Pub Date : 2025-01-23DOI: 10.1016/j.polymer.2025.128078
Jiahao Mao, Jierui Zhou, Yang Cao, Mukerrem Cakmak
This study examines the morphological evolution of melt-cast Poly(ethylene terephthalate) (PET) thin films under nonlinear deformation strategies, specifically stretching and cycling, to analyze their structural, mechanical, and electrical properties. Capacitor-grade thin films were melt-cast and subjected to uniaxial deformation using an instrumented stretching machine that applied programmable deformations. During deformation, real-time mechano-optical data, including birefringence, true strain, and true stress, were collected above the glass transition temperature (Tg).Stress-induced crystallization emerged as the primary mechanism during stretching, as thermally induced crystallization was suppressed due to high viscosity in the rubbery temperatures near Tg. Strain oscillations after steady deformations at various strain levels promoted crystallization and relaxed oriented amorphous chains. This process enhanced crystalline orientation and crystallinity, particularly in stretching and oscillation tests compared to stretching and holding tests. At higher deformation levels, the orientation of amorphous domains transitioned to oriented crystalline structures. Increased crystallinity and crystalline and amorphous chain orientation enhanced electrical breakdown. The strain oscillation played a crucial role in promoting crystallinity enhancement while minimizing amorphous chain orientation, leading to lower electrical breakdown. These results highlight the substantial influence of the amorphous phase and its chain orientation on the electrical breakdown of PET films.
{"title":"IMPACT OF UNIAXIAL STRAIN PROGRAMMING ON MORPHOLOGY AND ELECTRICAL PROPERTIES OF PET FROM AMORPHOUS PRECURSORS","authors":"Jiahao Mao, Jierui Zhou, Yang Cao, Mukerrem Cakmak","doi":"10.1016/j.polymer.2025.128078","DOIUrl":"https://doi.org/10.1016/j.polymer.2025.128078","url":null,"abstract":"This study examines the morphological evolution of melt-cast Poly(ethylene terephthalate) (PET) thin films under nonlinear deformation strategies, specifically stretching and cycling, to analyze their structural, mechanical, and electrical properties. Capacitor-grade thin films were melt-cast and subjected to uniaxial deformation using an instrumented stretching machine that applied programmable deformations. During deformation, real-time mechano-optical data, including birefringence, true strain, and true stress, were collected above the glass transition temperature (Tg).Stress-induced crystallization emerged as the primary mechanism during stretching, as thermally induced crystallization was suppressed due to high viscosity in the rubbery temperatures near Tg. Strain oscillations after steady deformations at various strain levels promoted crystallization and relaxed oriented amorphous chains. This process enhanced crystalline orientation and crystallinity, particularly in stretching and oscillation tests compared to stretching and holding tests. At higher deformation levels, the orientation of amorphous domains transitioned to oriented crystalline structures. Increased crystallinity and crystalline and amorphous chain orientation enhanced electrical breakdown. The strain oscillation played a crucial role in promoting crystallinity enhancement while minimizing amorphous chain orientation, leading to lower electrical breakdown. These results highlight the substantial influence of the amorphous phase and its chain orientation on the electrical breakdown of PET films.","PeriodicalId":405,"journal":{"name":"Polymer","volume":"20 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143027025","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 : 2025-01-23DOI: 10.1016/j.polymer.2025.128079
Jiaxin He, Hongtao Shan, Xueting Cao, Jianjun Zhou, Hong Huo
Understanding the factors affecting stability is crucial for achieving commercial success with doped conjugated polymers (CPs). In this work, we sequentially doped poly(3-hexylthiophene) (P3HT) films with 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) from chlorobenzene/acetonitrile (CB/AN) solvent blends and stored the doped P3HT films under inert conditions at room temperature. The sequential doping of the P3HT film was accompanied by solution doping when CB was used to prepare the F4TCNQ solution. By combining UV‒visible‒near infrared (UV‒vis‒NIR) spectroscopy, Fourier transform infrared (FTIR) spectroscopy, and grazing-incidence wide-angle X-ray diffraction (GIXRD) measurements, we found that with prolonged storage time, the microstructures of doped P3HT produced by sequential doping could retain crystalline structures; however, the crystalline aggregates produced by solution doping would recover back to amorphous chains. The diffidence between the microstructures leads to the conductivity σ, the carrier density n and mobility μ of the P3HT film doped with F4TCNQ from CB/AN blend decreased faster than that doped from pure AN. Two doping mechanisms, namely, integer charge transfer (ICT) and charge transfer complexes (CTCs), occurred in each freshly doped P3HT film. The order of the ICT phase influenced its stability, regardless of its formation from solution doping or sequential doping. The lower the order of the ICT phase is, the better its stability. Both the ICT and CTC phases were unstable at room temperature, yet no interconversion between them was observed.
{"title":"Effects of dopant solution solvent on the stability of doped P3HT films","authors":"Jiaxin He, Hongtao Shan, Xueting Cao, Jianjun Zhou, Hong Huo","doi":"10.1016/j.polymer.2025.128079","DOIUrl":"https://doi.org/10.1016/j.polymer.2025.128079","url":null,"abstract":"Understanding the factors affecting stability is crucial for achieving commercial success with doped conjugated polymers (CPs). In this work, we sequentially doped poly(3-hexylthiophene) (P3HT) films with 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) from chlorobenzene/acetonitrile (CB/AN) solvent blends and stored the doped P3HT films under inert conditions at room temperature. The sequential doping of the P3HT film was accompanied by solution doping when CB was used to prepare the F4TCNQ solution. By combining UV‒visible‒near infrared (UV‒vis‒NIR) spectroscopy, Fourier transform infrared (FTIR) spectroscopy, and grazing-incidence wide-angle X-ray diffraction (GIXRD) measurements, we found that with prolonged storage time, the microstructures of doped P3HT produced by sequential doping could retain crystalline structures; however, the crystalline aggregates produced by solution doping would recover back to amorphous chains. The diffidence between the microstructures leads to the conductivity σ, the carrier density <em>n</em> and mobility <em>μ</em> of the P3HT film doped with F4TCNQ from CB/AN blend decreased faster than that doped from pure AN. Two doping mechanisms, namely, integer charge transfer (ICT) and charge transfer complexes (CTCs), occurred in each freshly doped P3HT film. The order of the ICT phase influenced its stability, regardless of its formation from solution doping or sequential doping. The lower the order of the ICT phase is, the better its stability. Both the ICT and CTC phases were unstable at room temperature, yet no interconversion between them was observed.","PeriodicalId":405,"journal":{"name":"Polymer","volume":"76 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143026982","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}
Low-density polyethylene (LDPE) is an excellent insulating material that ensures the safe and reliable operation of high-voltage direct current (HVDC) cables. The insulation properties of LDPE can be improved by doping with voltage stabilizers. Due to its electron-withdrawing property, [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) has the potential to be used as a voltage stabilizer to improve the DC insulation performance of LDPE, especially the high temperature insulation performance of cable insulation. Therefore, the impact of PCBM on carrier trap characteristics and micro charge transport at high temperatures and high fields requires further study. LDPE is used as the matrix material to prepare composites with concentrations of 0.5 and 1wt%. The experimental results show that the Weibull characteristic breakdown strength can be increased by 10.5% and the DC electrical conductivity can be reduced by 73.6% at 90 °C, when the PCBM doping concentration is 0.5wt%. These results can be explained by trap characteristics and molecular chain displacement. It reveals that the introduction of PCBM can effectively increase the trap density, which can capture more charge carriers, resulting in a decrease in carrier mobility and electrical conductivity. Quantum chemical calculations indicate that owing to the high electron affinity and low ionization potential of PCBM, it is more prone to attracting and capturing electrons, thereby efficiently absorbing high-energy electron energy. Moreover, PCBM makes the amorphous region more tightly ordered, which manifests as an improvement in crystallinity. It also enhances the friction coefficient of the molecular chain and suppresses the molecular chain displacement in LDPE, which is verified by charge transport and molecular displacement modulated model simulations. This study provides a new method for improving the properties of cable insulation materials.
{"title":"Highly insulating LDPE compounds at high temperature: the effect of electron-withdrawing PCBM on DC dielectric properties","authors":"Minhui Zhu, Daomin Min, Shihang Wang, Yihang Jiang","doi":"10.1016/j.polymer.2025.128052","DOIUrl":"https://doi.org/10.1016/j.polymer.2025.128052","url":null,"abstract":"Low-density polyethylene (LDPE) is an excellent insulating material that ensures the safe and reliable operation of high-voltage direct current (HVDC) cables. The insulation properties of LDPE can be improved by doping with voltage stabilizers. Due to its electron-withdrawing property, [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) has the potential to be used as a voltage stabilizer to improve the DC insulation performance of LDPE, especially the high temperature insulation performance of cable insulation. Therefore, the impact of PCBM on carrier trap characteristics and micro charge transport at high temperatures and high fields requires further study. LDPE is used as the matrix material to prepare composites with concentrations of 0.5 and 1wt%. The experimental results show that the Weibull characteristic breakdown strength can be increased by 10.5% and the DC electrical conductivity can be reduced by 73.6% at 90 °C, when the PCBM doping concentration is 0.5wt%. These results can be explained by trap characteristics and molecular chain displacement. It reveals that the introduction of PCBM can effectively increase the trap density, which can capture more charge carriers, resulting in a decrease in carrier mobility and electrical conductivity. Quantum chemical calculations indicate that owing to the high electron affinity and low ionization potential of PCBM, it is more prone to attracting and capturing electrons, thereby efficiently absorbing high-energy electron energy. Moreover, PCBM makes the amorphous region more tightly ordered, which manifests as an improvement in crystallinity. It also enhances the friction coefficient of the molecular chain and suppresses the molecular chain displacement in LDPE, which is verified by charge transport and molecular displacement modulated model simulations. This study provides a new method for improving the properties of cable insulation materials.","PeriodicalId":405,"journal":{"name":"Polymer","volume":"51 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143027026","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 : 2025-01-20DOI: 10.1016/j.polymer.2025.128065
Simão V. Pandeirada, Catarina F. Araújo, Mariela M. Nolasco, Pedro D. Vaz, Svemir Rudić, Armando J.D. Silvestre, Nathanael Guigo, Paulo Ribeiro-Claro, Andreia F. Sousa
The development of furandicarboxylic acid (FDCA) based polymers and materials is a rapidly growing research field in both academia and industry, driven by the need to replace fossil-based polymers with more sustainable alternatives. Despite the unequivocal potential of poly(ethylene 2,5-furandicarboxylate) (2,5-PEF), many other furanic polyesters, such as poly(ethylene 3,4-furandicarboxylate) (3,4-PEF), synthetized from the 3,4-FDCA isomer, remain underexplored. This study is the first to explore the conformational preferences of 3,4-PEF polyester using vibrational spectroscopy and density functional theory calculations. Additionally, a comprehensive thermal characterization of 3,4-PEF addresses current gaps in the literature.The results suggest that, in crystalline domains, 3,4-PEF chains adopt the ss-t conformation, where the 3,4-FDCA segment exhibits a syn-syn motif and the ethylene glycol (EG) segment is in the trans conformation (ss-t). In amorphous regions, however, multiple conformations coexist, with syn-syn-gauche (ss-g) and anti-syn-gauche (as-g) segments accounting for the bulk of the population distribution. As previously observed for 2,5-PEF, the formation of C-H···O interactions in the crystalline domain is the main driver for the crystallization preferences of 3,4-PEF. The energetic gain from interchain C-H···O bond formation compensates for the energy penalty associated with the ss-g/as-g to ss-t conformational transition.Differential scanning calorimetry (DSC) analysis revealed that 3,4-PEF has a glass transition temperature (Tg) of 39 °C and a melting temperature (Tm) of 155 °C. Kinetic studies showed that the fastest crystallization rate for 3,4-PEF occurs at 110 °C, with a half crystallization time of 12 min. Interestingly, 3,4-PEF crystallizes faster than 2,5-PEF at its optimal crystallization temperature (170 °C), though still more slowly than poly(ethylene terephthalate). These findings suggest that 3,4-PEF holds promise as a renewable polymer with fast crystallization behaviour.
{"title":"Unveiling the uncommon crystallization features of 3,4-PEF, a thermal and DFT study","authors":"Simão V. Pandeirada, Catarina F. Araújo, Mariela M. Nolasco, Pedro D. Vaz, Svemir Rudić, Armando J.D. Silvestre, Nathanael Guigo, Paulo Ribeiro-Claro, Andreia F. Sousa","doi":"10.1016/j.polymer.2025.128065","DOIUrl":"https://doi.org/10.1016/j.polymer.2025.128065","url":null,"abstract":"The development of furandicarboxylic acid (FDCA) based polymers and materials is a rapidly growing research field in both academia and industry, driven by the need to replace fossil-based polymers with more sustainable alternatives. Despite the unequivocal potential of poly(ethylene 2,5-furandicarboxylate) (2,5-PEF), many other furanic polyesters, such as poly(ethylene 3,4-furandicarboxylate) (3,4-PEF), synthetized from the 3,4-FDCA isomer, remain underexplored. This study is the first to explore the conformational preferences of 3,4-PEF polyester using vibrational spectroscopy and density functional theory calculations. Additionally, a comprehensive thermal characterization of 3,4-PEF addresses current gaps in the literature.The results suggest that, in crystalline domains, 3,4-PEF chains adopt the <em>ss-t</em> conformation, where the 3,4-FDCA segment exhibits a <em>syn-syn</em> motif and the ethylene glycol (EG) segment is in the <em>trans</em> conformation (<em>ss-t</em>). In amorphous regions, however, multiple conformations coexist, with <em>syn-syn-gauche (ss-g)</em> and <em>anti-syn-gauche (as-g)</em> segments accounting for the bulk of the population distribution. As previously observed for 2,5-PEF, the formation of C-H···O interactions in the crystalline domain is the main driver for the crystallization preferences of 3,4-PEF. The energetic gain from interchain C-H···O bond formation compensates for the energy penalty associated with the <em>ss-g/as-g</em> to <em>ss-t</em> conformational transition.Differential scanning calorimetry (DSC) analysis revealed that 3,4-PEF has a glass transition temperature (<em>T</em><sub><em>g</em></sub>) of 39 °C and a melting temperature (<em>T</em><sub><em>m</em></sub>) of 155 °C. Kinetic studies showed that the fastest crystallization rate for 3,4-PEF occurs at 110 °C, with a half crystallization time of 12 min. Interestingly, 3,4-PEF crystallizes faster than 2,5-PEF at its optimal crystallization temperature (170 °C), though still more slowly than poly(ethylene terephthalate). These findings suggest that 3,4-PEF holds promise as a renewable polymer with fast crystallization behaviour.","PeriodicalId":405,"journal":{"name":"Polymer","volume":"6 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990749","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 : 2025-01-19DOI: 10.1016/j.polymer.2025.128059
Marcela Cristine de Alencar Lira, Válmer Azevedo de Sousa Filho, Rafael Braga da Cunha, Jaini Miscilene de Araújo, Pankaj Agrawal, Gustavo de Figueiredo Brito, Tomás Jeferson Alves de Mélo
The demand for flexible and functional materials in additive manufacturing has spurred interest in polymer blends with shape memory capabilities. PETG, though widely used in 3D printing, lacks the flexibility required for advanced applications. The incorporation of SEBS elastomers, especially those grafted with maleic anhydride (SEBS-g-MA), into PETG matrices enhances flexibility while introducing shape memory properties. This study investigates PETG/SEBS and PETG/SEBS-g-MA blends prepared via fused filament fabrication (FFF) for 4D printing. FTIR and SEM analyses revealed a co-continuous morphology for PETG/SEBS-g-MA blends, indicating good interfacial adhesion, which improved mechanical properties and shape memory performance. In contrast, PETG/SEBS blends exhibited a sea-island morphology with reduced compatibilization. Blends with 13% styrene content in SEBS showed high flexibility, with modulus values of 2–5 MPa and elongations over 230%, producing soft, elastic materials. Shape memory performance, evaluated in water and via rheometry, demonstrated near-100% recovery and fixation for all blends, with water-activated recovery outperforming torsion tests. Filaments (1.6–1.8 mm diameter) were successfully produced, enabling 4D printing applications. Blends like PETG/SEBS-g-MA (30% styrene) showed superior dimensional control and printing ease due to improved compatibilization. In conclusion, PETG/SEBS and PETG/SEBS-g-MA blends offer a significant improvement in flexibility and shape memory capabilities, making them ideal candidates for 4D printing. The combination of excellent mechanical properties, high shape recovery, and successful filament production underscores their potential for use in dynamic and adaptive printed structures.
{"title":"4D Printing Behavior of PETG/SEBS Blends: A Comparative Study of Reactive and Non-Reactive SEBS with Varied Styrene Content","authors":"Marcela Cristine de Alencar Lira, Válmer Azevedo de Sousa Filho, Rafael Braga da Cunha, Jaini Miscilene de Araújo, Pankaj Agrawal, Gustavo de Figueiredo Brito, Tomás Jeferson Alves de Mélo","doi":"10.1016/j.polymer.2025.128059","DOIUrl":"https://doi.org/10.1016/j.polymer.2025.128059","url":null,"abstract":"The demand for flexible and functional materials in additive manufacturing has spurred interest in polymer blends with shape memory capabilities. PETG, though widely used in 3D printing, lacks the flexibility required for advanced applications. The incorporation of SEBS elastomers, especially those grafted with maleic anhydride (SEBS-g-MA), into PETG matrices enhances flexibility while introducing shape memory properties. This study investigates PETG/SEBS and PETG/SEBS-g-MA blends prepared via fused filament fabrication (FFF) for 4D printing. FTIR and SEM analyses revealed a co-continuous morphology for PETG/SEBS-g-MA blends, indicating good interfacial adhesion, which improved mechanical properties and shape memory performance. In contrast, PETG/SEBS blends exhibited a sea-island morphology with reduced compatibilization. Blends with 13% styrene content in SEBS showed high flexibility, with modulus values of 2–5 MPa and elongations over 230%, producing soft, elastic materials. Shape memory performance, evaluated in water and via rheometry, demonstrated near-100% recovery and fixation for all blends, with water-activated recovery outperforming torsion tests. Filaments (1.6–1.8 mm diameter) were successfully produced, enabling 4D printing applications. Blends like PETG/SEBS-g-MA (30% styrene) showed superior dimensional control and printing ease due to improved compatibilization. In conclusion, PETG/SEBS and PETG/SEBS-g-MA blends offer a significant improvement in flexibility and shape memory capabilities, making them ideal candidates for 4D printing. The combination of excellent mechanical properties, high shape recovery, and successful filament production underscores their potential for use in dynamic and adaptive printed structures.","PeriodicalId":405,"journal":{"name":"Polymer","volume":"30 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142989272","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}
This article presents the synthesis of a porous hybrid material, comprising a melamine-terephthaldehyde-based two-dimensional π-conjugated covalent organic framework (COF) grown on a zinc-based metal-organic framework-5 (MOF-5). This hybrid material serves as a drug-loading platform for delivering penicillin G sodium salt. The material leverages the unique interactions between its benzene ring structure and β-lactam drugs, such as penicillin G sodium salt, as well as π-π stacking interactions, cations, and aromatic systems for drug adsorption. The pH responsiveness of the release phase is attributed to the attack of hydrogen ions on these interactions within the corrosion inhibition system. SEM, infrared spectrometry, and X-ray diffraction results confirm the successful synthesis of MOF@COFs. Drug adsorption experiments indicate that the material’s maximum loading capacity reaches 51.23% ± 0.57. Release experiments at different pH levels reveal that MOF@COFs exhibit pH responsiveness, achieving an optimal release rate and duration at pH 5.0, with a release time of approximately 12 hours. Bacterial and biological toxicity tests confirm the material’s expected antibacterial efficacy and safety for practical applications.
{"title":"Crystalline porous frameworks (MOF@COF) for adsorption-desorption analysis of β-lactam drugs","authors":"Ren Li, Yueyuan Zhu, Xiuwen Zhang, Shuangying Li, Dong Wang, Zhaopeng Liu, Xinyao Wang, Yushun Hou, Shaoxiang Li","doi":"10.1016/j.polymer.2024.127973","DOIUrl":"https://doi.org/10.1016/j.polymer.2024.127973","url":null,"abstract":"This article presents the synthesis of a porous hybrid material, comprising a melamine-terephthaldehyde-based two-dimensional π-conjugated covalent organic framework (COF) grown on a zinc-based metal-organic framework-5 (MOF-5). This hybrid material serves as a drug-loading platform for delivering penicillin G sodium salt. The material leverages the unique interactions between its benzene ring structure and β-lactam drugs, such as penicillin G sodium salt, as well as π-π stacking interactions, cations, and aromatic systems for drug adsorption. The pH responsiveness of the release phase is attributed to the attack of hydrogen ions on these interactions within the corrosion inhibition system. SEM, infrared spectrometry, and X-ray diffraction results confirm the successful synthesis of MOF@COFs. Drug adsorption experiments indicate that the material’s maximum loading capacity reaches 51.23% ± 0.57. Release experiments at different pH levels reveal that MOF@COFs exhibit pH responsiveness, achieving an optimal release rate and duration at pH 5.0, with a release time of approximately 12 hours. Bacterial and biological toxicity tests confirm the material’s expected antibacterial efficacy and safety for practical applications.","PeriodicalId":405,"journal":{"name":"Polymer","volume":"8 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142989274","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 : 2025-01-18DOI: 10.1016/j.polymer.2025.128062
Ahmed Olalekan Omoniyi, Mingda Yang, Wei Bai, Olayinka Oderinde, Fengwei Gao, Yang Zhou, Jianfu Zhang, Yuanfeng Wu, Zhongmin Su
Traditional encryption technologies using single-fluorescent materials are increasingly vulnerable to attacks due to their predictable responses to stimuli. Furthermore, conventional waterborne polyurethane (WPU) film fabrication methods, such as casting, suffer from long drying times and inconsistent thickness, limiting scalability for advanced applications. To address these issues, we developed cephalopod-inspired WPU composite films that integrate 6,7-dihydroxy coumarin (6,7-CU) and perylene tetracarboxylic acid (PTCA) as fluorophores in segregated layers. This colloidal system achieves good emulsion stability and interfacial interactions, which play a crucial role in the films' complex functionality. The dyes’ hydroxy and carboxylic acid groups strengthen both optical properties and mechanical strength of WPU, achieving a tensile strength of 24 MPa in a 100 μm thin film. Using the electrochemical demulsification-induced fast solidification (DIFS) method, we achieved rapid drying and uniform film formation, overcoming the limitations of traditional casting. This method leverages controlled interfacial dynamics to produce films with sophisticated multicolor responses and improved encryption complexity. Density functional theory (DFT) calculations further reveal the films' stimuli-responsiveness, providing insights into the influence of interfacial mechanisms on their reversible color transformations under UV light and pH changes. Applications in data engraving and QR code labeling demonstrate the films' potential in secure information encryption and anti-counterfeiting technologies.
{"title":"Rapid fabrication of cephalopod-inspired fluorophore-integrated waterborne polyurethane films for customizable patterns and cryptographic encryption","authors":"Ahmed Olalekan Omoniyi, Mingda Yang, Wei Bai, Olayinka Oderinde, Fengwei Gao, Yang Zhou, Jianfu Zhang, Yuanfeng Wu, Zhongmin Su","doi":"10.1016/j.polymer.2025.128062","DOIUrl":"https://doi.org/10.1016/j.polymer.2025.128062","url":null,"abstract":"Traditional encryption technologies using single-fluorescent materials are increasingly vulnerable to attacks due to their predictable responses to stimuli. Furthermore, conventional waterborne polyurethane (WPU) film fabrication methods, such as casting, suffer from long drying times and inconsistent thickness, limiting scalability for advanced applications. To address these issues, we developed cephalopod-inspired WPU composite films that integrate 6,7-dihydroxy coumarin (6,7-CU) and perylene tetracarboxylic acid (PTCA) as fluorophores in segregated layers. This colloidal system achieves good emulsion stability and interfacial interactions, which play a crucial role in the films' complex functionality. The dyes’ hydroxy and carboxylic acid groups strengthen both optical properties and mechanical strength of WPU, achieving a tensile strength of 24 MPa in a 100 μm thin film. Using the electrochemical demulsification-induced fast solidification (DIFS) method, we achieved rapid drying and uniform film formation, overcoming the limitations of traditional casting. This method leverages controlled interfacial dynamics to produce films with sophisticated multicolor responses and improved encryption complexity. Density functional theory (DFT) calculations further reveal the films' stimuli-responsiveness, providing insights into the influence of interfacial mechanisms on their reversible color transformations under UV light and pH changes. Applications in data engraving and QR code labeling demonstrate the films' potential in secure information encryption and anti-counterfeiting technologies.","PeriodicalId":405,"journal":{"name":"Polymer","volume":"10 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-01-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142989273","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 : 2025-01-18DOI: 10.1016/j.polymer.2025.128072
Xiaohuan Bu, Wei Zhao, Xin Li, Wenjie Zhang, Yuancheng Zhang, Ge Shi, Yanjie He, Zhe Cui, Peng Fu, Xinchang Pang, Hong Wu, Xiaomeng Zhang, Minying Liu
Polyamide 66 (PA66) with less entangled structure, high crystallinity and excellent mechanical properties was fabricated in this work by direct solid-state polymerization (DSSP) method. The polymerization process and mechanism of DSSP were systematically investigated. Results demonstrate that DSSP is a transition process from salt crystal directly to polymer crystal, enabling the production of PA66 with a less entangled and highly crystalline structure. DSSP sample exhibits a crystallinity of 51.8% as tested by WAXD, and 59.7% when measured via DSC, surpassing the crystallinity of the majority of PA66 fibers. Furthermore, the sample achieves a maximum melting point of 271.7 °C. Correspondingly, mechanical properties and heat distortion temperature of DSSP sample are also improved. Therefore, this work enhances the in-depth understanding of polymerization mechanism of DSSP, and provides an efficient, scalable approach for fabricating polymers with less entanglement, high crystallinity, and exceptional performance characteristics.
{"title":"Large-scale Fabrication of Less Entangled Polyamide by Direct Solid-state Polymerization and the Impact of Entanglement on Crystal Structure and Performance","authors":"Xiaohuan Bu, Wei Zhao, Xin Li, Wenjie Zhang, Yuancheng Zhang, Ge Shi, Yanjie He, Zhe Cui, Peng Fu, Xinchang Pang, Hong Wu, Xiaomeng Zhang, Minying Liu","doi":"10.1016/j.polymer.2025.128072","DOIUrl":"https://doi.org/10.1016/j.polymer.2025.128072","url":null,"abstract":"Polyamide 66 (PA66) with less entangled structure, high crystallinity and excellent mechanical properties was fabricated in this work by direct solid-state polymerization (DSSP) method. The polymerization process and mechanism of DSSP were systematically investigated. Results demonstrate that DSSP is a transition process from salt crystal directly to polymer crystal, enabling the production of PA66 with a less entangled and highly crystalline structure. DSSP sample exhibits a crystallinity of 51.8% as tested by WAXD, and 59.7% when measured via DSC, surpassing the crystallinity of the majority of PA66 fibers. Furthermore, the sample achieves a maximum melting point of 271.7 °C. Correspondingly, mechanical properties and heat distortion temperature of DSSP sample are also improved. Therefore, this work enhances the in-depth understanding of polymerization mechanism of DSSP, and provides an efficient, scalable approach for fabricating polymers with less entanglement, high crystallinity, and exceptional performance characteristics.","PeriodicalId":405,"journal":{"name":"Polymer","volume":"101 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-01-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142989275","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}
Eco-friendly plastics are an emerging class of sustainable polymers. However, the process of developing high-performance sustainable polymers often requires the preparation of high-purity monomers from less pure biomass feedstocks. This process is not only complex, but also makes the bio-based feedstock less atom-economical, resulting in higher product costs. In this study, it is proposed to develop cyclic epoxy monomer from tung oil (TO), which are reacted with citric acid (CA) in simple curing reaction to prepare tung oil-based epoxy resins with sustainable recycling properties. These epoxy resins are thermally stable and possess tunable mechanical properties. The dynamic reversible covalent bonding of β-hydroxy esters introduced in the crosslinked network gives the polymer both reprocessable and chemically recyclable properties. In addition, the abundant hydroxyl are able to produce a variety of non-covalent interactions with the adherent substrate, thus exhibiting excellent adhesive properties. The combination of plant oil, thermoplastic-like behavior, and sustainable recycling provides new ideas for the development of new plant oil-based eco-friendly polymer materials.
{"title":"Eco-friendly epoxy resin derived from tung oil and their sustainable recycling","authors":"Jindong Li, Guodong Xu, Yaowen Hu, Jingjing Fan, Zhongkai Wang, Yongliang Ding","doi":"10.1016/j.polymer.2025.128069","DOIUrl":"https://doi.org/10.1016/j.polymer.2025.128069","url":null,"abstract":"Eco-friendly plastics are an emerging class of sustainable polymers. However, the process of developing high-performance sustainable polymers often requires the preparation of high-purity monomers from less pure biomass feedstocks. This process is not only complex, but also makes the bio-based feedstock less atom-economical, resulting in higher product costs. In this study, it is proposed to develop cyclic epoxy monomer from tung oil (TO), which are reacted with citric acid (CA) in simple curing reaction to prepare tung oil-based epoxy resins with sustainable recycling properties. These epoxy resins are thermally stable and possess tunable mechanical properties. The dynamic reversible covalent bonding of <em>β</em>-hydroxy esters introduced in the crosslinked network gives the polymer both reprocessable and chemically recyclable properties. In addition, the abundant hydroxyl are able to produce a variety of non-covalent interactions with the adherent substrate, thus exhibiting excellent adhesive properties. The combination of plant oil, thermoplastic-like behavior, and sustainable recycling provides new ideas for the development of new plant oil-based eco-friendly polymer materials.","PeriodicalId":405,"journal":{"name":"Polymer","volume":"30 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142988266","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}
Zn-Al layered double hydroxides (Zn-Al LDHs) were prepared in situ on the surface of zirconium phosphate (ZrP) nanosheets in order to improve the lubricating capabilities of LDHs in waterborne epoxy (WEP). Subsequently, ZrP-LDHs (ZL) were functionally modified with tannic acid (TA) and cerium ions (Ce(Ⅲ)) to prepare ZrP-LDH-PTA-Ce(Ⅲ) (TCZL) nanohybrids. Subsequently, the WEP coating was combined with TCZL to create a dual-purpose coating exhibiting wear resistance and anti-corrosion properties. The tribological test results demonstrated that the WEP coating containing TCZL (TCZL/WEP) exhibited a 75.27% lower wear rate than the blank WEP coating. Furthermore, the Electrochemical impedance spectroscopy (EIS) showed that the impedance modulus at 0.01 Hz (|Z|0.01 Hz) of the TCZL/WEP coating was roughly 2 orders of magnitude higher than that of the blank WEP coating after 35 days of corrosion. In summary, TCZL/WEP exhibits excellent wear resistance and anti-corrosion performance. This high-performance functional coating exhibits excellent anti-corrosion and excellent wear resistance, with numerous application opportunities across multiple industries.
{"title":"In situ growth of layered double hydroxides on zirconium phosphate for reinforcing anti-corrosion and wear resistance of waterborne epoxy coatings","authors":"Ruiqin Guo, Caiyou Ding, Yuan Liu, Xiaoling Cheng, Li Zhang, Wenlin Zhao, Xinxin Sheng","doi":"10.1016/j.polymer.2025.128048","DOIUrl":"https://doi.org/10.1016/j.polymer.2025.128048","url":null,"abstract":"Zn-Al layered double hydroxides (Zn-Al LDHs) were prepared in situ on the surface of zirconium phosphate (ZrP) nanosheets in order to improve the lubricating capabilities of LDHs in waterborne epoxy (WEP). Subsequently, ZrP-LDHs (ZL) were functionally modified with tannic acid (TA) and cerium ions (Ce(Ⅲ)) to prepare ZrP-LDH-PTA-Ce(Ⅲ) (TCZL) nanohybrids. Subsequently, the WEP coating was combined with TCZL to create a dual-purpose coating exhibiting wear resistance and anti-corrosion properties. The tribological test results demonstrated that the WEP coating containing TCZL (TCZL/WEP) exhibited a 75.27% lower wear rate than the blank WEP coating. Furthermore, the Electrochemical impedance spectroscopy (EIS) showed that the impedance modulus at 0.01 Hz (|Z|<sub>0.01 Hz</sub>) of the TCZL/WEP coating was roughly 2 orders of magnitude higher than that of the blank WEP coating after 35 days of corrosion. In summary, TCZL/WEP exhibits excellent wear resistance and anti-corrosion performance. This high-performance functional coating exhibits excellent anti-corrosion and excellent wear resistance, with numerous application opportunities across multiple industries.","PeriodicalId":405,"journal":{"name":"Polymer","volume":"30 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142988265","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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