this study explores the fluid properties of three polymer melts with the same number of entanglements,Z,achieved by adjusting the entanglement length Ne,while investigating the evolution of polymer melt conformation and entanglement under high-rate elongational flow.The identification of a master curve indicates consistent normalized linear viscoelastic behavior.Surprising findings regarding the steady-state viscosity at various elongational rates(Wi_(R)>4.7)for polymer melts with the same Z have been uncovered,challenging existing tube models.Nevertheless,the study demonstrates the potential for normalizing the steady-state elongational viscosity at high rates(Wi_(R)>4.7)by scaling with the square of the chain contour length.Additionally,the observed independence of viscosity on the elongational rate at high rates suggests that higher rates lead to a more significant alignment of polymer chains,a decrease in entanglement,and a stretching in contour length of polymer chains.Molecular-level tracking of tagged chains further supports the assumption of no entanglement under rapid elongation,emphasizing the need for further research on disentanglement in polymer melts subjected to high-rate elongational flow.These results carry significant implications for understanding and predicting the behavior of polymer melts under high-rate elongational flow conditions.
文摘A two steps direct copolymerisation process was developed. The first step is to produce oligomer and then the oligomer of lactic acid/glycolic acid (90/10) is polymerized with binary catalyst tin chloride dihydrate/p-toluenesulfonic acid. In this way, the direct synthesis of copoly (lactic acid/glycolic acid) without any organic solvent was investigated. The properties and structures of products were characterized by nuclear magnetic resonance (NMR), differential scanning calorimetry (DSC), X-ray diffraction and so on. The results show that comparatively high molecular weight copolymer of lactic acid and glycolic acid can be prepared by direct processing under appropriate technological conditions.
基金The authors gratefully a.cknowledge financial supportfrom th6 Natiol-al Natural Science Foundatiol- of CI-h-a. The number of
文摘Based on the molecular theory of non-linear viscoelasticity with constrained entanglements in polymer melts, the material functions in simple shear flow were formulated, the theoretical relations between. eta((gamma) over dot), psi (10)((gamma) over dot) and shear rate ((gamma) over dot), and topologically constrained dimension number n ' and a were derived. Linear viscoelastic parameters (eta (0) and G(N)(0)) and topologically constrained dimension number (n ' a and <(<upsilon>)over bar>) as a function of the primary molecular weight (M-n), molecular weight between entanglements (M-C) and the entanglement sites sequence distribution in polymer chain were determined. A new method for determination of viscoelastic parameters (eta (0), psi (10), G(N)(0) and J(e)(0)), topologically constrained dimension number (n ', a and v) and molecular weight (M-n, M-c and M-e) from the shear flow measurements was proposed. It was used to determine those parameters and structures of HDPE, making a good agreement between these values and those obtained by other methods. The agreement affords a quantitative verification for the molecular theory of nonlinear viscoelasticity with constrained entanglement in polymer melts.
文摘An integral constitutive equation and a set of material functions for describing the strain history of polymer melts were formulated in terms of the Cauchy-Green and Finger tensors. A simple memory function and the dependence of ηo and τt on M3.4 were derived from the theory of non-linear viscoelasticity with constraints of entanglements for polymer melts and substituted into the Oldroye-Walters-Fredickson constitutive equation. An integral constitutive equation for polymer melts was consequently obtained. Some material functions of the constitutive equation related to certain 'test flow' are examined as follows : (1) simple steady shear flow; (2) steady elongation flow; (3) small-amplitude oscillatory shear flow; (4) stress growth upon the inception of steady shear elongation flow; (5) stress relaxation (modulus and compllance). These theoretical relations for simple steady shear flow were compared with experimental data from our laboratory and references for various polymer melts and concentrated solutions. A good agreement between the theory and experiment was achieved.
基金This project is supported by the National Natural Science Foundation of China
文摘Conceptually, an imagined conformation ellipsoid is supposed to represent the shape of a polymer chain for polymer melts in flow fields and to be equivalent to the volume element in a mathematical sense in continuum mechanics. A power law dependence of shear modulus of polymer melts on detC, referred to as envelope volume, is proposed. Based on those assumptions and the non-linear relation of shear modulus, a phenomenological viscoelastic model is derived. The model is tested in simple shear flow, simple elongational flow, oscillatory shear flow, and relaxation process after flow suddenly stopped. The results show that the model works well to predict the change of internal structure and viscoelastic performance of polymer melts in flow fields.
文摘An approach of stochastically statistical mechanics and a unified molecular theory of nonlinear viscoelasticity with constraints of Nagai chain entanglement for polymer melts have been proposed. A multimode model structure for a single polymer chain with n tail segments and N reversible entanglement sites on the test polymer chain is developed. Based on the above model structure and the mechanism of molecular flow by the dynamical reorganization of entanglement sites, the probability distribution function of the end-to-end vectr for a single polymer chain at entangled state and the viscoelastic free energy of deformation for polymer melts are calculated by using the method of the stochastically statistical mechanics. The four types of stress-strain relation and the memory function are derived from this thery. The above theoretical relations are verified by the experimentaf data for various polymer melts. These relations are found to be in good agreement with the experimental results
基金This work was supported by the research grants from the National Nature Science Foundation of China (No. 20174024) and the Special Founds for Major State Basic Research Projects (G199906408)
文摘A constitutive model of quasi-Newtonian fluid based on the type of flow is used in abrupt planar contraction now.The numerical results from finite element analysis are consistent with experimental data for stress patterns and velocityprofiles in the flow field. The chain conformations of polymer melts are then investigated in such a planar contraction byusing the phenomenological model with internal parameters proposed by the author. That is, the shape and orientation ofpolymer chain coils are predicted and discussed in different flow regions of the contraction flow field that possess simpleshear flow, extensional flow, vortical flow, and mixed flow respectively.
基金financially supported by the National Natural Science Foundation of China(Nos.21790343,21574142 and 21174154)the National Key Research and Development Program of China(No.2016YFB1100800)。
文摘Dissipative particle dynamics(DPD)with bond uncrossability shows a great potential in studying entangled polymers,however relatively little is known of applicability range of entangled DPD model to be use as a model for ideal chains and properly describe the full dynamics of entangled melts.Therefore,we perform a comprehensive study on structure,dynamics and linear viscoelasticity of a typical DPD entangled model system,semiflexible linear polymer melt.These polymers obey Flory's ideality hypothesis in chain dimensions,but their local structure exhibits nonideal behavior due to weak correlated hole effect.Both monomer motion and viscoelasticity relaxation reproduce the full pictures as predicted by reptation theory.The stronger chain length dependent diffusion coefficient and relaxation time as well as dynamic moduli are in close agreement with predictions of modern tube model that accounts for additional relaxation mechanisms besides chain reptation.However,an anomalous sub-diffusive center of mass motion is observed both before and after the intermediate reptation regime and the cross-correlation between chains is not negligible even these polymers obey stress-optical law,indicating limitations of the reptation theory.Hence semiflexible linear entangled DPD model can correctly describe statics and dynamics of entangled polymer melts.
基金financially supported by the National Natural Science Foundation of China(Nos.21474111 and 21790340)the Key Research Program of Frontier Sciences,CAS(No.QYZDY-SSW-SLH027)
文摘The dynamic properties of polymer melts are investigated in the range of normal liquid regime to the supercooled liquid regime. The polymer is modeled as a coarse-grained bead-spring model with chain length ranging from 5 to 160. The mean squared displacement and non-Gaussian parameter are used to describe the self diffusion of polymer beads. We find slow dynamics with decreasing temperature and increasing chain length. The time evolution of non-Gaussian parameters shows two peaks （or one peak one shoulder） in the a-relaxation time, τa, regime and sub-diffusion time regime, respectively, where the first primary peak indicates the dynamic heterogeneity stemmed from the motion of beads, and the secondary peak is the result of correlated motion along a polymer chain. Moreover, the relaxation of polymer beads shows clear two-step decay in supercooled melts and the dynamics shows growing heterogeneity with decreasing temperature. As chain length is increased, a peak of the dynamic susceptibility occurs, and the peak height, x＊4, increases and then reaches a plateau. The curves of the height of the first peak of a2, a2＊, versus τa and the curves of x＊4 versus τa follow two master curves for different chain lengths. Our results indicate the similarity of dynamic heterogeneity dominated by the motion of single bead even the chain length is different. It is interesting to find that the Stokes-Einstein （SE） relation between ra and diffusion coefficient D, D-rq 1, is highly length-scale dependent. The SE relation breaks down in both normal melts regime and supercooled regime at large magnitude of wave vectors, attributed to the non-Brownian motion arising from the chain connectivity and growing heterogeneity due to supercooling. However, the SE relation is reconstructed when the probing length scale is large （at small magnitude of wave vectors）. Our results show a hierarchical physical picture of the supercooled polymeric dynamics.
文摘By introducing a vibrating force field into the extrusion process of polymer melt, an experimental equipment of constant velocity type dynamic rheometer of capillary (CVDRC) was designed. A set of experimental procedures was established, by which the dynamic rheological parameters of polymer can be acquired, and a set of data management methods to undergo time-domain or frequency-domain analysis was set up for dynamic rheological data of polymer melt. Meantime, the characterization formula of polymer melt's rheological behavior in a vibrating force field was set up. The instantaneous value of capillary entry pressure, capillary volume flow rate and their phase difference were measured and analyzed, and the melt apparent viscosity, which describes the rheological behavior of polymer melt in a vibrating force field, was obtained.
基金the National Natural Science Foundation of China for providing financial support(Nos.51374060 and 51374059)
文摘The influence of fluorine on the structure of CaO Si（）e-Al2Oa Na2O-CaF2 continuous-casting-type slag was measured by Raman spectroscopy, and the degree of polymerization of mould flux and the structural behavior of F- in the melt were investigated by classifying and quantifying the structural species of F ions. The results exhibit that the main structural units of Si O tetrahedra are Q1, Q1 and Q2, and the actual measured number of non bridging oxygen ions in the [SiO4 ]-tetrahedra （denoted by NBO/T） in creases from 2. 73 to 3.44 with increasing the molar ratio of F to （F＋O） （denoted by XF/X（F-O ） from 0.06 to 0. 19. It means that the degree of polymerization o1 meh structure decreases with an increase in XE/X（F＋O）. In addition, most of F- ions were distributed in Si-O tetrahedra and Al-O tetrahedra. With increasing XF/X（F＋O）, the complex structural units Al-Otetrahedra are gradually replaced hy discrete structural units A1F4 because of the breakage of Al-O bonds in Al-Otetrahedra by F ions, and the SiO （bridging oxygen） bonds of SiO tetrahedra are broken to form [SiOnF1-n]-tetrahedra by F ions coordinating with Si4 ＋ .
基金Supported by the National Science and Technology Support Program of China(No.2013BAE02B01)the Special Project on the Integration of Industry,Education and Research of Guangdong Province(No.2013B090500003)the Commissioner Workstation Project of Guangdong Province(No.2014A090906002)
文摘Nylon 10 T and Nylon 10T/1010 samples were synthesized by direct melt polymerization. The non-isothermal crystallization kinetics of Nylon 10 T and Nylon 10T/1010 was investigated by means of differential scanning calorimetry(DSC). Jeziorny equation and Mo equation were applied to describe the non-isothermal crystallization kinetics of the Nylon 10 T and the Nylon 10T/1010. The activation energies for non-isothermal crystallization were obtained by Vyazovkin's method and Friedman's method, respectively. These results showed that Jeziorny equation and Mo equation well described the non-isothermal crystallization kinetics of the Nylon 10 T and the Nylon 10T/1010. It was found that the values of the activation energy for non-isothermal crystallization of the Nylon 10T/1010 were lower than those of the Nylon 10 T at a given temperature or relative crystallinity degree,which revealed that crystallization ability of the Nylon 10T/1010 was higher. The crystal morphology was observed by means of a polarized optical microscope(POM) and X-ray diffraction(XRD). It was found that the addition of sebacic acid comonomer not only did not change the crystal form of the Nylon 10 T, but also significantly increased the number and decreased the size of spherulites. Comparing with the Nylon 10 T, the crystallization rate was increased with the addition of the sebacic acid comonomer.
基金This research was supported, in part, by grants from the National Science Foundation (NSF-DMR Intemational Program 96-16255 (F. R. and P. H. G.) and NSF-DMR Polymer Program 93-12823 and 96-16255 (J. Y., G. S., J. L. and P. H. G.)) and Grant Agency of the
文摘The morphology and crytal structure of poly(p-phenylene terephthalate) (PPT), prepared by confined thin filmmelt (CTFMP) and solution (CTFSP) and bulk solution polymerization, were characterized by transmission electronmicroscopy, electron dimaction and molecular modeling. The unit cell is monoclinic (P2_1/a space group) with parameters a =7.89, b = 5.49, c = 12.65 A, α=γ= 90°, β=100.33°, density = 1.48 g/cm^3, the a, b and β values differing slightly from thosereported previously in the literature. A degree of variation in relative intensities of hk0 reflections in, apparently, untilted[001] ED patterns was observed from a given sample, suggesting some variation in molecular packing. ED evidence wasfound for a second phase, with [001] appearing the same as for phase Ⅱ of the related poly(p-oxybenzoate) (PpOBA)polymer. CTFMP crystals polymerized above 220℃ (up to 370℃) and CTFSP crystals polymerized at 300℃ consisted oflamellae 100-200 A thick.
基金Funded by the Program (BG20190227001) of High-end Foreign Experts of the State Administration of Foreign Experts Affairs (SAFEA)the 2021 Innovative Training Program for College Students in Hubei Province。
文摘Terephthalic acid,2,5-furandicarboxylic acid and 1,8-octanediol were adopted as monomers and antimony trioxide as catalyst,and poly(terephthalic acid-2,5-furandicarboxylic acid-1,8-octanediol) copolyesters identified as PEOT-x,where x is the mole fraction of furandicarboxylic acid in the samples,were synthesized by direct esterification.The molecular structure of the copolyesters was characterized by FTIR and 1H NMR spectroscopy.Gel permeation chromatography (GPC),differential scanning calorimetry (DSC),and thermogravimetric analysis (TGA) were used to characterize the molecular weight,molar mass dispersity,glass transition temperature,and thermal stability of the copolyesters,respectively.The mechanical properties of the samples were also investigated.The number-average molecular weight (M_(n)) of the samples varies from 9 700-18 800 g/mol,and molar mass dispersity (■=M_(w)/M_(n)) from 2.15-3.34.The initial decomposition temperature of the copolyesters is in the 332-356 ℃ range,with maximum decomposition rates at 390-410 ℃,while the glass transition temperature (Tg) varies from 0-33 ℃.Mechanical test shows that PEOT-10 has the highest tensile strength,while PEOT-90 has the largest tensile modulus and elongation at break.The experimental results show that these copolyesters can be synthesized with relatively high molecular weights,good thermal stability,and fair mechanical properties,which makes them excellent replacements for commercial polyesters,such as PET,and these properties can be tuned through the relative amounts of biomass monomer 2,5-furandicarboxylic acid used in the reactions.
基金Supported by the National Science and Technology Support Program of China(No.2013BAE02B01)the Special Project on the Integration of Industry,Education and Research of Guangdong Province(No.2013B090500003)the Commissioner Workstation Project of Guangdong Province(No.2014A090906002)
文摘Nylon 10T and nylon 10T/1010 samples were synthesized by direct melt polymerization.The isothermal crystallization kinetics of nylon 10T and nylon 10T/1010 was investigated by means of differential scanning calorimetry（DSC）.The crystallization kinetics under isothermal condition has been analyzed by the Avrami equation.It was found that the Avrami equation was well-suited to describe the isothermal crystallization kinetics,combined with the results of the Turnbull-Fisher equation.The values of Tm^0 and Kg were obtained by Hoffman-Weeks and Lauritzen-Hoffman equations,respectively.The activation energies for isothermal crystallization of nylon 10T and nylon 10T/1010 were determined using the Arrhenius equation and found to be-123.24 and-81.86 kJ·mol^（-1）,respectively,which reveals that the crystallization ability of nylon 10T/1010was lower than that of nylon 10T during the isothermal crystallization process.The crystal morphology was observed by means of polarized optical microscopy（POM）and X-ray diffraction（XRD）.It was found that the addition of sebacic acid comonomer did not change the crystal form of nylon 10T,but significantly increased the number and decreased the size of spherulites.
文摘A wholly-aromatic thermotropic liquid crystalline polymer (WATLCP) composed of p-hydroxybenzoic acid (HBA), 4,4'-dihydroxy bisphenyl (BP), terephthalic acid (TPA), m-phthalic acid (MPA) was synthesized. It was symbolized by BP-LCP. Using a similar method, a new copolymer BP-PSF was prepared. BP-PSF has a semi-flexible chain polysulfone and a rigid-rod chain like BP-LCP. By FT-IR, polarizing microscope and DSC technique, the structures and properties of BP-LCP and BP-PSF were studied.
