Teng Ma, Yaxin An, Zezhang T. Wen, Jiaxin Zhang, Dandan Lian, Jianjun Lu, Hua Wang
ABSTRACT This study innovatively used polyethylene glycol (PEG) as a multifunctional modifier to prepare nano‐zinc oxide and polyhexamethylene guanidine hydrochloride (Nano ZnO/PHMG) hybrid melt‐blown antibacterial composite materials by twin‐screw blending. PEG overcame traditional additives' single‐function limitation, achieving dual structural regulation and antibacterial enhancement. PEG rheological properties were modulated to produce multistage fiber structures, improving filtration performance, while simultaneously optimizing antibacterial component distribution through its water solubility. Systematic experiments revealed how PEG‐regulated local viscosity affected multistage fiber formation and pore distribution, directly impacting filtration performance. At 12% PEG loading (ABA‐PP‐12PEG), optimal comprehensive performance was demonstrated: 77.45% filtration efficiency (153.5% increased) with 34.0% lower resistance (11.28 Pa). Post‐treatment further enhanced performance to 80.06% efficiency and 10.68 Pa resistance. Antibacterial rates surged 6.7‐fold from 1.78 to 12.01.
{"title":"Multifunctional Micro/Nano‐Scale Nonwoven With Antibacterial Properties for Efficient Capture of <scp>PM<sub>0.3</sub></scp>","authors":"Teng Ma, Yaxin An, Zezhang T. Wen, Jiaxin Zhang, Dandan Lian, Jianjun Lu, Hua Wang","doi":"10.1002/pen.70090","DOIUrl":"https://doi.org/10.1002/pen.70090","url":null,"abstract":"ABSTRACT This study innovatively used polyethylene glycol (PEG) as a multifunctional modifier to prepare nano‐zinc oxide and polyhexamethylene guanidine hydrochloride (Nano ZnO/PHMG) hybrid melt‐blown antibacterial composite materials by twin‐screw blending. PEG overcame traditional additives' single‐function limitation, achieving dual structural regulation and antibacterial enhancement. PEG rheological properties were modulated to produce multistage fiber structures, improving filtration performance, while simultaneously optimizing antibacterial component distribution through its water solubility. Systematic experiments revealed how PEG‐regulated local viscosity affected multistage fiber formation and pore distribution, directly impacting filtration performance. At 12% PEG loading (ABA‐PP‐12PEG), optimal comprehensive performance was demonstrated: 77.45% filtration efficiency (153.5% increased) with 34.0% lower resistance (11.28 Pa). Post‐treatment further enhanced performance to 80.06% efficiency and 10.68 Pa resistance. Antibacterial rates surged 6.7‐fold from 1.78 to 12.01.","PeriodicalId":20281,"journal":{"name":"Polymer Engineering and Science","volume":"65 10","pages":"5544-5560"},"PeriodicalIF":0.0,"publicationDate":"2025-08-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147333045","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ABSTRACT Utilizing unsaturated fatty acids from sunflower oil refining sludge is strategically important for improving oil utilization efficiency and promoting environmental outcomes. Unsaturated fatty acid methyl esters (U‐FAMEs) were extracted and applied as a precursor for epoxidation in this work. A maximum content of the epoxide groups (4.0 mol/L) in the epoxidized sunflower oil (ESO) was achieved with optimized epoxidation conditions: a molar ratio of U‐FAMEs, acetic acid, and hydrogen peroxide (H 2 O 2 ) of 0.5:1.0:1 after being reacted at 50°C and 100 rpm for 7 h. Via a solution casting method, ESO was then combined with tapioca, corn starch, and tigernut starches to produce bioplastics, and their mechanical properties, transparency, and waterproof performance were evaluated. The results demonstrate that the bioplastic synthesized with ESO and silylated tapioca starch exhibited superior heat stability with a maximum decomposition temperature at 322.2°C, while the one synthesized with ESO and silylated tigernut starches showed enhanced mechanical properties (tensile strength: 4.6 MPa; elongation at break: 22.9%). These results suggest that unsaturated fatty acids derived from sunflower oil refining sludge can be used as a potential precursor in bioplastic fabrication and offer valuable insights for the development of biodegradable alternatives to traditional plastics.
{"title":"A Novel Approach to Starch‐Based Bioplastics Development by Fatty Acid Epoxides Coupling","authors":"Huixian Guo, Qiuming Peng, Xueying Liu, Jin‐Yuan Hu, Xiao‐Shuang Cai, Wenting Yin, Hua‐Min Liu","doi":"10.1002/pen.70063","DOIUrl":"https://doi.org/10.1002/pen.70063","url":null,"abstract":"ABSTRACT Utilizing unsaturated fatty acids from sunflower oil refining sludge is strategically important for improving oil utilization efficiency and promoting environmental outcomes. Unsaturated fatty acid methyl esters (U‐FAMEs) were extracted and applied as a precursor for epoxidation in this work. A maximum content of the epoxide groups (4.0 mol/L) in the epoxidized sunflower oil (ESO) was achieved with optimized epoxidation conditions: a molar ratio of U‐FAMEs, acetic acid, and hydrogen peroxide (H 2 O 2 ) of 0.5:1.0:1 after being reacted at 50°C and 100 rpm for 7 h. Via a solution casting method, ESO was then combined with tapioca, corn starch, and tigernut starches to produce bioplastics, and their mechanical properties, transparency, and waterproof performance were evaluated. The results demonstrate that the bioplastic synthesized with ESO and silylated tapioca starch exhibited superior heat stability with a maximum decomposition temperature at 322.2°C, while the one synthesized with ESO and silylated tigernut starches showed enhanced mechanical properties (tensile strength: 4.6 MPa; elongation at break: 22.9%). These results suggest that unsaturated fatty acids derived from sunflower oil refining sludge can be used as a potential precursor in bioplastic fabrication and offer valuable insights for the development of biodegradable alternatives to traditional plastics.","PeriodicalId":20281,"journal":{"name":"Polymer Engineering and Science","volume":"65 10","pages":"5378-5388"},"PeriodicalIF":0.0,"publicationDate":"2025-07-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147382088","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Xianwu Cao, Shiqi Yang, Qilong Huang, Zhiyan Pan, Yixin Xie, Yizhang Tong, Kui He
ABSTRACT Thermoplastic polyimides (PI) are attractive for wide‐ranging industrial applications owing to easier processability compared to traditional thermosetting PI. Unfortunately, most thermoplastic PI is endowed with thermoplasticity and processability by introducing flexible segments at the expense of heat resistance. Herein, a series of thermoplastic PI films with a twisted non‐coplanar structure, flexible ether bond, and pendant methyl group were synthesized via quaternary copolymerization. Controlling the molecular chain structures of such PI films by tuning the molar ratio of dianhydride to diamine was found to offer PI more comprehensive properties. The structure–property relationship of quaternary copolymerized PI with more diversified groups studied in this paper would offer guidance for solving the problem of difficult coexistence of heat resistance and thermoplasticity in thermoplastic PI.
{"title":"Thermoplastic Polyimides With Enhanced Processability and Thermal Stability via Molecular Structure Modulation","authors":"Xianwu Cao, Shiqi Yang, Qilong Huang, Zhiyan Pan, Yixin Xie, Yizhang Tong, Kui He","doi":"10.1002/pen.70064","DOIUrl":"https://doi.org/10.1002/pen.70064","url":null,"abstract":"ABSTRACT Thermoplastic polyimides (PI) are attractive for wide‐ranging industrial applications owing to easier processability compared to traditional thermosetting PI. Unfortunately, most thermoplastic PI is endowed with thermoplasticity and processability by introducing flexible segments at the expense of heat resistance. Herein, a series of thermoplastic PI films with a twisted non‐coplanar structure, flexible ether bond, and pendant methyl group were synthesized via quaternary copolymerization. Controlling the molecular chain structures of such PI films by tuning the molar ratio of dianhydride to diamine was found to offer PI more comprehensive properties. The structure–property relationship of quaternary copolymerized PI with more diversified groups studied in this paper would offer guidance for solving the problem of difficult coexistence of heat resistance and thermoplasticity in thermoplastic PI.","PeriodicalId":20281,"journal":{"name":"Polymer Engineering and Science","volume":"65 10","pages":"5389-5401"},"PeriodicalIF":0.0,"publicationDate":"2025-07-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147333329","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ABSTRACT Hydrophobically modified ethoxylated urethane (HEUR), a typical polymer associative thickener, is extensively applied in aqueous coatings, textile printing, and resin coatings to regulate the rheological properties of the system. However, conventional branched HEURs face two critical limitations: (1) the risk of excessive cross‐linking during the chain‐expansion stage due to high monomer reactivity; (2) the phase‐separation phenomenon in some branched HEUR aqueous solutions upon standing. To overcome these challenges, we designed and synthesized a polyhydroxy hyperbranched structure (PU‐OH 3‐6 ). This structure features two main advantages: a larger central backbone and a greater spacing between active groups (OH). The hyperbranched HEUR 3‐6 synthesized using PU‐OH 3‐6 as a branched‐type chain extender is more controllable and viable in the production process. Moreover, various testing methods were employed to assess the thickening performance, salt resistance, and water retention of HEUR in a pure‐water system. The results indicated that the branched structures of HEUR 3‐6 have better thickening properties compared with the previously reported HEUR with a linear structure (HEUR L ), and branched HEUR with using gamma‐triol (HEUR GI ), pentaerythritol (HEUR P ), and xylitol (HEUR X ) to expand the chain. Among them, HEUR 5 demonstrated the best thickening effect in pure‐water systems, while in salt‐containing solutions, HEUR 6 with a six‐branched degree showed more pronounced anti‐electrolyte properties.
{"title":"Synthesis and Properties of Branched Waterborne Polyurethane Thickener With Multiple Arms","authors":"Haikuan Chen, Xiaoyi Sun, Ning Qing, Liuyan Tang","doi":"10.1002/pen.70030","DOIUrl":"https://doi.org/10.1002/pen.70030","url":null,"abstract":"ABSTRACT Hydrophobically modified ethoxylated urethane (HEUR), a typical polymer associative thickener, is extensively applied in aqueous coatings, textile printing, and resin coatings to regulate the rheological properties of the system. However, conventional branched HEURs face two critical limitations: (1) the risk of excessive cross‐linking during the chain‐expansion stage due to high monomer reactivity; (2) the phase‐separation phenomenon in some branched HEUR aqueous solutions upon standing. To overcome these challenges, we designed and synthesized a polyhydroxy hyperbranched structure (PU‐OH 3‐6 ). This structure features two main advantages: a larger central backbone and a greater spacing between active groups (OH). The hyperbranched HEUR 3‐6 synthesized using PU‐OH 3‐6 as a branched‐type chain extender is more controllable and viable in the production process. Moreover, various testing methods were employed to assess the thickening performance, salt resistance, and water retention of HEUR in a pure‐water system. The results indicated that the branched structures of HEUR 3‐6 have better thickening properties compared with the previously reported HEUR with a linear structure (HEUR L ), and branched HEUR with using gamma‐triol (HEUR GI ), pentaerythritol (HEUR P ), and xylitol (HEUR X ) to expand the chain. Among them, HEUR 5 demonstrated the best thickening effect in pure‐water systems, while in salt‐containing solutions, HEUR 6 with a six‐branched degree showed more pronounced anti‐electrolyte properties.","PeriodicalId":20281,"journal":{"name":"Polymer Engineering and Science","volume":"65 9","pages":"4916-4931"},"PeriodicalIF":0.0,"publicationDate":"2025-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147334208","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ravi Chandra Madasani, Vinay Reddy Lokasani, Mohammad Motaher Hossain
Polymer degradation due to prolonged exposure to moisture environments is a major concern for applications where long-term durability is needed. This deterioration over time could be delayed by improving the hydrophobic properties of polymers. While many surface modification techniques have been developed over the years, in-depth understanding of the effects of surface modification on hydrophobicity and long-term durability of polymers still awaits significant learning. This study investigates the influence of surface modification, specifically, surface texturing on polymer hydrophobicity by introducing various texture types and geometries on Ultrahigh Molecular Weight Polyethylene (UHMWPE) and High Density Polyethylene (HDPE) surfaces. Hydrophobicity is evaluated by the contact angle measurements using DI water and bovine serum. The results show that introduction of surface textures significantly increases the contact angle, and, thereby, improving the hydrophobicity. Contact angle of textured HDPE surfaces increases to a maximum of 156.7° in DI water and 160.8° in bovine serum for square protrusions, compared to 104.7° and 108.6° in DI water and bovine serum, for smooth surfaces, respectively. For UHMWPE, textured surfaces achieve a maximum contact angle of 157.3° in DI water and 159.8° in bovine serum for hemispherical protrusions, compared to the smooth surface values of 98.4° in DI water and 104.0° in bovine serum. This improvement in hydrophobicity, achieved by introducing surface textures, significantly improves the resistance to moisture absorption in polymers, specifically in HDPE, with textured surfaces showing a moisture absorption of less than 1.5% compared to the smooth surface moisture absorption of 4.5%, over 90 days of immersion in DI water. A wetted surface fraction ratio is proposed to describe the relationship between surface texture and wetting of the polymer surfaces using transition state modeling approach, as this approach provides more in-depth insights on the relationship compared to the conventional Cassie-Baxter and Wenzel models. The study provides guidelines for enhancing hydrophobicity and moisture resistance, and, therefore, long-term durability of polymers used in biomedical, automotive, aerospace, electronics, and household applications.
{"title":"SURFACE TEXTURING TO IMPROVE HYDROPHOBICITY AND MOISTURE RESISTANCE OF POLYMERS.","authors":"Ravi Chandra Madasani, Vinay Reddy Lokasani, Mohammad Motaher Hossain","doi":"10.1002/pen.70040","DOIUrl":"https://doi.org/10.1002/pen.70040","url":null,"abstract":"<p><p>Polymer degradation due to prolonged exposure to moisture environments is a major concern for applications where long-term durability is needed. This deterioration over time could be delayed by improving the hydrophobic properties of polymers. While many surface modification techniques have been developed over the years, in-depth understanding of the effects of surface modification on hydrophobicity and long-term durability of polymers still awaits significant learning. This study investigates the influence of surface modification, specifically, surface texturing on polymer hydrophobicity by introducing various texture types and geometries on Ultrahigh Molecular Weight Polyethylene (UHMWPE) and High Density Polyethylene (HDPE) surfaces. Hydrophobicity is evaluated by the contact angle measurements using DI water and bovine serum. The results show that introduction of surface textures significantly increases the contact angle, and, thereby, improving the hydrophobicity. Contact angle of textured HDPE surfaces increases to a maximum of 156.7° in DI water and 160.8° in bovine serum for square protrusions, compared to 104.7° and 108.6° in DI water and bovine serum, for smooth surfaces, respectively. For UHMWPE, textured surfaces achieve a maximum contact angle of 157.3° in DI water and 159.8° in bovine serum for hemispherical protrusions, compared to the smooth surface values of 98.4° in DI water and 104.0° in bovine serum. This improvement in hydrophobicity, achieved by introducing surface textures, significantly improves the resistance to moisture absorption in polymers, specifically in HDPE, with textured surfaces showing a moisture absorption of less than 1.5% compared to the smooth surface moisture absorption of 4.5%, over 90 days of immersion in DI water. A wetted surface fraction ratio is proposed to describe the relationship between surface texture and wetting of the polymer surfaces using transition state modeling approach, as this approach provides more in-depth insights on the relationship compared to the conventional Cassie-Baxter and Wenzel models. The study provides guidelines for enhancing hydrophobicity and moisture resistance, and, therefore, long-term durability of polymers used in biomedical, automotive, aerospace, electronics, and household applications.</p>","PeriodicalId":20281,"journal":{"name":"Polymer Engineering and Science","volume":" ","pages":""},"PeriodicalIF":3.2,"publicationDate":"2025-07-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12356130/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144966006","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ABSTRACT Nanofillers are widely used to enhance the properties of polymeric materials due to their small particle size and high specific surface area. In this study, functionalized silica‐based Janus nanosheets (JNS) grafted with styrene–acrylonitrile copolymer (SAN) chains on one side and epoxy groups on the opposite side have been synthesized, termed SAN‐Silica‐epoxy JNS, and incorporated as modifiers into the acrylonitrile‐butadiene‐styrene copolymer/polyethylene terephthalate (ABS/PET) blends for fused deposition modeling (FDM) applications via melt‐extrusion processing. Compared to the unmodified blends, ABS/PET blends with the addition of only 0.5 phr SAN‐silica‐epoxy JNS exhibited significant property enhancements, where the melt flow rate was increased by 47.9%, layer adhesion was enhanced by 115.7%, and warpage degree was reduced by 48.8%. Furthermore, the mechanical performance of ABS/PET blends was endowed with simultaneous optimization, such as a 74% increase in impact strength and a 13% increase in tensile strength. This work introduces a strategy for developing 3D printing materials that combine excellent 3D printing processability with superior mechanical performance through interfacial compatibility optimization and nanofiller reinforcement.
{"title":"Enhancing the Properties of <scp>ABS</scp>/<scp>PET</scp> Blends for <scp>3D</scp> Printing by Functionalized Janus Nanosheets","authors":"Yujia Liu, Hui He, Cheng Zhang, Hongyu Zhai, Luyun Han, Cheng Yang","doi":"10.1002/pen.70045","DOIUrl":"https://doi.org/10.1002/pen.70045","url":null,"abstract":"ABSTRACT Nanofillers are widely used to enhance the properties of polymeric materials due to their small particle size and high specific surface area. In this study, functionalized silica‐based Janus nanosheets (JNS) grafted with styrene–acrylonitrile copolymer (SAN) chains on one side and epoxy groups on the opposite side have been synthesized, termed SAN‐Silica‐epoxy JNS, and incorporated as modifiers into the acrylonitrile‐butadiene‐styrene copolymer/polyethylene terephthalate (ABS/PET) blends for fused deposition modeling (FDM) applications via melt‐extrusion processing. Compared to the unmodified blends, ABS/PET blends with the addition of only 0.5 phr SAN‐silica‐epoxy JNS exhibited significant property enhancements, where the melt flow rate was increased by 47.9%, layer adhesion was enhanced by 115.7%, and warpage degree was reduced by 48.8%. Furthermore, the mechanical performance of ABS/PET blends was endowed with simultaneous optimization, such as a 74% increase in impact strength and a 13% increase in tensile strength. This work introduces a strategy for developing 3D printing materials that combine excellent 3D printing processability with superior mechanical performance through interfacial compatibility optimization and nanofiller reinforcement.","PeriodicalId":20281,"journal":{"name":"Polymer Engineering and Science","volume":"65 10","pages":"5149-5161"},"PeriodicalIF":0.0,"publicationDate":"2025-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147331084","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ABSTRACT Phase change materials (PCMs) hold promise for advanced thermal management, yet their rigid behavior often restricts effective contact with curved or irregular surfaces—leading to inefficient heat transfer. To address this gap, we report a coaxially electrospun fiber composite integrating shape memory polyurethane (SMPU) and polyethylene glycol (PEG). The rationale behind this study lies in the need to overcome air gaps that arise when conventional PCMs fail to conform to nonplanar substrates, compromising the latent heat exchange crucial for thermoregulation. Leveraging coaxial electrospinning, we tuned fiber alignment and PEG content to fabricate composites capable of both shape fixation and phase‐change–assisted temperature control. Mechanical and shape memory tests confirmed performance, with final shape fixation and recovery rates exceeding 80% and 90%, respectively. Crucially, pre‐deforming the SMPU@PEG membrane to match complex substrates reduced interfacial air layers and increased the temperature difference by up to 6.77°C and 3.67°C compared with a non‐pre‐deformed sample. This improved thermal regulation underscores the synergistic advantage of shape memory functionality and phase‐change latent heat in optimizing conformal contact and heat transfer. Our study both enhances comprehension of merging shape memory features with PCMs and has real‐world uses for wearable tech reliant on efficient curved—surface thermoregulation.
{"title":"Coaxial Electrospun <scp>SMPU</scp> @ <scp>PEG</scp> Composites for Enhanced Thermal Regulation on Curved Surfaces","authors":"Xiaoyu Guan, Qian Cheng, Anqi Li, Hongyang Wang, Chunyan Lou, Wangyang Lü, Heng Zhang, Rui Wang","doi":"10.1002/pen.27265","DOIUrl":"https://doi.org/10.1002/pen.27265","url":null,"abstract":"ABSTRACT Phase change materials (PCMs) hold promise for advanced thermal management, yet their rigid behavior often restricts effective contact with curved or irregular surfaces—leading to inefficient heat transfer. To address this gap, we report a coaxially electrospun fiber composite integrating shape memory polyurethane (SMPU) and polyethylene glycol (PEG). The rationale behind this study lies in the need to overcome air gaps that arise when conventional PCMs fail to conform to nonplanar substrates, compromising the latent heat exchange crucial for thermoregulation. Leveraging coaxial electrospinning, we tuned fiber alignment and PEG content to fabricate composites capable of both shape fixation and phase‐change–assisted temperature control. Mechanical and shape memory tests confirmed performance, with final shape fixation and recovery rates exceeding 80% and 90%, respectively. Crucially, pre‐deforming the SMPU@PEG membrane to match complex substrates reduced interfacial air layers and increased the temperature difference by up to 6.77°C and 3.67°C compared with a non‐pre‐deformed sample. This improved thermal regulation underscores the synergistic advantage of shape memory functionality and phase‐change latent heat in optimizing conformal contact and heat transfer. Our study both enhances comprehension of merging shape memory features with PCMs and has real‐world uses for wearable tech reliant on efficient curved—surface thermoregulation.","PeriodicalId":20281,"journal":{"name":"Polymer Engineering and Science","volume":"65 9","pages":"4546-4557"},"PeriodicalIF":0.0,"publicationDate":"2025-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147331551","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ABSTRACT The amphiphilic hydrophobic associative polyacrylamide (HAPAM) was synthesized via free radical copolymerization using hexadecyl allyl dimethyl ammonium chloride (C16DMAAC), acrylic acid (AA), acrylamide (AM), and 2‐acrylamido‐2‐methylpropanesulfonic acid (AMPS) as raw materials. Additionally, the oil amide sulfobetaine (OSB) amphoteric surfactant was synthesized from oil amide dimethyl tertiary amine, sodium sulfite (NaHSO 3 ), and epichlorohydrin. The impact of various charged surfactants (SDS, DTAB, OSB, and AEO) on the binding properties of HAPAM in NaCl solution was investigated through measurements of apparen t viscosity, dynamic light scattering, cryogenic scanning electron microscopy, and rheological analysis. The results indicated that the viscosity of HAPAM in NaCl solution exhibited a parabolic relationship, first rising and then falling, with increasing concentrations of SDS and OSB. Upon the addition of OSB, the temperature and shear resistance of the polymer system were significantly enhanced. Compared to the system before surfactant addition, the maximum viscosity increased by approximately 10 mPa (70%) after shearing at 120°C. At different concentrations of OSB and SDS, the viscosity increased by 133%–157%, the hydration radius of HAPAM expanded by 2.28 to 6.22 times, and the absolute value of the zeta potential increased by 27.66 mV. Microscopic morphological observations revealed that the polymer system formed a three‐dimensional network structure of intermolecular association with the addition of surfactants, ultimately creating a dense spatial structure. However, this phenomenon was not as pronounced for cationic and nonionic surfactants. These findings, corroborated by molecular dynamics simulations, confirmed that an appropriate amount of anionic surfactants can enhance hydrophobic binding, expand electrostatic repulsion between anions, and significantly improve the resistance and electrostatic shielding effect of HAPAM against salt solution compression bilayer. This study provides valuable insights into the effects of surfactants on the cross‐linking structure and binding properties of HAPAM in NaCl solution, offering guidance for improving the recovery rate in binary composite flooding applications.
{"title":"Study on the Strong Association and Synergistic Temperature and Salt Resistance Mechanism of Differential Charge Surfactants and Ionic Polymer Systems","authors":"Chengwei Zuo, Pingli Liu, Pengfei Chen, Gang Xiong, Xiaojiang Li, Zhenfu Jia","doi":"10.1002/pen.70022","DOIUrl":"https://doi.org/10.1002/pen.70022","url":null,"abstract":"ABSTRACT The amphiphilic hydrophobic associative polyacrylamide (HAPAM) was synthesized via free radical copolymerization using hexadecyl allyl dimethyl ammonium chloride (C16DMAAC), acrylic acid (AA), acrylamide (AM), and 2‐acrylamido‐2‐methylpropanesulfonic acid (AMPS) as raw materials. Additionally, the oil amide sulfobetaine (OSB) amphoteric surfactant was synthesized from oil amide dimethyl tertiary amine, sodium sulfite (NaHSO 3 ), and epichlorohydrin. The impact of various charged surfactants (SDS, DTAB, OSB, and AEO) on the binding properties of HAPAM in NaCl solution was investigated through measurements of apparen t viscosity, dynamic light scattering, cryogenic scanning electron microscopy, and rheological analysis. The results indicated that the viscosity of HAPAM in NaCl solution exhibited a parabolic relationship, first rising and then falling, with increasing concentrations of SDS and OSB. Upon the addition of OSB, the temperature and shear resistance of the polymer system were significantly enhanced. Compared to the system before surfactant addition, the maximum viscosity increased by approximately 10 mPa (70%) after shearing at 120°C. At different concentrations of OSB and SDS, the viscosity increased by 133%–157%, the hydration radius of HAPAM expanded by 2.28 to 6.22 times, and the absolute value of the zeta potential increased by 27.66 mV. Microscopic morphological observations revealed that the polymer system formed a three‐dimensional network structure of intermolecular association with the addition of surfactants, ultimately creating a dense spatial structure. However, this phenomenon was not as pronounced for cationic and nonionic surfactants. These findings, corroborated by molecular dynamics simulations, confirmed that an appropriate amount of anionic surfactants can enhance hydrophobic binding, expand electrostatic repulsion between anions, and significantly improve the resistance and electrostatic shielding effect of HAPAM against salt solution compression bilayer. This study provides valuable insights into the effects of surfactants on the cross‐linking structure and binding properties of HAPAM in NaCl solution, offering guidance for improving the recovery rate in binary composite flooding applications.","PeriodicalId":20281,"journal":{"name":"Polymer Engineering and Science","volume":"65 9","pages":"4810-4821"},"PeriodicalIF":0.0,"publicationDate":"2025-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/pdfdirect/10.1002/pen.70022","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147333660","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Zhenxing Liu, Min Zhang, Xiaolin Zhao, Song Gao, Guangyong Liu
ABSTRACT This study evaluates brominated butyl rubber (BIIR) and natural rubber (NR) as sealing materials for lithium‐ion batteries by investigating their electrolyte resistance. BIIR, synthesized through bromination of butyl rubber (IIR), demonstrates enhanced chemical stability and aging resistance due to its polar CBr bonds and dense molecular architecture. NR, composed primarily of cis‐1,4‐polyisoprene, offers superior elasticity and processability. Vulcanized samples of BIIR and NR are immersed in pure and mixed solutions of ethylene carbonate (EC), diethyl carbonate (DEC), and ethyl methyl carbonate (EMC) at 45°C, 60°C, and 80°C, respectively. Swelling behavior and transport properties are analyzed by calculating diffusion ( D ), solubility ( S ), and permeability ( P ) coefficients. Results reveal that BIIR exhibits 42%–58% lower swelling ratios than NR under high‐temperature (80°C) and polar electrolyte (EC‐rich) conditions due to its compact molecular structure. NR displays selective adsorption behavior, with transient mass increases of 15%–20% during initial solvent exposure. Temperature elevation accelerates transport rates, reducing equilibrium swelling time by 65%–72% for BIIR compared to NR. These findings establish BIIR as a promising candidate for high‐temperature battery sealing applications, while the cost‐effectiveness and resilience of NR, on the other hand, remain advantageous under moderate conditions.
{"title":"Comparative Study on the Transport Characteristics and Electrolyte Resistance of Brominated Butyl Rubber‐ and Natural Rubber‐Based Rubber Films Using the Mass Uptake Measurement","authors":"Zhenxing Liu, Min Zhang, Xiaolin Zhao, Song Gao, Guangyong Liu","doi":"10.1002/pen.70025","DOIUrl":"https://doi.org/10.1002/pen.70025","url":null,"abstract":"ABSTRACT This study evaluates brominated butyl rubber (BIIR) and natural rubber (NR) as sealing materials for lithium‐ion batteries by investigating their electrolyte resistance. BIIR, synthesized through bromination of butyl rubber (IIR), demonstrates enhanced chemical stability and aging resistance due to its polar CBr bonds and dense molecular architecture. NR, composed primarily of cis‐1,4‐polyisoprene, offers superior elasticity and processability. Vulcanized samples of BIIR and NR are immersed in pure and mixed solutions of ethylene carbonate (EC), diethyl carbonate (DEC), and ethyl methyl carbonate (EMC) at 45°C, 60°C, and 80°C, respectively. Swelling behavior and transport properties are analyzed by calculating diffusion ( D ), solubility ( S ), and permeability ( P ) coefficients. Results reveal that BIIR exhibits 42%–58% lower swelling ratios than NR under high‐temperature (80°C) and polar electrolyte (EC‐rich) conditions due to its compact molecular structure. NR displays selective adsorption behavior, with transient mass increases of 15%–20% during initial solvent exposure. Temperature elevation accelerates transport rates, reducing equilibrium swelling time by 65%–72% for BIIR compared to NR. These findings establish BIIR as a promising candidate for high‐temperature battery sealing applications, while the cost‐effectiveness and resilience of NR, on the other hand, remain advantageous under moderate conditions.","PeriodicalId":20281,"journal":{"name":"Polymer Engineering and Science","volume":"65 9","pages":"4843-4853"},"PeriodicalIF":0.0,"publicationDate":"2025-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/pdfdirect/10.1002/pen.70025","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147332333","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Zitong Shen, Jiashang Chen, Jiaqi Bian, Xing Xiang, Siwen Bi
ABSTRACT To mitigate the aggregation of inorganic fillers in composite solid electrolytes, we synthesized a three‐armed polyester polyurethane oligomer (TAPU) through a two‐step polymerization. The curing degree of TAPU was quantitatively analyzed based on the infrared absorption of isocyanate groups, and the curing kinetics were investigated and integrated with the crystalline properties of the cured TAPU. TAPU had a strong solvation ability for lithium salt, and the ionic conductivity of the electrolyte reached 1.48 × 10 −4 S cm −1 at room temperature, which is much higher than that of linear polycaprolactone electrolytes. The LLZTO particles modified with TAPU exhibited enhanced dispersion stability in the composite electrolyte system, effectively suppressing nanoparticle aggregation and improving interfacial compatibility between the ceramic fillers and polymer matrix. The Li//5% LLZTO‐TAPU//Li coin cells were prepared by in situ curing and had excellent cycle stability of up to 768 h at 50°C, which was five times higher than that of PCL electrolytes. Compared with linear polymer solid electrolytes, nonlinear topological polymer provided more functional groups for high ion conduction and cycling stability in lithium batteries.
为了减少无机填料在复合固体电解质中的聚集，我们通过两步聚合合成了一种三臂聚酯聚氨酯低聚物（TAPU）。基于异氰酸酯基团的红外吸收定量分析了TAPU的固化程度，研究了固化动力学，并结合固化后TAPU的结晶性能进行了研究。TAPU对锂盐具有较强的溶剂化能力，电解质的离子电导率在室温下达到1.48 × 10−4 S cm−1，远高于线性聚己内酯电解质。经TAPU修饰的LLZTO颗粒在复合电解质体系中的分散稳定性增强，有效抑制了纳米颗粒聚集，改善了陶瓷填料与聚合物基体之间的界面相容性。采用原位固化法制备Li//5% LLZTO - TAPU//Li硬币电池，电池在50℃下的循环稳定性可达768 h，是PCL电解质的5倍。与线性聚合物固体电解质相比，非线性拓扑聚合物为锂电池提供了更多的官能团，具有较高的离子传导和循环稳定性。
{"title":"Three‐Armed Polycaprolactone‐Based Polyurethane for High‐Performance Composite Solid‐State Electrolytes","authors":"Zitong Shen, Jiashang Chen, Jiaqi Bian, Xing Xiang, Siwen Bi","doi":"10.1002/pen.70006","DOIUrl":"https://doi.org/10.1002/pen.70006","url":null,"abstract":"ABSTRACT To mitigate the aggregation of inorganic fillers in composite solid electrolytes, we synthesized a three‐armed polyester polyurethane oligomer (TAPU) through a two‐step polymerization. The curing degree of TAPU was quantitatively analyzed based on the infrared absorption of isocyanate groups, and the curing kinetics were investigated and integrated with the crystalline properties of the cured TAPU. TAPU had a strong solvation ability for lithium salt, and the ionic conductivity of the electrolyte reached 1.48 × 10 −4 S cm −1 at room temperature, which is much higher than that of linear polycaprolactone electrolytes. The LLZTO particles modified with TAPU exhibited enhanced dispersion stability in the composite electrolyte system, effectively suppressing nanoparticle aggregation and improving interfacial compatibility between the ceramic fillers and polymer matrix. The Li//5% LLZTO‐TAPU//Li coin cells were prepared by in situ curing and had excellent cycle stability of up to 768 h at 50°C, which was five times higher than that of PCL electrolytes. Compared with linear polymer solid electrolytes, nonlinear topological polymer provided more functional groups for high ion conduction and cycling stability in lithium batteries.","PeriodicalId":20281,"journal":{"name":"Polymer Engineering and Science","volume":"65 9","pages":"4707-4716"},"PeriodicalIF":0.0,"publicationDate":"2025-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147331491","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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