Pub Date : 2024-11-16DOI: 10.1016/j.polymer.2024.127788
Yong Chen, An Liu
As a natural isoflavone compound, glabridin (GLD) has excellent skin-whitening properties, but its biomedical applications are greatly limited due to its poor water solubility and low skin permeability. In the current work, GLD was complexed with hydroxypropyl-β-cyclodextrin (HP-β-CD) to form a GLD/HP-β-CD inclusion complex that would improve the water solubility and skin permeability by changing the physicochemical properties of GLD, including the formation of intermolecular hydrogen bonds and amorphous transformation. The cytotoxicity of GLD/HP-β-CD on HaCaT keratinocytes is lower than that of GLD, while it has a more substantial inhibitory effect on melanin than GLD. Furthermore, a dual thermo- and pH-responsive hydrogel called PCG was established as the carrier of GLD/HP-β-CD. The PCG hydrogel presented a porous structure, biodegradability, and excellent biocompatibility. GLD had a dual thermo- and pH-responsive release behavior from the PCG hydrogel and displayed an accelerated release rate at weakly acidic pH conditions compared to the neutral pH environment. Moreover, GLD/HP-β-CD/PCG hydrogel can significantly inhibit melanin deposition in vivo. Taken together, this study provides a low toxicity and high efficiency new method for the application of GLD in biomedical fields, demonstrating its enormous potential in skin-whitening.
{"title":"Skin-whitening effect of hydroxypropyl-β-cyclodextrin/glabridin inclusion complex loaded on a dual thermo/pH-sensitive hydrogel","authors":"Yong Chen, An Liu","doi":"10.1016/j.polymer.2024.127788","DOIUrl":"https://doi.org/10.1016/j.polymer.2024.127788","url":null,"abstract":"As a natural isoflavone compound, glabridin (GLD) has excellent skin-whitening properties, but its biomedical applications are greatly limited due to its poor water solubility and low skin permeability. In the current work, GLD was complexed with hydroxypropyl-β-cyclodextrin (HP-β-CD) to form a GLD/HP-β-CD inclusion complex that would improve the water solubility and skin permeability by changing the physicochemical properties of GLD, including the formation of intermolecular hydrogen bonds and amorphous transformation. The cytotoxicity of GLD/HP-β-CD on HaCaT keratinocytes is lower than that of GLD, while it has a more substantial inhibitory effect on melanin than GLD. Furthermore, a dual thermo- and pH-responsive hydrogel called PCG was established as the carrier of GLD/HP-β-CD. The PCG hydrogel presented a porous structure, biodegradability, and excellent biocompatibility. GLD had a dual thermo- and pH-responsive release behavior from the PCG hydrogel and displayed an accelerated release rate at weakly acidic pH conditions compared to the neutral pH environment. Moreover, GLD/HP-β-CD/PCG hydrogel can significantly inhibit melanin deposition <em>in vivo</em>. Taken together, this study provides a low toxicity and high efficiency new method for the application of GLD in biomedical fields, demonstrating its enormous potential in skin-whitening.","PeriodicalId":405,"journal":{"name":"Polymer","volume":"35 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142642638","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
To investigate the impact of spray polyurea (SPUA) modifiers on the microstructure and performance of asphalt, SPUA powder prepared by cryogenic grinding was selected as modifier to explore the microscopic mechanisms of spray polyurea modified asphalt. Initially, the morphological characteristics of the SPUA modifiers were systematically characterized using morphological methods. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) were conducted to examine the effects of SPUA on the thermodynamic properties of asphalt. Finally, molecular dynamics simulations were utilized to model SPUA modified asphalt at different concentrations. Critical parameters such as cohesive energy density, solubility parameters, interaction energy, free volume, and radial distribution function (RDF) were analyzed to elucidate the microscopic mechanisms underlying the experimental results. The results indicate that the surface morphology of SPUA includes several pore structures, which enhance the tight and continuous bonding at the SPUA asphalt interface, thereby enhancing the microstructural stability of the modified asphalt. Additionally, incorporating SPUA increased the decomposition temperature of the asphalt binder, improving its thermal stability. This phenomenon is further validated by molecular dynamics simulations, which show that with increasing amounts of polyurethane, both the cohesive energy density and interaction energy of the asphalt system significantly increase, thereby enhancing the structural strength of the asphalt system. However, while low SPUA concentrations enhance the surface roughness of the asphalt, excessive SPUA may disrupt the uniform dispersion of the asphalt binder. This leads to a reduction in the difference in solubility parameters between the two components, diminishing compatibility, and decreasing the free volume fraction of the asphalt while increasing the peak of the radial distribution function curve. Such changes adversely affect the flowability and stability of the modified asphalt.
{"title":"Microscopic effect and mechanism of spray polyurea modifier on the asphalt binder: experimental characterization and molecular dynamics simulations","authors":"Xiaolong Sun, Hualong Xu, Xuehui Zheng, Xiao Qin, Tao Guo, Jianfeng Gao","doi":"10.1016/j.polymer.2024.127807","DOIUrl":"https://doi.org/10.1016/j.polymer.2024.127807","url":null,"abstract":"To investigate the impact of spray polyurea (SPUA) modifiers on the microstructure and performance of asphalt, SPUA powder prepared by cryogenic grinding was selected as modifier to explore the microscopic mechanisms of spray polyurea modified asphalt. Initially, the morphological characteristics of the SPUA modifiers were systematically characterized using morphological methods. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) were conducted to examine the effects of SPUA on the thermodynamic properties of asphalt. Finally, molecular dynamics simulations were utilized to model SPUA modified asphalt at different concentrations. Critical parameters such as cohesive energy density, solubility parameters, interaction energy, free volume, and radial distribution function (RDF) were analyzed to elucidate the microscopic mechanisms underlying the experimental results. The results indicate that the surface morphology of SPUA includes several pore structures, which enhance the tight and continuous bonding at the SPUA asphalt interface, thereby enhancing the microstructural stability of the modified asphalt. Additionally, incorporating SPUA increased the decomposition temperature of the asphalt binder, improving its thermal stability. This phenomenon is further validated by molecular dynamics simulations, which show that with increasing amounts of polyurethane, both the cohesive energy density and interaction energy of the asphalt system significantly increase, thereby enhancing the structural strength of the asphalt system. However, while low SPUA concentrations enhance the surface roughness of the asphalt, excessive SPUA may disrupt the uniform dispersion of the asphalt binder. This leads to a reduction in the difference in solubility parameters between the two components, diminishing compatibility, and decreasing the free volume fraction of the asphalt while increasing the peak of the radial distribution function curve. Such changes adversely affect the flowability and stability of the modified asphalt.","PeriodicalId":405,"journal":{"name":"Polymer","volume":"98 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142642955","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-16DOI: 10.1016/j.polymer.2024.127815
Jun Zhang, Kainan Guo, Jinke Guo, Md All Amin Newton, Tingxiao Li, Binjie Xin
All fibrous electronic skin based on excellent flexibility and piezoelectric properties could be widely applied in monitoring and healthcare sensing. The accumulative moisture during application scenarios, just as violent sweat or a damp environment, can affect the stability and sensitivity of the piezoelectric signal. Here, a bilayer piezoelectric sensor was fabricated using a layer-by-layer electrospinning technique. The inner layer is composed of hydrophobic piezoelectric polyvinylidene fluoride (PVDF)-zinc oxide (ZnO) nanofibers, while the outer layer consists of hydrophilic piezoelectric polyacrylonitrile (PAN)-barium titanate (BTO) nanofibers. The unidirectional moisture-wicking performance based on the hydrophilic-hydrophobic gradient of PVDF/ZnO-PAN/BTO nanofiber membranes (PZ-PBNF) could conduct liquid within 1 s. Incorporating inorganic ZnO and BTO nanoparticles provides a practical approach to enhancing the piezoelectric output performance (277.5 mV). These fibrous PZ-PBNF membranes also exhibit excellent stretchability properties (breaking elongation of 110%) and air permeability (12.065 mm/s). This innovative electronic skin with directional water transport and sensing functions could ensure long-term wear comfort for practical application in emerging wearable technologies and all healthcare ranges.
{"title":"Unidirectional Moisture-Wicking PAN/BTO-PVDF/ZnO All Fibrous Bilayer Breathable Electronic Skin for Health Sensing","authors":"Jun Zhang, Kainan Guo, Jinke Guo, Md All Amin Newton, Tingxiao Li, Binjie Xin","doi":"10.1016/j.polymer.2024.127815","DOIUrl":"https://doi.org/10.1016/j.polymer.2024.127815","url":null,"abstract":"All fibrous electronic skin based on excellent flexibility and piezoelectric properties could be widely applied in monitoring and healthcare sensing. The accumulative moisture during application scenarios, just as violent sweat or a damp environment, can affect the stability and sensitivity of the piezoelectric signal. Here, a bilayer piezoelectric sensor was fabricated using a layer-by-layer electrospinning technique. The inner layer is composed of hydrophobic piezoelectric polyvinylidene fluoride (PVDF)-zinc oxide (ZnO) nanofibers, while the outer layer consists of hydrophilic piezoelectric polyacrylonitrile (PAN)-barium titanate (BTO) nanofibers. The unidirectional moisture-wicking performance based on the hydrophilic-hydrophobic gradient of PVDF/ZnO-PAN/BTO nanofiber membranes (PZ-PBNF) could conduct liquid within 1 s. Incorporating inorganic ZnO and BTO nanoparticles provides a practical approach to enhancing the piezoelectric output performance (277.5 mV). These fibrous PZ-PBNF membranes also exhibit excellent stretchability properties (breaking elongation of 110%) and air permeability (12.065 mm/s). This innovative electronic skin with directional water transport and sensing functions could ensure long-term wear comfort for practical application in emerging wearable technologies and all healthcare ranges.","PeriodicalId":405,"journal":{"name":"Polymer","volume":"17 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142642641","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-16DOI: 10.1016/j.polymer.2024.127811
Pengjie Chao, Qicheng Su, Yuqing Liao, Donglin Shen, Daize Mo, Lanqing Li
The isomeric chlorination of the conjugated side chain is an effective method to improve the photoelectronic properties of polymers, but has not been well investigated in electrochromic performance. Herein, two new D-A-D type isomeric monomers, EQx-α-Cl and EQx-β-Cl, based on 2,3-bis(5-chloro-4-(2-ethylhexyl)thioph-en-2-yl)-6,7-difluoro-5,8-di(thiophen-2-yl)quinoxaline (Qx-α-Cl) and 2,3-bis(4-chloro-5-(2-ethylhexyl)thiophen-2-yl)-6,7-difluoro-5,8-di(thiophen-2-yl)quinoxaline (Qx-β-Cl) as the acceptor units by the isomeric chlorination of the different position of the conjugated thiophene side chain were designed and synthesized. Then their D-A-D type polymers (PEQx-α-Cl and PEQx-β-Cl) were synthesized by electrochemical polymerization. EQx-α-Cl not only exhibits slight red-shifted absorption onset and much stronger absorption with molar extinction coefficient of 1.16×105 M-1 cm-1 but also shows lower onset oxidation potential (Eonset) of 0.65 V compared with those of EQx-β-Cl (7.26×104 M-1 cm-1 and 0.73 V). And PEQx-α-Cl displayed yellow green at neutral state and dark green at oxidation state, respectively, and showed much better electrochemical stability and electrochromic performance including the higher optical contrast 37.7% and the CE value of 319 cm2 C-1 at 890 nm in comparison with PEQx-β-Cl, which was beneficial to design the electrochromic materials toward adaptive camouflage application. These results demonstrated that the isomeric chlorination strategy of conjugated side chain is a promising approach which may open up a new horizon for designing and synthesizing the high-performance electrochromic polymers.
{"title":"Isomeric chlorination of conjugated thiophene side chain based on quinoxaline to design high-performance electrochromic polymers","authors":"Pengjie Chao, Qicheng Su, Yuqing Liao, Donglin Shen, Daize Mo, Lanqing Li","doi":"10.1016/j.polymer.2024.127811","DOIUrl":"https://doi.org/10.1016/j.polymer.2024.127811","url":null,"abstract":"The isomeric chlorination of the conjugated side chain is an effective method to improve the photoelectronic properties of polymers, but has not been well investigated in electrochromic performance. Herein, two new D-A-D type isomeric monomers, EQx-<em>α</em>-Cl and EQx-<em>β</em>-Cl, based on 2,3-bis(5-chloro-4-(2-ethylhexyl)thioph-en-2-yl)-6,7-difluoro-5,8-di(thiophen-2-yl)quinoxaline (Qx-<em>α</em>-Cl) and 2,3-bis(4-chloro-5-(2-ethylhexyl)thiophen-2-yl)-6,7-difluoro-5,8-di(thiophen-2-yl)quinoxaline (Qx-<em>β</em>-Cl) as the acceptor units by the isomeric chlorination of the different position of the conjugated thiophene side chain were designed and synthesized. Then their D-A-D type polymers (PEQx-<em>α</em>-Cl and PEQx-<em>β</em>-Cl) were synthesized by electrochemical polymerization. EQx-<em>α</em>-Cl not only exhibits slight red-shifted absorption onset and much stronger absorption with molar extinction coefficient of 1.16×10<sup>5</sup> M<sup>-1</sup> cm<sup>-1</sup> but also shows lower onset oxidation potential (<em>E</em><sub>onset</sub>) of 0.65 V compared with those of EQx-<em>β</em>-Cl (7.26×10<sup>4</sup> M<sup>-1</sup> cm<sup>-1</sup> and 0.73 V). And PEQx-<em>α</em>-Cl displayed yellow green at neutral state and dark green at oxidation state, respectively, and showed much better electrochemical stability and electrochromic performance including the higher optical contrast 37.7% and the <em>CE</em> value of 319 cm<sup>2</sup> C<sup>-1</sup> at 890 nm in comparison with PEQx-<em>β</em>-Cl, which was beneficial to design the electrochromic materials toward adaptive camouflage application. These results demonstrated that the isomeric chlorination strategy of conjugated side chain is a promising approach which may open up a new horizon for designing and synthesizing the high-performance electrochromic polymers.","PeriodicalId":405,"journal":{"name":"Polymer","volume":"25 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142642636","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-16DOI: 10.1016/j.polymer.2024.127855
Jiawei Yang, Feifei Wang, Chaobo Liang, Shaofeng Zhou, Jin Huang, Guizhe Zhao, Yaqing Liu
This study investigates the integration of Trans-1,4-poly(isoprene-co-butadiene) rubber (TBIR) with natural rubber (NR) and cis-1,4-polybutadiene rubber (BR) to enhance the abrasion resistance of rubber composites. The NR/BR blend, a significant material in the rubber industry, is limited by poor interfacial compatibility and non-uniform filler distribution, resulting in heightened abrasion and failure. The addition of TBIR, along with carbon black (CB) and graphene oxide (GO), aims to achieve synergistic reinforcement. The results show that with 20 phr TBIR, the DIN abrasion of the composites decreased by 13.8%, meeting the ISO 10247 standard for high-abrasion conveyor belt cover rubber. The improvement in wear resistance is attributed to TBIR's crystalline nature, which enhances tear strength, hardness, and elongation at break. TBIR also acts as an interface compatibility agent, improving the network structure of the rubber and fillers, thus enhancing composite performance. Observations of Schallamach waves, abrasion surface, and debris morphology indicate that the primary surface abrasion mechanism for the NR/BR/TBIR composites is abrasive abrasion. Regression analysis reveals that the abrasion resistance of the NR/BR/TBIR composites correlates with their mechanical properties and thermal conductivity, with higher tear strength, hardness, and elongation at break correlating with reduced surface damage due to abrasive abrasion. This research provides valuable insights into the development of high-abrasion-resistant natural rubber composites and the investigation of abrasion resistance mechanisms in rubber composites.
{"title":"Trans-1,4-Poly(isoprene-co-butadiene) Rubber Enhances Abrasion Resistance in Natural Rubber and Polybutadiene Composites","authors":"Jiawei Yang, Feifei Wang, Chaobo Liang, Shaofeng Zhou, Jin Huang, Guizhe Zhao, Yaqing Liu","doi":"10.1016/j.polymer.2024.127855","DOIUrl":"https://doi.org/10.1016/j.polymer.2024.127855","url":null,"abstract":"This study investigates the integration of Trans-1,4-poly(isoprene-co-butadiene) rubber (TBIR) with natural rubber (NR) and cis-1,4-polybutadiene rubber (BR) to enhance the abrasion resistance of rubber composites. The NR/BR blend, a significant material in the rubber industry, is limited by poor interfacial compatibility and non-uniform filler distribution, resulting in heightened abrasion and failure. The addition of TBIR, along with carbon black (CB) and graphene oxide (GO), aims to achieve synergistic reinforcement. The results show that with 20 phr TBIR, the DIN abrasion of the composites decreased by 13.8%, meeting the ISO 10247 standard for high-abrasion conveyor belt cover rubber. The improvement in wear resistance is attributed to TBIR's crystalline nature, which enhances tear strength, hardness, and elongation at break. TBIR also acts as an interface compatibility agent, improving the network structure of the rubber and fillers, thus enhancing composite performance. Observations of Schallamach waves, abrasion surface, and debris morphology indicate that the primary surface abrasion mechanism for the NR/BR/TBIR composites is abrasive abrasion. Regression analysis reveals that the abrasion resistance of the NR/BR/TBIR composites correlates with their mechanical properties and thermal conductivity, with higher tear strength, hardness, and elongation at break correlating with reduced surface damage due to abrasive abrasion. This research provides valuable insights into the development of high-abrasion-resistant natural rubber composites and the investigation of abrasion resistance mechanisms in rubber composites.","PeriodicalId":405,"journal":{"name":"Polymer","volume":"8 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142642640","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The surface treatment of ultra-high molecular weight polyethylene (UHMWPE) fibers is one of the key technologies for the application of UHMWPE fibers composites. In this paper, the interface transition layer of polydopamine (PDA) and polyhedral oligomeric silsesquioxane (POSS) co-deposited on the surface of corona pre-treatment fiber fabric is used to the uniform and efficient distribution of loads between the fibers and the resin matrix, especially to significantly improve the flexural modulus of UHMWPE fiber fabric composites. Under 2.5 kW corona pre-treatment, 4 g/L of dopamine hydrochloride and 2 wt.% of γ-Aminopropyl triethoxysilane aqueous solution, the impact strength, flexural strength, and modulus of UH-C2.5@PDA/PA2 fiber fabric/epoxy composites are greatly improved to 218.6 kJ/m2, 151.7 MPa, and 7.8 GPa, respectively, which are 72 %, 106 % and 143 % higher than those of the untreated UHMWPE fiber composites. It may be attributed to: (1) the corona pre-treatment of UHMWPE fiber induces larger amount of active sites on fiber surface and higher surface energy, leading to a better wettability and adhesion with the matrix resin; (2) the mechanical interlocking engagement between the fibers and nano-POSS particles effectively prevents fibers extraction from the matrix resin and increases the friction of relative sliding; (3) POSS can strengthen the transition layer. The failure of UHMWPE fiber reinforced composites can be mainly attributed to energy absorption of matrix resin fracture, interface damage and relative sliding between matrix resin and fibers, fiber yield deformation and fiber fracture.
{"title":"A novel PDA/POSS transition layer on the surface of UHMWPE fibers by co-depositing to improve the mechanical properties of composites","authors":"Yu Zhang, Zhaoyuan Jing, Guodong Jiang, Fanmin Kong, Xiaolian Wu, Yanhua Bao, Sheng Cui, Yucai Shen","doi":"10.1016/j.polymer.2024.127856","DOIUrl":"https://doi.org/10.1016/j.polymer.2024.127856","url":null,"abstract":"The surface treatment of ultra-high molecular weight polyethylene (UHMWPE) fibers is one of the key technologies for the application of UHMWPE fibers composites. In this paper, the interface transition layer of polydopamine (PDA) and polyhedral oligomeric silsesquioxane (POSS) co-deposited on the surface of corona pre-treatment fiber fabric is used to the uniform and efficient distribution of loads between the fibers and the resin matrix, especially to significantly improve the flexural modulus of UHMWPE fiber fabric composites. Under 2.5 kW corona pre-treatment, 4 g/L of dopamine hydrochloride and 2 wt.% of γ-Aminopropyl triethoxysilane aqueous solution, the impact strength, flexural strength, and modulus of <span><span>UH-C2.5@PDA/PA2</span><svg aria-label=\"Opens in new window\" focusable=\"false\" height=\"20\" viewbox=\"0 0 8 8\"><path d=\"M1.12949 2.1072V1H7V6.85795H5.89111V2.90281L0.784057 8L0 7.21635L5.11902 2.1072H1.12949Z\"></path></svg></span> fiber fabric/epoxy composites are greatly improved to 218.6 kJ/m<sup>2</sup>, 151.7 MPa, and 7.8 GPa, respectively, which are 72 %, 106 % and 143 % higher than those of the untreated UHMWPE fiber composites. It may be attributed to: (1) the corona pre-treatment of UHMWPE fiber induces larger amount of active sites on fiber surface and higher surface energy, leading to a better wettability and adhesion with the matrix resin; (2) the mechanical interlocking engagement between the fibers and nano-POSS particles effectively prevents fibers extraction from the matrix resin and increases the friction of relative sliding; (3) POSS can strengthen the transition layer. The failure of UHMWPE fiber reinforced composites can be mainly attributed to energy absorption of matrix resin fracture, interface damage and relative sliding between matrix resin and fibers, fiber yield deformation and fiber fracture.","PeriodicalId":405,"journal":{"name":"Polymer","volume":"5 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142642679","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-15DOI: 10.1016/j.polymer.2024.127844
Ritima Banerjee, Yongjin Li, Suprakas Sinha Ray
This article provides a critical overview of the fundamentals related to the migration and localization of nanoparticles in immiscible polymer blends, with a discussion on recent advances, including knowledge gaps related to the effect of nanofiller localization on the properties of polymer blend composites. Thermodynamic equilibrium primarily guides the migration and localization of nanoparticles in immiscible polymer blends. However, the effect of kinetics cannot be ignored when nanoparticles are initially distributed in a thermodynamically less favored phase. By controlling various process parameters during melt processing, one can exploit the effect of kinetics for tailoring the localization of nanoparticles. Furthermore, filler particles can be localized at the interface by surface modification of the filler particles and inducing interfacial reactions or by tailoring their wettability using surface functionalization. Such control of the migration of nanoparticles is crucial for getting desired properties, such as high electrical conductivity and low percolation threshold of conductive polymer blend nanocomposites. By providing a holistic understanding of all critical aspects (thermodynamic and kinetic) related to the control of migration of all commonly used nanoparticles and its subsequent effect on properties, this review offers a direction for future advances in the development of high-performance multiphase nanocomposite materials used for various high-end applications.
{"title":"Nanoparticle-induced morphology evolution and property expression in immiscible polymer blend composites−A review of fundamental understanding on nanoparticle migration and interface crossing","authors":"Ritima Banerjee, Yongjin Li, Suprakas Sinha Ray","doi":"10.1016/j.polymer.2024.127844","DOIUrl":"https://doi.org/10.1016/j.polymer.2024.127844","url":null,"abstract":"This article provides a critical overview of the fundamentals related to the migration and localization of nanoparticles in immiscible polymer blends, with a discussion on recent advances, including knowledge gaps related to the effect of nanofiller localization on the properties of polymer blend composites. Thermodynamic equilibrium primarily guides the migration and localization of nanoparticles in immiscible polymer blends. However, the effect of kinetics cannot be ignored when nanoparticles are initially distributed in a thermodynamically less favored phase. By controlling various process parameters during melt processing, one can exploit the effect of kinetics for tailoring the localization of nanoparticles. Furthermore, filler particles can be localized at the interface by surface modification of the filler particles and inducing interfacial reactions or by tailoring their wettability using surface functionalization. Such control of the migration of nanoparticles is crucial for getting desired properties, such as high electrical conductivity and low percolation threshold of conductive polymer blend nanocomposites. By providing a holistic understanding of all critical aspects (thermodynamic and kinetic) related to the control of migration of all commonly used nanoparticles and its subsequent effect on properties, this review offers a direction for future advances in the development of high-performance multiphase nanocomposite materials used for various high-end applications.","PeriodicalId":405,"journal":{"name":"Polymer","volume":"7 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142637491","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-15DOI: 10.1016/j.polymer.2024.127852
Xin Song , Chao Zhou , Li Liu , Guangfeng Wu
Novel castor oil-based waterborne polyurethane (CWPU) sizing coatings prepared by replacing traditional petroleum-based petrochemical products with natural renewable bio-extracts are attracting the attentions in the carbon fibre (CF) reinforced epoxy (EP) composites industries. However, CWPU coatings prepared using only castor oil (CO), diisocyanate, and carboxylate hydrophilic chain extender suffer from poor thermal stability, insufficient mechanical strength and weak adhesion. For enhancing the thermo-mechanical properties of CWPU coatings, as well as the surface wettability and interfacial adhesion to the substrates when serving as fibre sizing coatings and as interphases of the CF/EP composites, a compound cross-linker with tri-acrylate branched and tri-isocyanate chain-endings was synthesized and used to prepare hyperbranched CWPU with CO-acrylate-isocyanate interpenetrating cross-linking networks. CWPU coatings revealed favourable thermodynamic performance achieving a T5% decomposition temperature and toughness of 271.8 °C and 36.2 MJ/m3. CWPU coatings imparted excellent wettability to CF through oxygen-containing polar groups and synergy between covalent/hydrogen bonding, resulting in an increase in fibre surface energy to 61.0 mN/m. Stable and robust interphases were constructed in the CF/EP composites by CWPU coatings through "polar similarity compatibility" and multiple physico-chemical reactions. The flexural modulus, interlaminar shear strength, and interfacial shear strength of CWPU-CF/EP were increased by 54.8 %, 36.6 %, and 58.9 %, respectively, compared with those of the unsized CF/EP composites. The research contributes to the development and industrial production of high-performance, eco-friendly bio-based water soluble organic coatings.
{"title":"Hyperbranched bio-based waterborne sizing coating for enhancing the wettability of carbon fibre and interfacial adhesion of fibre/epoxy composites","authors":"Xin Song , Chao Zhou , Li Liu , Guangfeng Wu","doi":"10.1016/j.polymer.2024.127852","DOIUrl":"10.1016/j.polymer.2024.127852","url":null,"abstract":"<div><div>Novel castor oil-based waterborne polyurethane (CWPU) sizing coatings prepared by replacing traditional petroleum-based petrochemical products with natural renewable bio-extracts are attracting the attentions in the carbon fibre (CF) reinforced epoxy (EP) composites industries. However, CWPU coatings prepared using only castor oil (CO), diisocyanate, and carboxylate hydrophilic chain extender suffer from poor thermal stability, insufficient mechanical strength and weak adhesion. For enhancing the thermo-mechanical properties of CWPU coatings, as well as the surface wettability and interfacial adhesion to the substrates when serving as fibre sizing coatings and as interphases of the CF/EP composites, a compound cross-linker with tri-acrylate branched and tri-isocyanate chain-endings was synthesized and used to prepare hyperbranched CWPU with CO-acrylate-isocyanate interpenetrating cross-linking networks. CWPU coatings revealed favourable thermodynamic performance achieving a T5% decomposition temperature and toughness of 271.8 °C and 36.2 MJ/m<sup>3</sup>. CWPU coatings imparted excellent wettability to CF through oxygen-containing polar groups and synergy between covalent/hydrogen bonding, resulting in an increase in fibre surface energy to 61.0 mN/m. Stable and robust interphases were constructed in the CF/EP composites by CWPU coatings through \"polar similarity compatibility\" and multiple physico-chemical reactions. The flexural modulus, interlaminar shear strength, and interfacial shear strength of CWPU-CF/EP were increased by 54.8 %, 36.6 %, and 58.9 %, respectively, compared with those of the unsized CF/EP composites. The research contributes to the development and industrial production of high-performance, eco-friendly bio-based water soluble organic coatings.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"315 ","pages":"Article 127852"},"PeriodicalIF":4.1,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142642975","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-15DOI: 10.1016/j.polymer.2024.127822
Jinqi Chen, Cong Luo, Yanhua Niu, Guangxian Li
Gel polymer electrolyte (GPE) is one of the promising candidates to overcome the defects of liquid and solid electrolyte for lithium metal batteries (LMBs). The obstacle for the practical application of GPEs lies in achieving a balance between ion transport, mechanical properties and interface stability. In this work, a star shaped polymer matrix polyhedral oligomeric silsesquioxane-polymethyl methacrylate (POSS-PMMA) is successfully synthesized with POSS as the core via atom transfer radical polymerization (ATRP) method. 1-ethyl-3-methylimidazole bis(trifluoromethanesulfon)imide ([EMIM][TFSI]) and bistrifluoromethanesulfonimide lithium salt (LiTFSI) are blended with the matrix to increase ionic conductivity. Attributed to the star structure and the lithium ion migration channel provided by POSS, the synthesized GPE possesses excellent balanced mechanical and electrochemical properties. To further stabilize the Li/GPE interface, a polymer and plastic crystalline electrolyte (PPCE) is coated as interface modification layer on both sides of GPE. Benefitting from the design, the synthesized GPE reaches a highly stable Li striping/plating cycling for 1000 h at 0.1 mA cm−2 with ionic conductivity of 3.5×10−4 S cm−1, Li+ transference number of 0.35, and electrochemical stability window of 4.9 V. Furthermore, the Li||POSS-PMMA-PPCE||LiFePO4 (LFP) full cell shows a high capacity retention of 99.5% after 100 cycles at 0.2 C under room temperature (RT), and the high voltage Li||POSS-PMMA-PPCE||LiNi1-x-yMnxCoyO2 (NCM811) cell shows a high capacity retention of 88.3% after 50 cycles at 0.1 C under RT. This work opens up a new frontier to stabilize the Li/GPE interface and enables safe operation of room temperature lithium metal batteries.
凝胶聚合物电解质（GPE）是克服锂金属电池（LMB）液态和固态电解质缺陷的有前途的候选材料之一。凝胶聚合物电解质的实际应用障碍在于实现离子传输、机械性能和界面稳定性之间的平衡。本研究通过原子转移自由基聚合（ATRP）方法，成功合成了以 POSS 为核心的星形聚合物基质多面体低聚硅倍半氧烷-甲基丙烯酸甲酯（POSS-PMMA）。1-ethyl-3-methylimidazole bis(trifluoromethanesulfon)imide ([EMIM][TFSI]) 和 bistrifluoromethanesulfonimide lithium salt (LiTFSI) 与基体混合以增加离子导电性。由于星形结构和 POSS 提供的锂离子迁移通道，合成的 GPE 具有优异的机械和电化学平衡特性。为了进一步稳定锂/GPE界面，在 GPE 的两侧涂覆了聚合物和塑料结晶电解质（PPCE）作为界面改性层。得益于这一设计，合成的 GPE 在 0.1 mA cm-2 下可实现 1000 h 高度稳定的锂剥离/电镀循环，离子电导率为 3.5×10-4 S cm-1，锂+转移数为 0.35，电化学稳定性窗口为 4.9 V。此外，Li||POSS-PMMA-PPCE||LiFePO4（LFP）全电池在室温（RT）下 0.2 C 条件下循环 100 次后显示出 99.5% 的高容量保持率，高压 Li||POSS-PMMA-PPCE||LiNi1-x-yMnxCoyO2 （NCM811）电池在室温（RT）下 0.1 C 条件下循环 50 次后显示出 88.3% 的高容量保持率。这项工作开辟了稳定锂/GPE 界面的新领域，使室温锂金属电池能够安全运行。
{"title":"A star polymer POSS-PMMA based gel electrolyte with balanced electrochemical and mechanical properties for lithium metal battery","authors":"Jinqi Chen, Cong Luo, Yanhua Niu, Guangxian Li","doi":"10.1016/j.polymer.2024.127822","DOIUrl":"https://doi.org/10.1016/j.polymer.2024.127822","url":null,"abstract":"Gel polymer electrolyte (GPE) is one of the promising candidates to overcome the defects of liquid and solid electrolyte for lithium metal batteries (LMBs). The obstacle for the practical application of GPEs lies in achieving a balance between ion transport, mechanical properties and interface stability. In this work, a star shaped polymer matrix polyhedral oligomeric silsesquioxane-polymethyl methacrylate (POSS-PMMA) is successfully synthesized with POSS as the core via atom transfer radical polymerization (ATRP) method. 1-ethyl-3-methylimidazole bis(trifluoromethanesulfon)imide ([EMIM][TFSI]) and bistrifluoromethanesulfonimide lithium salt (LiTFSI) are blended with the matrix to increase ionic conductivity. Attributed to the star structure and the lithium ion migration channel provided by POSS, the synthesized GPE possesses excellent balanced mechanical and electrochemical properties. To further stabilize the Li/GPE interface, a polymer and plastic crystalline electrolyte (PPCE) is coated as interface modification layer on both sides of GPE. Benefitting from the design, the synthesized GPE reaches a highly stable Li striping/plating cycling for 1000 h at 0.1 mA cm<sup>−2</sup> with ionic conductivity of 3.5×10<sup>−4</sup> S cm<sup>−1</sup>, Li<sup>+</sup> transference number of 0.35, and electrochemical stability window of 4.9 V. Furthermore, the Li||POSS-PMMA-PPCE||LiFePO<sub>4</sub> (LFP) full cell shows a high capacity retention of 99.5% after 100 cycles at 0.2 C under room temperature (RT), and the high voltage Li||POSS-PMMA-PPCE||LiNi<sub>1-x-y</sub>MnxCo<sub>y</sub>O<sub>2</sub> (NCM811) cell shows a high capacity retention of 88.3% after 50 cycles at 0.1 C under RT. This work opens up a new frontier to stabilize the Li/GPE interface and enables safe operation of room temperature lithium metal batteries.","PeriodicalId":405,"journal":{"name":"Polymer","volume":"5 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142642682","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-15DOI: 10.1016/j.polymer.2024.127832
Xiaodan Li , Rui He , Zecong Wei , Shiyun Meng , Zhenhua Fan
Cyanate ester resin (CE), a high-performance and low dielectric materials, was modified with amino hollow silica (HSMs-NH2) and polyimide resin (PI) to form an IPN structure. Reducing the crosslinking density of the composite system and accompanying with its steric hindrance effect, PI increased the free volume of the composite material. The hollow structure introduced by HSMs-NH2 further enhanced a low dielectric property. IPN structure and HSMs-NH2 also significantly improved the impact toughness of HSMs-NH2/PI/CE composites. The bonding between the Si–O–Si and HSMs-NH2 offered an excellent heat resistance and as well surface bonding capability to matrix, which reduced the decomposition and effectively improved their thermal stability. Simultaneously, profited by the hydrophobicity of Si–O–Si, HSMs-NH2/PI/CE composite materials enabled to keep low dielectric properties in humid environments.
{"title":"Nanoporous and IPN structural composite material of cyanate ester modified by hollow silica and polyimide","authors":"Xiaodan Li , Rui He , Zecong Wei , Shiyun Meng , Zhenhua Fan","doi":"10.1016/j.polymer.2024.127832","DOIUrl":"10.1016/j.polymer.2024.127832","url":null,"abstract":"<div><div>Cyanate ester resin (CE), a high-performance and low dielectric materials, was modified with amino hollow silica (HSMs-NH<sub>2</sub>) and polyimide resin (PI) to form an IPN structure. Reducing the crosslinking density of the composite system and accompanying with its steric hindrance effect, PI increased the free volume of the composite material. The hollow structure introduced by HSMs-NH<sub>2</sub> further enhanced a low dielectric property. IPN structure and HSMs-NH<sub>2</sub> also significantly improved the impact toughness of HSMs-NH<sub>2</sub>/PI/CE composites. The bonding between the Si–<em>O</em>–Si and HSMs-NH<sub>2</sub> offered an excellent heat resistance and as well surface bonding capability to matrix, which reduced the decomposition and effectively improved their thermal stability. Simultaneously, profited by the hydrophobicity of Si–<em>O</em>–Si, HSMs-NH<sub>2</sub>/PI/CE composite materials enabled to keep low dielectric properties in humid environments.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"315 ","pages":"Article 127832"},"PeriodicalIF":4.1,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142637493","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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