Pub Date : 2024-12-24DOI: 10.1016/j.polymer.2024.127974
Hongnan Zhang, Taoyuan Liu, Ke Li, Xiaohong Qin
Nowadays, modern industries are rapidly developing, which is caused by a significant amount of high-temperature exhaust gases in the atmosphere, and it contains complex pollutants, formaldehyde, solid particles, and harmful gases that are discharged. For this scenario, the conventional filtering materials are challenged for prevention of high-temperature exhaust gas formaldehyde volatilization because they are composed of metal and inorganic materials caused by oxidation-prone and resilient wear. A recently introduced technique to fabricate composite nanofiber membranes with high strength, modulus, efficiency, low resistance for high-temperature exhaust gas filtering, and its capability to adsorb formaldehyde was discussed in this study. Initially, Polyamide acid (PAA) solution and silicon dioxide (SiO2) nanomicrospheres are used as raw materials for producing electrostatic and thermal imidization Polyimide (PI/SiO2) nanofiber membranes (NFMs) in co-spinning processes. Furthermore, zeoliticimidazolate framework-8 (ZIF-8) was transferred into PI/SiO2 NFMs and produced the PI/SiO2@ZIF-8 NFM. These findings show that adding SiO2 nanomicrospheres reduced the fiber packing density as well as air filtration resistance, and PI/SiO2@ZIF-8 NFMs achieve up to 99.703% filtration efficiency and maintain a pressure drop of 178.7 Pa. The weight loss rate is only 4% at temperatures above 300 °C, and the heat resistance is outstanding. Moreover, the PI/SiO2@ZIF-8 NFMs demonstrate a good formaldehyde adsorption performance with a saturation adsorption capacity for formaldehyde within 4 hours of 41.58 mg/g, which is more than 12 times that of the PI/SiO2 NFMs without ZIF-8.
{"title":"PI/SiO2@ZIF-8 nanofiber membrane with excellent high temperature exhaust gas filtration performance and efficiently formaldehyde adsorption capacity","authors":"Hongnan Zhang, Taoyuan Liu, Ke Li, Xiaohong Qin","doi":"10.1016/j.polymer.2024.127974","DOIUrl":"https://doi.org/10.1016/j.polymer.2024.127974","url":null,"abstract":"Nowadays, modern industries are rapidly developing, which is caused by a significant amount of high-temperature exhaust gases in the atmosphere, and it contains complex pollutants, formaldehyde, solid particles, and harmful gases that are discharged. For this scenario, the conventional filtering materials are challenged for prevention of high-temperature exhaust gas formaldehyde volatilization because they are composed of metal and inorganic materials caused by oxidation-prone and resilient wear. A recently introduced technique to fabricate composite nanofiber membranes with high strength, modulus, efficiency, low resistance for high-temperature exhaust gas filtering, and its capability to adsorb formaldehyde was discussed in this study. Initially, Polyamide acid (PAA) solution and silicon dioxide (SiO<sub>2</sub>) nanomicrospheres are used as raw materials for producing electrostatic and thermal imidization Polyimide (PI/SiO<sub>2</sub>) nanofiber membranes (NFMs) in co-spinning processes. Furthermore, zeoliticimidazolate framework-8 (ZIF-8) was transferred into PI/SiO<sub>2</sub> NFMs and produced the PI/SiO2@ZIF-8 NFM. These findings show that adding SiO<sub>2</sub> nanomicrospheres reduced the fiber packing density as well as air filtration resistance, and PI/SiO2@ZIF-8 NFMs achieve up to 99.703% filtration efficiency and maintain a pressure drop of 178.7 Pa. The weight loss rate is only 4% at temperatures above 300 °C, and the heat resistance is outstanding. Moreover, the PI/SiO2@ZIF-8 NFMs demonstrate a good formaldehyde adsorption performance with a saturation adsorption capacity for formaldehyde within 4 hours of 41.58 mg/g, which is more than 12 times that of the PI/SiO2 NFMs without ZIF-8.","PeriodicalId":405,"journal":{"name":"Polymer","volume":"87 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142884531","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 : 2024-12-24DOI: 10.1016/j.polymer.2024.127983
Hiroki Yamamoto, Francis McCallum, Hui Peng, Idriss Blakey, Shin Hasegawa, Yasunari Maekawa, Takahiro Kozawa, Andrew K. Whittaker
The self-assembly of block copolymers (BCP) has appeared over the past two decades as a promising method for future patterning techniques for manufacture of integrated circuits and memory devices. However, generation of sub-20 nm feature sizes is challenging using conventional BCPs such as polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA). The realization of further miniaturization at scales of sub-10 nm in semiconductor devices depends on the design and development of new BCP materials. This study reports the synthesis of novel BCPs composed of polystyrene (PS) and polymers of 3-hydroxy-1-methacryloyloxyadamantane (HAdMA) by reversible addition-fragmentation chain-transfer (RAFT). The PHAdMA block has an elevated glass transition temperature (Tg) and is a bulky and sterically hindered segment. In this study we have demonstrated the synthetic conditions to achieve controlled polymer molecular weights and molecular weight dispersity. The physical properties, including solubility, thermal stability, film-forming capacity, self-assembly in solvent annealing and thermal annealing of polystyrene-block-poly(3-hydroxy-1-methacryloyloxyadamantane) (PS-b-PHAdMA) are reported in detail and indicate that this block copolymer is an excellent candidate for next-generation lithography materials. In particular, the analysis of the microphase morphologies in PS-b-PHAdMA thin films using atomic force microscopy (AFM) and small angle X-ray scattering (SAXS) showed clear evidence of ordering of the BCPs into cylinders. This study significantly expands the ability of block copolymer lithography for producing patterns, an essential requirement for nanoscale device fabrication.
{"title":"Synthesis of Polystyrene-block-poly(3-hydroxy-1-methacryloyloxyadamantane) (PS-b-PHAdMA) via RAFT Polymerization as Candidate Block Copolymers for Next Generation Lithography","authors":"Hiroki Yamamoto, Francis McCallum, Hui Peng, Idriss Blakey, Shin Hasegawa, Yasunari Maekawa, Takahiro Kozawa, Andrew K. Whittaker","doi":"10.1016/j.polymer.2024.127983","DOIUrl":"https://doi.org/10.1016/j.polymer.2024.127983","url":null,"abstract":"The self-assembly of block copolymers (BCP) has appeared over the past two decades as a promising method for future patterning techniques for manufacture of integrated circuits and memory devices. However, generation of sub-20 nm feature sizes is challenging using conventional BCPs such as polystyrene-<em>block</em>-poly(methyl methacrylate) (PS-<em>b</em>-PMMA). The realization of further miniaturization at scales of sub-10 nm in semiconductor devices depends on the design and development of new BCP materials. This study reports the synthesis of novel BCPs composed of polystyrene (PS) and polymers of 3-hydroxy-1-methacryloyloxyadamantane (HAdMA) by reversible addition-fragmentation chain-transfer (RAFT). The PHAdMA block has an elevated glass transition temperature (T<sub>g</sub>) and is a bulky and sterically hindered segment. In this study we have demonstrated the synthetic conditions to achieve controlled polymer molecular weights and molecular weight dispersity. The physical properties, including solubility, thermal stability, film-forming capacity, self-assembly in solvent annealing and thermal annealing of polystyrene-<em>block</em>-poly(3-hydroxy-1-methacryloyloxyadamantane) (PS-<em>b</em>-PHAdMA) are reported in detail and indicate that this block copolymer is an excellent candidate for next-generation lithography materials. In particular, the analysis of the microphase morphologies in PS-<em>b</em>-PHAdMA thin films using atomic force microscopy (AFM) and small angle X-ray scattering (SAXS) showed clear evidence of ordering of the BCPs into cylinders. This study significantly expands the ability of block copolymer lithography for producing patterns, an essential requirement for nanoscale device fabrication.","PeriodicalId":405,"journal":{"name":"Polymer","volume":"1 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142884533","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 : 2024-12-22DOI: 10.1016/j.polymer.2024.127976
Arnaud W. Laramée, Jiayi Chen, Mélanie Le Faou, Christian Pellerin
The detailed structural characterization of electrospun fibers is crucial for understanding their processing-structure-properties relationships and optimizing their preparation. While many advanced applications of electrospun fibers incorporate multiple components, our current knowledge is predominantly based on one-component fibers, raising questions about its applicability to more complex materials. In this work, we investigate electrospun fibers composed of miscible blends of polystyrene (PS) with poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) to identify the key factors that impact their structure. Confocal Raman microscopy is employed to quantify the molecular orientation of PS and PPO at the single fiber level. The results reveal that PPO is much more oriented than PS at all compositions, with a widening gap as the PPO content increases. This unexpected behavior for a miscible blend coincides with a broadening of the glass transition, attributed to increased composition fluctuations at higher PPO content. The results suggest that a difference in solvent affinity between the two polymers, where PPO is less solvated than PS, reduces the relaxation of PPO and promotes that of PS, especially at high PPO content. This work demonstrates that electrospun fibers of miscible blends do not behave as a mere average of the properties of their constituents. Instead, the relative polymer-solvent affinity emerges as a central factor shaping their molecular organization.
{"title":"Molecular Orientation and Solvent Affinity in Electrospun Fibers of Miscible Blends","authors":"Arnaud W. Laramée, Jiayi Chen, Mélanie Le Faou, Christian Pellerin","doi":"10.1016/j.polymer.2024.127976","DOIUrl":"https://doi.org/10.1016/j.polymer.2024.127976","url":null,"abstract":"The detailed structural characterization of electrospun fibers is crucial for understanding their processing-structure-properties relationships and optimizing their preparation. While many advanced applications of electrospun fibers incorporate multiple components, our current knowledge is predominantly based on one-component fibers, raising questions about its applicability to more complex materials. In this work, we investigate electrospun fibers composed of miscible blends of polystyrene (PS) with poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) to identify the key factors that impact their structure. Confocal Raman microscopy is employed to quantify the molecular orientation of PS and PPO at the single fiber level. The results reveal that PPO is much more oriented than PS at all compositions, with a widening gap as the PPO content increases. This unexpected behavior for a miscible blend coincides with a broadening of the glass transition, attributed to increased composition fluctuations at higher PPO content. The results suggest that a difference in solvent affinity between the two polymers, where PPO is less solvated than PS, reduces the relaxation of PPO and promotes that of PS, especially at high PPO content. This work demonstrates that electrospun fibers of miscible blends do not behave as a mere average of the properties of their constituents. Instead, the relative polymer-solvent affinity emerges as a central factor shaping their molecular organization.","PeriodicalId":405,"journal":{"name":"Polymer","volume":"52 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142870042","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 : 2024-12-22DOI: 10.1016/j.polymer.2024.127978
Diana-Andreea Blaj, Cristian Peptu
Over the past decade, metal-free catalysis in the ring-opening polymerization of lactides has gained significant attention. Amine catalysts have enabled precise control over ring-opening processes, but transesterification side reactions, which impact polymer structure and properties, may also occur. Size exclusion chromatography was mainly used to quantify these processes and correlate their occurrence with synthesis parameters. However, mass spectrometry proved highly accurate in identifying transesterifications of polylactides. This study proposes a semiquantitative assessment of transesterification using MALDI MS during β-cyclodextrin-oligolactide synthesis via ring-opening oligomerization of D,L-lactide initiated by β-cyclodextrin. The degree of transesterification (Tr) and the relative rate of transesterification were measured to evaluate the influence of reaction parameters (temperature, solvents, concentration, molar ratios, and organocatalysts) on these side reactions. Parallel analysis of number average molecular mass and Tr evolution provided insights into the role of various organocatalysts (4-dimethylaminopyridine, imidazole, (-)-sparteine, 1,8-diazabicyclo[5.4.0]-undec-7-ene, and 1,5,7-triazabicyclo[4.4.0]dec-5-ene) in optimizing the synthesis process.
{"title":"MALDI MS quantification of transesterification reactions in β-cyclodextrin-oligolactides systems","authors":"Diana-Andreea Blaj, Cristian Peptu","doi":"10.1016/j.polymer.2024.127978","DOIUrl":"https://doi.org/10.1016/j.polymer.2024.127978","url":null,"abstract":"Over the past decade, metal-free catalysis in the ring-opening polymerization of lactides has gained significant attention. Amine catalysts have enabled precise control over ring-opening processes, but transesterification side reactions, which impact polymer structure and properties, may also occur. Size exclusion chromatography was mainly used to quantify these processes and correlate their occurrence with synthesis parameters. However, mass spectrometry proved highly accurate in identifying transesterifications of polylactides. This study proposes a semiquantitative assessment of transesterification using MALDI MS during β-cyclodextrin-oligolactide synthesis via ring-opening oligomerization of D,L-lactide initiated by β-cyclodextrin. The degree of transesterification (<em>Tr</em>) and the relative rate of transesterification were measured to evaluate the influence of reaction parameters (temperature, solvents, concentration, molar ratios, and organocatalysts) on these side reactions. Parallel analysis of number average molecular mass and <em>Tr</em> evolution provided insights into the role of various organocatalysts (4-dimethylaminopyridine, imidazole, (-)-sparteine, 1,8-diazabicyclo[5.4.0]-undec-7-ene, and 1,5,7-triazabicyclo[4.4.0]dec-5-ene) in optimizing the synthesis process.","PeriodicalId":405,"journal":{"name":"Polymer","volume":"64 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874683","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 : 2024-12-22DOI: 10.1016/j.polymer.2024.127975
Zecheng Cao, Xiaojiao Kang, Wei Lü, Hongcheng Wang
With the advancement of economic development and the increasing complexity of commodity distribution, efficient and precise anti-counterfeiting measures have garnered significant attention in recent decades. This challenge necessitates the development of flexible films exhibiting both superior mechanical and optical properties to accommodate various anti-counterfeiting applications. This study introduces a composite film comprised of waterborne polyurethane (WPU), gelatin quantum dots (QDs), and glycerol. Glycerol, employed as a plasticizer, enhances the film's plasticity by disrupting hydrogen bonds within the matrix. The tensile strength decreased from 7.7 MPa to 1.73 MPa, while the elongation at break increased from 410% to 656%, compared to the samples without glycerol. The resulting films exhibit advantageous properties, including facile preparation, high transmittance, excellent optical properties, and excellent mechanical performance. Additionally, the photoluminescence intensity decreased by only 15% after being placed in air for 30 days. They demonstrate commendable stability under ambient temperature and environmental conditions, making them suitable for diverse and intricate anti-counterfeiting applications. The emission wavelength of the composite films was tuned by adjusting the cation ratio of the QDs, and the mechanical properties can be adjusted by varying the QD and glycerol contents. This work offers valuable insights for the development of advanced flexible materials for anti-counterfeiting purposes.
{"title":"Eco-friendly fabrication and luminescent properties of flexible Ag-In-Zn-S/ZnS QD-WPU composite film","authors":"Zecheng Cao, Xiaojiao Kang, Wei Lü, Hongcheng Wang","doi":"10.1016/j.polymer.2024.127975","DOIUrl":"https://doi.org/10.1016/j.polymer.2024.127975","url":null,"abstract":"With the advancement of economic development and the increasing complexity of commodity distribution, efficient and precise anti-counterfeiting measures have garnered significant attention in recent decades. This challenge necessitates the development of flexible films exhibiting both superior mechanical and optical properties to accommodate various anti-counterfeiting applications. This study introduces a composite film comprised of waterborne polyurethane (WPU), gelatin quantum dots (QDs), and glycerol. Glycerol, employed as a plasticizer, enhances the film's plasticity by disrupting hydrogen bonds within the matrix. The tensile strength decreased from 7.7 MPa to 1.73 MPa, while the elongation at break increased from 410% to 656%, compared to the samples without glycerol. The resulting films exhibit advantageous properties, including facile preparation, high transmittance, excellent optical properties, and excellent mechanical performance. Additionally, the photoluminescence intensity decreased by only 15% after being placed in air for 30 days. They demonstrate commendable stability under ambient temperature and environmental conditions, making them suitable for diverse and intricate anti-counterfeiting applications. The emission wavelength of the composite films was tuned by adjusting the cation ratio of the QDs, and the mechanical properties can be adjusted by varying the QD and glycerol contents. This work offers valuable insights for the development of advanced flexible materials for anti-counterfeiting purposes.","PeriodicalId":405,"journal":{"name":"Polymer","volume":"40 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142870043","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 : 2024-12-21DOI: 10.1016/j.polymer.2024.127968
Gloria Signorato, Lea R. Klauke, Philipp Haida, Tobias Vossmeyer, Volker Abetz
The field of stimuli-responsive soft materials is rapidly evolving, particularly with recent advances in the design and fabrication of magnetic soft materials. Magnetically responsive elastomers, which incorporate magnetic particles into an elastomeric matrix, exhibit rapid and reversible actuation in the presence of a magnetic field, making them highly suitable for the development of flexible, remote-controlled soft robots. However, conventional crosslinked elastomer materials often lack recyclability and the versatile properties associated with vitrimer materials. Vitrimers, which are dynamically crosslinked polymers, can be reprocessed upon heating and offer valuable features such as recyclability and self-healing. In this study, we developed vitrimer nanocomposites by incorporating 5 to 15 wt.% superparamagnetic iron oxide nanoparticles (SPIONs) into a vinylogous urethane vitrimer matrix, yielding materials that exhibit both thermal and magnetic responsiveness. Furthermore, a novel acetoacetylated ligand with a phosphonic acid anchoring group was utilized to modify the surface of SPIONs, enhancing their stability and enabling their covalent linking to the vitrimer matrix. The crosslinking of the nanoparticles to the matrix improves the mechanical properties, including increased tensile stress and strain. Since the nanoparticles are covalently bound to the matrix, the resulting material can be reprocessed and recycled without compromising the uniform distribution of SPIONs, thereby promoting a closed-loop cycle of reuse and recycling while preserving the mechanical and magnetic properties of the nanocomposites. The integration of SPIONs into vinylogous urethane vitrimers results in the development of sustainable advanced materials with enhanced stability and functionality, highlighting their potential across various applications.
{"title":"Superparamagnetic Iron Oxide Nanoparticle – Vitrimer Nanocomposites: Reprocessable and Multi-Responsive Materials","authors":"Gloria Signorato, Lea R. Klauke, Philipp Haida, Tobias Vossmeyer, Volker Abetz","doi":"10.1016/j.polymer.2024.127968","DOIUrl":"https://doi.org/10.1016/j.polymer.2024.127968","url":null,"abstract":"The field of stimuli-responsive soft materials is rapidly evolving, particularly with recent advances in the design and fabrication of magnetic soft materials. Magnetically responsive elastomers, which incorporate magnetic particles into an elastomeric matrix, exhibit rapid and reversible actuation in the presence of a magnetic field, making them highly suitable for the development of flexible, remote-controlled soft robots. However, conventional crosslinked elastomer materials often lack recyclability and the versatile properties associated with vitrimer materials. Vitrimers, which are dynamically crosslinked polymers, can be reprocessed upon heating and offer valuable features such as recyclability and self-healing. In this study, we developed vitrimer nanocomposites by incorporating 5 to 15 wt.% superparamagnetic iron oxide nanoparticles (SPIONs) into a vinylogous urethane vitrimer matrix, yielding materials that exhibit both thermal and magnetic responsiveness. Furthermore, a novel acetoacetylated ligand with a phosphonic acid anchoring group was utilized to modify the surface of SPIONs, enhancing their stability and enabling their covalent linking to the vitrimer matrix. The crosslinking of the nanoparticles to the matrix improves the mechanical properties, including increased tensile stress and strain. Since the nanoparticles are covalently bound to the matrix, the resulting material can be reprocessed and recycled without compromising the uniform distribution of SPIONs, thereby promoting a closed-loop cycle of reuse and recycling while preserving the mechanical and magnetic properties of the nanocomposites. The integration of SPIONs into vinylogous urethane vitrimers results in the development of sustainable advanced materials with enhanced stability and functionality, highlighting their potential across various applications.","PeriodicalId":405,"journal":{"name":"Polymer","volume":"78 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142867606","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 : 2024-12-20DOI: 10.1016/j.polymer.2024.127971
Bar Shlomo-Avitan, Majd Machour, Samah Saied Ahmad, Yoav Friedler, Shulamit Levenberg, Michael S. Silverstein
PolyHIPEs are macroporous polymers templated within high internal phase emulsions (HIPEs). The ability to tailor the macromolecular and porous structures makes polyHIPEs of interest for three dimensional tissue engineering scaffolds. In this work, polyHIPEs with densities ranging from 0.18 to 0.28 g/cc were synthesized from novel biodegradable poly(ɛ-caprolactone) (PCL) macromers based on methacrylated oligomeric PCL diols of various molecular weights. Different types of internal phases generated porous structures that varied from networks of channels to highly interconnected voids. The crosslinked macromolecular structure limited PCL crystallization, resulting in elastomeric behavior with moduli of around 20 kPa. The HIPEs proved suitable for 3D printing both in air and in an innovative gel-bath. The suitability of the polyHIPEs for tissue engineering applications was indicated by their moduli, by their complete degradation within 4 h in 3 M NaOH, and by the mesenchymal stem cells adhering and proliferating. The high level of viability can be attributed to the porosity that enables sufficient nutrient and waste diffusion. These results provide a foundation for designing 3D HIPE inks for printing macroporous tissue engineering scaffolds.
PolyHIPEs是在高内相乳剂（HIPEs）中模板化的大孔聚合物。定制大分子和多孔结构的能力使polyHIPEs成为三维组织工程支架的兴趣。在这项工作中，以不同分子量的甲基丙烯酸化聚己内酯低聚二醇为基础，用新型可生物降解的聚己内酯（PCL）大分子合成了密度为0.18至0.28 g/cc的聚hipes。不同类型的内部相产生的多孔结构从通道网络到高度互连的空隙不等。交联的大分子结构限制了PCL的结晶，导致模量约为20 kPa的弹性体行为。事实证明，HIPEs适用于在空气和创新的凝胶浴中进行3D打印。通过其模量、在3 M NaOH中4小时内完全降解以及间充质干细胞粘附和增殖，表明了多hipes在组织工程应用中的适用性。高水平的生存力可归因于孔隙度，使足够的营养物质和废物扩散。这些结果为大孔组织工程支架3D打印用HIPE油墨的设计提供了基础。
{"title":"Emulsion-templated macroporous polycaprolactone: Synthesis, degradation, additive manufacturing, and cell-growth","authors":"Bar Shlomo-Avitan, Majd Machour, Samah Saied Ahmad, Yoav Friedler, Shulamit Levenberg, Michael S. Silverstein","doi":"10.1016/j.polymer.2024.127971","DOIUrl":"https://doi.org/10.1016/j.polymer.2024.127971","url":null,"abstract":"PolyHIPEs are macroporous polymers templated within high internal phase emulsions (HIPEs). The ability to tailor the macromolecular and porous structures makes polyHIPEs of interest for three dimensional tissue engineering scaffolds. In this work, polyHIPEs with densities ranging from 0.18 to 0.28 g/cc were synthesized from novel biodegradable poly(ɛ-caprolactone) (PCL) macromers based on methacrylated oligomeric PCL diols of various molecular weights. Different types of internal phases generated porous structures that varied from networks of channels to highly interconnected voids. The crosslinked macromolecular structure limited PCL crystallization, resulting in elastomeric behavior with moduli of around 20 kPa. The HIPEs proved suitable for 3D printing both in air and in an innovative gel-bath. The suitability of the polyHIPEs for tissue engineering applications was indicated by their moduli, by their complete degradation within 4 h in 3 M NaOH, and by the mesenchymal stem cells adhering and proliferating. The high level of viability can be attributed to the porosity that enables sufficient nutrient and waste diffusion. These results provide a foundation for designing 3D HIPE inks for printing macroporous tissue engineering scaffolds.","PeriodicalId":405,"journal":{"name":"Polymer","volume":"55 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142867344","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 development of conductive hydrogels with high mechanical strength, self-healing and adhesive for applications in flexible electronics remains challenging. In this work, triblock copolymer poly(2-hydroxyethyl acrylate-co-1-benzyl-3-vinylimidazolium bromide)-b-polyazobenzene-b-poly(2-hydroxyethyl acrylate-co-1-benzyl-3-vinylimidazolium bromide) were synthesized through reversible addition-fragmentation chain transfer polymerization. The assembly of triblock copolymer, and cucurbit[8]uril based dynamic host-guest interactions were employed to fabricate 3D network of supramolecular hydrogel. Investigations on the properties of the supramolecular hydrogel show that the dynamic and reversible supramolecular interactions endow the hydrogel with high stretchability (1120%) and high self-healing efficient (98%, 48 h). Interestingly, the soft poly(2-hydroxyethyl acrylate) segments and intermediate functional groups contribute to the adhesive performance hydrogel. Thanks to its excellent conductivity, the as-obtained hydrogel exhibits remarkable capacity for detecting various levels of motion. The supramolecular hydrogel is great significance for the efficient development of wearable electronics and flexible devices with high mechanical strength, self-healing, adhesive, photo-responsivity, conductivity and biocompatibility.
{"title":"Self-healing, high mechanical strength and adhesive supramolecular hydrogel based on triblock copolymer for flexible electronics","authors":"Yingying Huang, Yuxuan Yang, Yuhao Yang, Shiying Chen, Simin Liu, Xiongzhi Zhang","doi":"10.1016/j.polymer.2024.127966","DOIUrl":"https://doi.org/10.1016/j.polymer.2024.127966","url":null,"abstract":"The development of conductive hydrogels with high mechanical strength, self-healing and adhesive for applications in flexible electronics remains challenging. In this work, triblock copolymer poly(2-hydroxyethyl acrylate-<em>co</em>-1-benzyl-3-vinylimidazolium bromide)-<em>b</em>-polyazobenzene-<em>b-</em>poly(2-hydroxyethyl acrylate-<em>co</em>-1-benzyl-3-vinylimidazolium bromide) were synthesized through reversible addition-fragmentation chain transfer polymerization. The assembly of triblock copolymer, and cucurbit[8]uril based dynamic host-guest interactions were employed to fabricate 3D network of supramolecular hydrogel. Investigations on the properties of the supramolecular hydrogel show that the dynamic and reversible supramolecular interactions endow the hydrogel with high stretchability (1120%) and high self-healing efficient (98%, 48 h). Interestingly, the soft poly(2-hydroxyethyl acrylate) segments and intermediate functional groups contribute to the adhesive performance hydrogel. Thanks to its excellent conductivity, the as-obtained hydrogel exhibits remarkable capacity for detecting various levels of motion. The supramolecular hydrogel is great significance for the efficient development of wearable electronics and flexible devices with high mechanical strength, self-healing, adhesive, photo-responsivity, conductivity and biocompatibility.","PeriodicalId":405,"journal":{"name":"Polymer","volume":"1 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142857976","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 : 2024-12-20DOI: 10.1016/j.polymer.2024.127970
Davide Tranchida, Dietmar Salaberger, Lada Vukusic, Gerhard Hubner, Mithun Goswami, Andreas Albrecht, Susana Filipe
Achieving the detailed knowledge of recycled materials composition is a formidable task due to the presence of organic and inorganic contaminations. Additionally, the complexity of the microstructure is far superior to the one of virgin materials where the production process is well controlled. Nonetheless, this task is of paramount importance because properties are affected in crucial ways. In this work we studied recycled polyolefin grades with several techniques, in particular through their adaptation to the analysis of this class of materials, to combine the information and obtain a detailed knowledge of their characteristics. Thermogravimetric Analysis (TGA), X-Ray Fluorescence (XRF), X-Ray Computed Tomography (CT) and Scanning Electron Microscopy (SEM) were used to characterize inorganic contaminations. CT and Fourier Transform Infrared Spectroscopy (FTIR) were used to characterize organic contaminations. Microstructure details were evaluated by Nuclear Magnetic Resonance (NMR) and fractionation and thermal analysis methods. Also the limitations of the various techniques are addressed.
{"title":"Advanced characterization of recycled polyolefins: a holistic approach to study their microstructure and contaminations","authors":"Davide Tranchida, Dietmar Salaberger, Lada Vukusic, Gerhard Hubner, Mithun Goswami, Andreas Albrecht, Susana Filipe","doi":"10.1016/j.polymer.2024.127970","DOIUrl":"https://doi.org/10.1016/j.polymer.2024.127970","url":null,"abstract":"Achieving the detailed knowledge of recycled materials composition is a formidable task due to the presence of organic and inorganic contaminations. Additionally, the complexity of the microstructure is far superior to the one of virgin materials where the production process is well controlled. Nonetheless, this task is of paramount importance because properties are affected in crucial ways. In this work we studied recycled polyolefin grades with several techniques, in particular through their adaptation to the analysis of this class of materials, to combine the information and obtain a detailed knowledge of their characteristics. Thermogravimetric Analysis (TGA), X-Ray Fluorescence (XRF), X-Ray Computed Tomography (CT) and Scanning Electron Microscopy (SEM) were used to characterize inorganic contaminations. CT and Fourier Transform Infrared Spectroscopy (FTIR) were used to characterize organic contaminations. Microstructure details were evaluated by Nuclear Magnetic Resonance (NMR) and fractionation and thermal analysis methods. Also the limitations of the various techniques are addressed.","PeriodicalId":405,"journal":{"name":"Polymer","volume":"27 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142867345","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 work demonstrates that environmental-friendly bio-based and biodegradable polylactide (PLA) can be significantly toughened by processing modification alone. The notched Izod impact strength of the prepared PLA increased from 3.4 kJ/m2 to 89.9 kJ/m2 without other components incorporated. We emphasized the changes in crystalline structure and traced the layer and network structures through etching experiment and dissolution experiment. The results manifested that the synergistic effect of layer structure formed by in-situ oriented crystallites and the network structure generated by stereocomplex crystallites (SCs) with stronger intermolecular force and high density tie chains was the dominant reason for the toughness enhancement. Moreover, the tensile strength and Vicat softening temperature of PLA was improved simultaneously, which reached 92.4 MPa and 167.6 °C, respectively. Notably, by comparing with the petroleum-based engineering plastics, the prepared PLA exhibits excellent comprehensive performance and can be used as a green engineering plastic to expand its potential applications.
{"title":"Synergistic Toughening of Polylactide by Layer Structure and Network Structure","authors":"Mingtao Sun, Ziqing Zhang, Yipeng He, Weixia Yan, Muhuo Yu, Keqing Han","doi":"10.1016/j.polymer.2024.127969","DOIUrl":"https://doi.org/10.1016/j.polymer.2024.127969","url":null,"abstract":"This work demonstrates that environmental-friendly bio-based and biodegradable polylactide (PLA) can be significantly toughened by processing modification alone. The notched Izod impact strength of the prepared PLA increased from 3.4 kJ/m<sup>2</sup> to 89.9 kJ/m<sup>2</sup> without other components incorporated. We emphasized the changes in crystalline structure and traced the layer and network structures through etching experiment and dissolution experiment. The results manifested that the synergistic effect of layer structure formed by in-situ oriented crystallites and the network structure generated by stereocomplex crystallites (SCs) with stronger intermolecular force and high density tie chains was the dominant reason for the toughness enhancement. Moreover, the tensile strength and Vicat softening temperature of PLA was improved simultaneously, which reached 92.4 MPa and 167.6 °C, respectively. Notably, by comparing with the petroleum-based engineering plastics, the prepared PLA exhibits excellent comprehensive performance and can be used as a green engineering plastic to expand its potential applications.","PeriodicalId":405,"journal":{"name":"Polymer","volume":"55 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142857973","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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