Pub Date : 2024-11-07DOI: 10.1016/j.polymer.2024.127796
Yanqiong Zheng , Chenchen Li , Bingjia Zhao , Siqi Zhang , Xuande Yang , Qingyu Zhang , Ryota Kabe , Xifeng Li
To inhibit the total reflection in the substrate-mode light loss of organic light-emitting diodes (OLEDs) and fully take advantage of the excellent light converging and out-coupling effect of the hexagonal array of microsphere, we in-situ fabricated the hexagonal array of polydimethylsiloxane (PDMS) microsphere onto the substrate of OLEDs via the porous template for substrate-mode light extraction. Firstly, regular honeycomb porous polystyrene (PS) template was prepared via a self-assembly “breath figure” process. The PS molecular weight, solvent, and humidity play an important role on the uniformity of pore distribution and pore diameter according to Young-Laplace equation. Based on the optimized porous PS template, the PDMS microsphere array was fabricated by pattern transferring, which indicates more prominent light diffraction than the flat PDMS film. Finite-difference time-domain (FDTD) simulation denotes that higher duty ratio of the PDMS microsphere array contributes to higher light out-coupling efficiency. Therefore, a PDMS microsphere array with larger duty ratio of 84.0 % was applied in the extraction of external light for the blue fluorescent OLED device. The maximum luminance, current efficiency, and power efficiency are all improved, and the external quantum efficiency (EQE) is increased by 18.81 % with spectral stability.
{"title":"In-situ fabricated hexagonal PDMS microsphere arrays for substrate-mode light extraction in blue fluorescent organic light emitting diodes","authors":"Yanqiong Zheng , Chenchen Li , Bingjia Zhao , Siqi Zhang , Xuande Yang , Qingyu Zhang , Ryota Kabe , Xifeng Li","doi":"10.1016/j.polymer.2024.127796","DOIUrl":"10.1016/j.polymer.2024.127796","url":null,"abstract":"<div><div>To inhibit the total reflection in the substrate-mode light loss of organic light-emitting diodes (OLEDs) and fully take advantage of the excellent light converging and out-coupling effect of the hexagonal array of microsphere, we in-situ fabricated the hexagonal array of polydimethylsiloxane (PDMS) microsphere onto the substrate of OLEDs via the porous template for substrate-mode light extraction. Firstly, regular honeycomb porous polystyrene (PS) template was prepared via a self-assembly “breath figure” process. The PS molecular weight, solvent, and humidity play an important role on the uniformity of pore distribution and pore diameter according to Young-Laplace equation. Based on the optimized porous PS template, the PDMS microsphere array was fabricated by pattern transferring, which indicates more prominent light diffraction than the flat PDMS film. Finite-difference time-domain (FDTD) simulation denotes that higher duty ratio of the PDMS microsphere array contributes to higher light out-coupling efficiency. Therefore, a PDMS microsphere array with larger duty ratio of 84.0 % was applied in the extraction of external light for the blue fluorescent OLED device. The maximum luminance, current efficiency, and power efficiency are all improved, and the external quantum efficiency (EQE) is increased by 18.81 % with spectral stability.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"315 ","pages":"Article 127796"},"PeriodicalIF":4.1,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142594253","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-07DOI: 10.1016/j.polymer.2024.127799
Sinduja Malarkodi Elangovan , Riza Paul , Parthiban Shanmugam , Gopal Shankar Krishnakumar
This study proposes to combine plant-derived galactomannan and MXene to form an organic-inorganic hydrogel network with integrative antibacterial and osteogenic properties. Oxidized galactomannan (OxGa) was blended with N-succinyl chitosan (NSC) and varying concentrations of Mxene, owing to its high reactivity and biocompatibility. The results indicated that Mxene-loaded OxGa/NSC scaffolds exhibited biomimetic topography, adequate mechanical features and excellent physicochemical properties with strong antibacterial properties against pathogenic microbes. The cell culture experiments showed dose-dependent cytotoxic behaviour. An optimized MXene content of ≤4 mg/ml revealed no cytotoxicity and augmented the proliferation of osteoblast cells. Similar results were obtained in gene expression analysis where ALP, COL1A1, RUNX2, and SOX2 genes showed up-regulation. In addition, the chorioallantoic membrane (CAM) assay also illustrated augmentation of angiogenesis without any toxicity. The overall results highlight the dual performance of OxGa/NSC-MXene scaffolds to exhibit anti-infection with simultaneous osteogenic properties, which is purely determined by the concentration of MXene. Therefore, regulating MXene concentration can serve as a chemical switch in imparting adequate antibacterial functions with the ability to allow new osseous generation. Our findings on the newly designed Mxene-loaded OxGa/NSC scaffolds can be a promising biomaterial for bone-related infections with a concurrent ability to promote osteogenesis.
{"title":"Synergistic integration of plant derived galactomannan and MXene to produce multifunctional nanocomposites with antibacterial and osteogenic properties","authors":"Sinduja Malarkodi Elangovan , Riza Paul , Parthiban Shanmugam , Gopal Shankar Krishnakumar","doi":"10.1016/j.polymer.2024.127799","DOIUrl":"10.1016/j.polymer.2024.127799","url":null,"abstract":"<div><div>This study proposes to combine plant-derived galactomannan and MXene to form an organic-inorganic hydrogel network with integrative antibacterial and osteogenic properties. Oxidized galactomannan (OxGa) was blended with N-succinyl chitosan (NSC) and varying concentrations of Mxene, owing to its high reactivity and biocompatibility. The results indicated that Mxene-loaded OxGa/NSC scaffolds exhibited biomimetic topography, adequate mechanical features and excellent physicochemical properties with strong antibacterial properties against pathogenic microbes. The cell culture experiments showed dose-dependent cytotoxic behaviour. An optimized MXene content of ≤4 mg/ml revealed no cytotoxicity and augmented the proliferation of osteoblast cells. Similar results were obtained in gene expression analysis where ALP, COL1A1, RUNX2, and SOX2 genes showed up-regulation. In addition, the chorioallantoic membrane (CAM) assay also illustrated augmentation of angiogenesis without any toxicity. The overall results highlight the dual performance of OxGa/NSC-MXene scaffolds to exhibit anti-infection with simultaneous osteogenic properties, which is purely determined by the concentration of MXene. Therefore, regulating MXene concentration can serve as a chemical switch in imparting adequate antibacterial functions with the ability to allow new osseous generation. Our findings on the newly designed Mxene-loaded OxGa/NSC scaffolds can be a promising biomaterial for bone-related infections with a concurrent ability to promote osteogenesis.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"315 ","pages":"Article 127799"},"PeriodicalIF":4.1,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142594233","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-07DOI: 10.1016/j.polymer.2024.127793
Yanxu Tian , Jiangang Zhang , Wen Cao , Xiong Liu , Xianming Zhang , Wenxing Chen , Jianna Bao
Poly(lactic acid) (PLA), which is recognized as a potential biodegradable material, brings serious fire concern because of its flammability with heavily molten drips. In this investigation, a bio-based flame retardant named CS@ATMP@MI (CAM) consisting of chitosan (CS), amino trimethylene phosphonic acid (ATMP), and methionine (MI) was developed through a simple and environmental-friendly synthesis approach. CAM provided effective flame retardancy and anti-dripping ability without compromising mechanical properties. PLA/CAM composites achieved a UL-94 V-0 rating with 1.0 wt% CAM and a limited oxygen index value of 28.4 % with 3.0 wt% CAM. The high efficiency is due to the high phosphate content in ATMP and the strong coordination between CS, ATMP, and MI. The cone calorimetry tests showed that adding 2.0 wt% CAM increased the total smoke production from 0.2 to 0.6 m2, and thermogravimetric analysis/infrared spectrum analysis indicated that combustible gas production was reduced over 50 % with 3.0 wt% CAM, demonstrating that phosphorus-nitrogen synergy in CAM could effectively capture free radicals and released inert gases. Char analysis showed that the PLA/CAM composites could form a thicker and denser char layer during combustion due to phosphorus-sulfur synergy, which promoted char formation to shield mass transfer. PLA/CAM composites maintained excellent mechanical performance, with a 3.0 wt% CAM increasing tensile strength from 53.9 to 57.3 MPa and Young's modulus from 1782 to 2262 MPa. This study presented a sustainable method for synthesizing an effective bio-based flame retardant and a strategy for producing eco-friendly, fire-resistant PLA composites for industrial applications.
{"title":"Green synthesis of a novel P/N/S containing bio-based flame retardant and its applications in poly(lactic acid): rapid self-extinguish, anti-dripping, and excellent mechanical performance","authors":"Yanxu Tian , Jiangang Zhang , Wen Cao , Xiong Liu , Xianming Zhang , Wenxing Chen , Jianna Bao","doi":"10.1016/j.polymer.2024.127793","DOIUrl":"10.1016/j.polymer.2024.127793","url":null,"abstract":"<div><div>Poly(lactic acid) (PLA), which is recognized as a potential biodegradable material, brings serious fire concern because of its flammability with heavily molten drips. In this investigation, a bio-based flame retardant named CS@ATMP@MI (CAM) consisting of chitosan (CS), amino trimethylene phosphonic acid (ATMP), and methionine (MI) was developed through a simple and environmental-friendly synthesis approach. CAM provided effective flame retardancy and anti-dripping ability without compromising mechanical properties. PLA/CAM composites achieved a UL-94 V-0 rating with 1.0 wt% CAM and a limited oxygen index value of 28.4 % with 3.0 wt% CAM. The high efficiency is due to the high phosphate content in ATMP and the strong coordination between CS, ATMP, and MI. The cone calorimetry tests showed that adding 2.0 wt% CAM increased the total smoke production from 0.2 to 0.6 m<sup>2</sup>, and thermogravimetric analysis/infrared spectrum analysis indicated that combustible gas production was reduced over 50 % with 3.0 wt% CAM, demonstrating that phosphorus-nitrogen synergy in CAM could effectively capture free radicals and released inert gases. Char analysis showed that the PLA/CAM composites could form a thicker and denser char layer during combustion due to phosphorus-sulfur synergy, which promoted char formation to shield mass transfer. PLA/CAM composites maintained excellent mechanical performance, with a 3.0 wt% CAM increasing tensile strength from 53.9 to 57.3 MPa and Young's modulus from 1782 to 2262 MPa. This study presented a sustainable method for synthesizing an effective bio-based flame retardant and a strategy for producing eco-friendly, fire-resistant PLA composites for industrial applications.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"315 ","pages":"Article 127793"},"PeriodicalIF":4.1,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142597630","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-07DOI: 10.1016/j.polymer.2024.127802
Hui Dong , Linlin Wang , Shengtao Zhang , Yunran Zhang , Wenjie Yang , Chunxiang Wei , SanE Zhu , Zhongxing Geng , Shibin Nie , Liangji Xu , Hongdian Lu , Wei Yang
Waterborne polyurethane (WPU) is increasingly favored because of its affordability, eco-friendliness, and water-based storage convenience. However, the inclusion of hydrophilic groups can diminish its mechanical strength and water resistance. Herein, a range of bio-based waterborne polyurethanes were synthesized by using economical and sustainable poly(trimethylene ether) glycol (PO3G), isophorone diisocyanate (IPDI), and poly(propylene glycol) (PPG) as raw materials. They exhibited superior mechanical properties, transparency, and corrosion resistance. We explored the effect of PO3G content on the properties of these bio-based WPU emulsions and films. The findings revealed that films with over 30 % PO3G content demonstrated a high tensile strength (above 10 MPa) and maintained a high elongation at break (above 4000 %), matching or surpassing existing bio-based WPU systems. The corrosion resistance of these films was also exceptional, with a high inhibition efficiency (above 99.97 %). This research introduces a new approach for creating high-performance bio-based WPUs with promising applications in coatings, leather, and biomedical materials.
{"title":"Ultra-tough, strong and transparent bio-based waterborne polyurethanes with exceptional anti-corrosion properties","authors":"Hui Dong , Linlin Wang , Shengtao Zhang , Yunran Zhang , Wenjie Yang , Chunxiang Wei , SanE Zhu , Zhongxing Geng , Shibin Nie , Liangji Xu , Hongdian Lu , Wei Yang","doi":"10.1016/j.polymer.2024.127802","DOIUrl":"10.1016/j.polymer.2024.127802","url":null,"abstract":"<div><div>Waterborne polyurethane (WPU) is increasingly favored because of its affordability, eco-friendliness, and water-based storage convenience. However, the inclusion of hydrophilic groups can diminish its mechanical strength and water resistance. Herein, a range of bio-based waterborne polyurethanes were synthesized by using economical and sustainable poly(trimethylene ether) glycol (PO3G), isophorone diisocyanate (IPDI), and poly(propylene glycol) (PPG) as raw materials. They exhibited superior mechanical properties, transparency, and corrosion resistance. We explored the effect of PO3G content on the properties of these bio-based WPU emulsions and films. The findings revealed that films with over 30 % PO3G content demonstrated a high tensile strength (above 10 MPa) and maintained a high elongation at break (above 4000 %), matching or surpassing existing bio-based WPU systems. The corrosion resistance of these films was also exceptional, with a high inhibition efficiency (above 99.97 %). This research introduces a new approach for creating high-performance bio-based WPUs with promising applications in coatings, leather, and biomedical materials.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"315 ","pages":"Article 127802"},"PeriodicalIF":4.1,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142594251","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}
A comprehensive study of benzoxazines derived from magnolol and five different substituted aniline moieties through Mannich condensation was carried out. The structural confirmation was ascertained using different spectral analyses. Mg-a exhibited a lowest polymerization temperature of 220 °C than that of other monomers. Whereas, poly (Mg-ea) showed relatively the higher initial thermal stability until 411 °C with char yield of 56 % at 850 °C and enhanced values of limiting oxygen index (LOI) and statistic heat resistance index (HRI) than rest of polybenzoxazines. The Mg-pfa benzoxazine monomer exhibits significant antibacterial behavior with a maximum of 22 mm zone of inhibition and less cytotoxicity with IC50 value of 162 μg/ml as well as better corrosion resistant properties with 99 % corrosion inhibition efficiency. The hydrophobic studies indicated that poly (Mg-tfa) exhibited the highest water contact angle (CA) value of 143°. Poly (Mg-tfa) coated cotton fabric was resistant to chemical and UV treatments along with the 97 % of oil water separating efficiency. Polybenzoxazine composites were derived from poly (Mg-fa) matrix and cashew nut shell residue ash (CNA) and cashew nut shell carbon (CNC) fillers to ascertain influence on thermal, dielectric and hydrophobic properties. Poly (Mg-fa) composites reinforced with 15 wt% of CNA and 15 wt% of CNC exhibited dielectric constant values of 2.71 and 6.91 respectively at a frequency of 1 MHz. Findings from multifaceted studies indicate that the polybenzoxazines and composites reported in the present work can be utilized for anti-corrosion, anti-microbial, oil-water separation and electronic applications for improved performance and enhanced longevity.
{"title":"Bio-inspired sustainable benzoxazine based composites containing aniline derivatives: A comprehensive study on anti-microbial, advanced coatings, oil-water separation and electronic utilizations","authors":"Priyanka Madesh , Balaji Krishnasamy , Thangaraju Dheivasigamani , Alagar Muthukaruppan","doi":"10.1016/j.polymer.2024.127801","DOIUrl":"10.1016/j.polymer.2024.127801","url":null,"abstract":"<div><div>A comprehensive study of benzoxazines derived from magnolol and five different substituted aniline moieties through Mannich condensation was carried out. The structural confirmation was ascertained using different spectral analyses. Mg-a exhibited a lowest polymerization temperature of 220 °C than that of other monomers. Whereas, poly (Mg-ea) showed relatively the higher initial thermal stability until 411 °C with char yield of 56 % at 850 °C and enhanced values of limiting oxygen index (LOI) and statistic heat resistance index (HRI) than rest of polybenzoxazines. The Mg-pfa benzoxazine monomer exhibits significant antibacterial behavior with a maximum of 22 mm zone of inhibition and less cytotoxicity with IC50 value of 162 μg/ml as well as better corrosion resistant properties with 99 % corrosion inhibition efficiency. The hydrophobic studies indicated that poly (Mg-tfa) exhibited the highest water contact angle (CA) value of 143°. Poly (Mg-tfa) coated cotton fabric was resistant to chemical and UV treatments along with the 97 % of oil water separating efficiency. Polybenzoxazine composites were derived from poly (Mg-fa) matrix and cashew nut shell residue ash (CNA) and cashew nut shell carbon (CNC) fillers to ascertain influence on thermal, dielectric and hydrophobic properties. Poly (Mg-fa) composites reinforced with 15 wt% of CNA and 15 wt% of CNC exhibited dielectric constant values of 2.71 and 6.91 respectively at a frequency of 1 MHz. Findings from multifaceted studies indicate that the polybenzoxazines and composites reported in the present work can be utilized for anti-corrosion, anti-microbial, oil-water separation and electronic applications for improved performance and enhanced longevity.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"315 ","pages":"Article 127801"},"PeriodicalIF":4.1,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142594557","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-07DOI: 10.1016/j.polymer.2024.127790
Bei Jiang , Zhaopeng Nie , Guiming Zhao , Bin Wang , Hongxing Xu , Xiansheng Zhang , Lili Wang
The combination of hydrogels and fabrics opens up significant opportunities for flexible materials, particularly in biomedicine and wearable technology. However, the weak interface caused by insufficient interactions between the different phases and the substantial modulus mismatch limit their broader application. In this research, flexible and amorphous polyvinyl alcohol (PVA) hydrogels were integrated with polar and elastic fabrics to create multifunctional composites via in-situ freeze-thawing technology. First, by incorporating antifreeze inorganic salts into the precursor solution, we effectively suppressed ice crystal growth during the cooling process, promoting a uniform and loosely aligned PVA chain structure. This led to the formation of an amorphous crosslinked network while simultaneously releasing free hydroxyl groups. These hydroxyl groups facilitate the formation of robust interfaces within the composite. In addition, an elastic fabric composed of a polyester-polyurethane fiber blend was selected. The polyester fibers, rich in carbonyl groups along their polymer chains, form strong hydrogen bonds with the free hydroxyl groups from the PVA hydrogel, creating a highly resilient interface. The polyurethane fibers contribute to a lower Young's modulus, as well as excellent elasticity and ductility, reducing the fabric's inherent stiffness and mitigating fiber pull-out failure. Further, the incorporation of CaCl2 not only created an environment rich in free ions, but also provided the amorphous structure with increasing spacing between adjacent polymer chains, facilitating the transportation of ions. Therefore, the composite exhibits adept sensing capabilities for intricate human body movements, fostering auspicious prospects in smart sensor applications.
{"title":"Matching combination of amorphous ionic hydrogel with elastic fabric enables integrated properties for wearable sensing","authors":"Bei Jiang , Zhaopeng Nie , Guiming Zhao , Bin Wang , Hongxing Xu , Xiansheng Zhang , Lili Wang","doi":"10.1016/j.polymer.2024.127790","DOIUrl":"10.1016/j.polymer.2024.127790","url":null,"abstract":"<div><div>The combination of hydrogels and fabrics opens up significant opportunities for flexible materials, particularly in biomedicine and wearable technology. However, the weak interface caused by insufficient interactions between the different phases and the substantial modulus mismatch limit their broader application. In this research, flexible and amorphous polyvinyl alcohol (PVA) hydrogels were integrated with polar and elastic fabrics to create multifunctional composites via in-situ freeze-thawing technology. First, by incorporating antifreeze inorganic salts into the precursor solution, we effectively suppressed ice crystal growth during the cooling process, promoting a uniform and loosely aligned PVA chain structure. This led to the formation of an amorphous crosslinked network while simultaneously releasing free hydroxyl groups. These hydroxyl groups facilitate the formation of robust interfaces within the composite. In addition, an elastic fabric composed of a polyester-polyurethane fiber blend was selected. The polyester fibers, rich in carbonyl groups along their polymer chains, form strong hydrogen bonds with the free hydroxyl groups from the PVA hydrogel, creating a highly resilient interface. The polyurethane fibers contribute to a lower Young's modulus, as well as excellent elasticity and ductility, reducing the fabric's inherent stiffness and mitigating fiber pull-out failure. Further, the incorporation of CaCl<sub>2</sub> not only created an environment rich in free ions, but also provided the amorphous structure with increasing spacing between adjacent polymer chains, facilitating the transportation of ions. Therefore, the composite exhibits adept sensing capabilities for intricate human body movements, fostering auspicious prospects in smart sensor applications.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"315 ","pages":"Article 127790"},"PeriodicalIF":4.1,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142594255","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-07DOI: 10.1016/j.polymer.2024.127803
Hai Wang , Xue Jin , Dongmei Cui
Solvent induced crystallization and phase transition is an interesting phenomenon that has been observed in many kinds of semicrystalline polymer. In the case of syndiotactic polystyrene (SPS) which exhibits complicated phase transition behavior, this process may be different when the phenyl rings are substituted by polarity groups. In our previous work, the crystal structures of a series of –OCH3 (OMe) substituted SPS and OMe-SPS/solvent complexes were analyzed (Macromolecules2021, 54, 1881 and Macromolecules2022, 55, 8222). In this particular work, the phase transition behavior of OMe-SPS, especially meta-OMe-SPS with different initial crystalline structures was discussed based on in situ 2-dimensional wide-angle X-ray diffractions (2D-WAXD) in the presence of organic solvent. It is found that meta-OMe-SPS in amorphous state and mesophase shows similar solvent induced phase transition like the cases of SPS. However Meanwhile, highly crystalline and oriented meta-OMe-SPS also exhibits organic solvent induced phase transition from β form with planar zigzag conformation into δ form with helical conformation, whichis has not been observed in SPS. The subsequent heating of meta-OMe-SPS δ and γ forms does not form β form, which is also unlike the situation of SPS δ/δe-γ-α/β transition. The OMe substituted group that changes the polarity of the phenyl rings may be the chemical structure region of affecting the chain conformation energy and phase transition behavior.
{"title":"Solvent induced crystallization and phase transition of syndiotactic polymethoxystyrene investigated using In situ wide angle X-ray diffraction","authors":"Hai Wang , Xue Jin , Dongmei Cui","doi":"10.1016/j.polymer.2024.127803","DOIUrl":"10.1016/j.polymer.2024.127803","url":null,"abstract":"<div><div>Solvent induced crystallization and phase transition is an interesting phenomenon that has been observed in many kinds of semicrystalline polymer. In the case of syndiotactic polystyrene (SPS) which exhibits complicated phase transition behavior, this process may be different when the phenyl rings are substituted by polarity groups. In our previous work, the crystal structures of a series of –OCH<sub>3</sub> (OMe) substituted SPS and OMe-SPS/solvent complexes were analyzed (<em>Macromolecules</em> <strong>2021</strong>, <em>54</em>, 1881 and <em>Macromolecules</em> <strong>2022</strong>, 55, <em>8222</em>). In this particular work, the phase transition behavior of OMe-SPS, especially meta-OMe-SPS with different initial crystalline structures was discussed based on in situ 2-dimensional wide-angle X-ray diffractions (2D-WAXD) in the presence of organic solvent. It is found that meta-OMe-SPS in amorphous state and mesophase shows similar solvent induced phase transition like the cases of SPS. <del>However</del> Meanwhile, highly crystalline and oriented meta-OMe-SPS also exhibits organic solvent induced phase transition from β form with planar zigzag conformation into δ form with helical conformation, which<del>is</del> has not been observed in SPS. The subsequent heating of meta-OMe-SPS δ and γ forms does not form β form, which is <del>also</del> unlike the situation of SPS δ/δ<sub>e</sub>-γ-α/β transition. The OMe substituted group that changes the polarity of the phenyl rings may be the chemical structure region of affecting the chain conformation energy and phase transition behavior.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"315 ","pages":"Article 127803"},"PeriodicalIF":4.1,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142597631","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-07DOI: 10.1016/j.polymer.2024.127795
Lina M. Romero , Daniel A. Palacio , Samir Esquivel , Gabriela A. Sánchez- Sanhueza , Mary Montaño , D. Rojas , A.F. Jaramillo , Carlos Medina , Cristóbal Montalba , Manuel F. Meléndrez
This paper introduces a simple procedure for developing composite materials with antibacterial and biocompatible properties using polylactic acid (PLA) and polypropylene (PP). These composites incorporate three variants of zeolites in different percentages as filler agents: pure zeolite (PZ), copper ion-saturated zeolite (LZ), and copper-ion-saturated zeolite with copper oxide nanoparticles (LZ-nCu). The composites were prepared by the extrusion method and manufactured by injection molding. The impact of these zeolites on various material properties was evaluated, including morphology, thermal stability, mechanical properties, antibacterial capacity, biocompatibility, water absorption, and chemical resistance. The results demonstrated that (i) the incorporation of zeolite into the PP matrix improved thermal stability and increased the tensile modulus of the composites. For PLA-based composites, although there was a slight decrease in these values compared to pure PLA, they remained within acceptable ranges; (ii) zeolite LZ and LZnCu composites at 5 and 10 % by weight effectively inhibited the growth of Gram-positive and Gram-negative bacteria within a maximum of 2 h of contact; and (iii) composites containing 10 % by weight of PZ, LZ, or LZ-nCu showed reduced mechanical properties due to a tendency to form agglomerates. Additionally, LZ and LZ-nCu composites with the same percentage proved highly toxic to human gingival fibroblast cells (HGFs). PLA/LZ-nCu at 5 % and PP/LZ at 5 % composites exhibited antibacterial properties with bactericidal effects upon contact, high biocompatibility, and lower water absorption compared to the pure polymeric matrix. These results highlight the operational effectiveness of the procedure and suggest the potential of these composites in biomedical applications, such as in vitro dentistry, without contamination risks.
{"title":"Contact antibacterial and biocompatible polymeric, composite with copper zeolite filler and copper oxide, nanoparticles: A step towards new raw materials for the biomedical industry","authors":"Lina M. Romero , Daniel A. Palacio , Samir Esquivel , Gabriela A. Sánchez- Sanhueza , Mary Montaño , D. Rojas , A.F. Jaramillo , Carlos Medina , Cristóbal Montalba , Manuel F. Meléndrez","doi":"10.1016/j.polymer.2024.127795","DOIUrl":"10.1016/j.polymer.2024.127795","url":null,"abstract":"<div><div>This paper introduces a simple procedure for developing composite materials with antibacterial and biocompatible properties using polylactic acid (PLA) and polypropylene (PP). These composites incorporate three variants of zeolites in different percentages as filler agents: pure zeolite (PZ), copper ion-saturated zeolite (LZ), and copper-ion-saturated zeolite with copper oxide nanoparticles (LZ-nCu). The composites were prepared by the extrusion method and manufactured by injection molding. The impact of these zeolites on various material properties was evaluated, including morphology, thermal stability, mechanical properties, antibacterial capacity, biocompatibility, water absorption, and chemical resistance. The results demonstrated that (i) the incorporation of zeolite into the PP matrix improved thermal stability and increased the tensile modulus of the composites. For PLA-based composites, although there was a slight decrease in these values compared to pure PLA, they remained within acceptable ranges; (ii) zeolite LZ and LZnCu composites at 5 and 10 % by weight effectively inhibited the growth of Gram-positive and Gram-negative bacteria within a maximum of 2 h of contact; and (iii) composites containing 10 % by weight of PZ, LZ, or LZ-nCu showed reduced mechanical properties due to a tendency to form agglomerates. Additionally, LZ and LZ-nCu composites with the same percentage proved highly toxic to human gingival fibroblast cells (HGFs). PLA/LZ-nCu at 5 % and PP/LZ at 5 % composites exhibited antibacterial properties with bactericidal effects upon contact, high biocompatibility, and lower water absorption compared to the pure polymeric matrix. These results highlight the operational effectiveness of the procedure and suggest the potential of these composites in biomedical applications, such as in vitro dentistry, without contamination risks.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"315 ","pages":"Article 127795"},"PeriodicalIF":4.1,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142594498","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-07DOI: 10.1016/j.polymer.2024.127794
Zhaopeng Hu , Xin Jiang , Yihu Song , Yongzhong Bao , Qiang Zheng
A novel secondary vulcanization-dilution process was employed to prepare ethylene-propylene-diene rubber/polypropylene (EPDM/PP) thermoplastic vulcanizates (TPVs) with uniform size, controllable crosslinking density, and content of rubber particles to assess their significant impact on rheological behavior using Fourier-rheology, shedding light on the interplay between microstructural features and macroscopic material properties. Through the application of the time-concentration superposition principle, a broad reinforcement spectrum is established, enhancing the understanding of TPV structure-property relationships. Also studied is the Mullins effect of the TPVs at two different temperatures, contributing to a deeper understanding of their deformation mechanisms. The results offer valuable insights for the formulation and processing of TPVs, emphasizing the importance of tailored particle characteristics for optimizing material performance.
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Pub Date : 2024-11-06DOI: 10.1016/j.polymer.2024.127798
Mohammed A.M.M. Al-Samet , Simge Kara , Engin Burgaz
In this study, fibrous membrane composites containing poly (vinylidene fluoride-co-hexafluoropropylene) P(VdF-co-HFP) copolymer and various amounts of magnesium borate Mg2B2O5 were prepared via electrospinning method. The crystallization behavior, thermal stability, microstructure, porosity, liquid electrolyte uptake and electrochemical performance of electrospun membranes were investigated in detail. X-ray diffraction (XRD) and differential scanning calorimetry (DSC) show that, the crystallinity of P(VdF-co-HFP) tends to decrease with increasing amount of Mg2B2O5 particles. The electrospun membrane containing P(VdF-co-HFP) and 2.5 wt% of Mg2B2O5 demonstrates stronger anti-shrinkage properties compared to those of commercial polypropylene (PP) or pure P(VdF-co-HFP) separators at 140 °C. The fibrous membrane consisting of 2.5 wt% Mg2B2O5 exhibits high electrolyte uptake (381 %), low interfacial resistance and good porosity at room temperature (81 %), even after heating at 140 °C the porosity becomes 78 %. Moreover, Li||LiFePO4 cell using P(VdF-co-HFP) separator with 2.5 wt% of Mg2B2O5 shows better discharge capacities of 167.5 and 146.8 mAh g−1 at 0.2 C and 5 C, respectively, compared to those of commercial PP separator which delivers only 158 and 127 mAh g−1 at 0.2 C and 5 C, respectively. [P(VdF-co-HFP) + 2.5 wt% Mg2B2O5] separator also provides discharge capacity retention of 99.9 % after 100 cycles at 9 C, in comparison with only 87 % for polypropylene separator. Such results reveal that P(VdF-co-HFP) membrane containing 2.5 wt% Mg2B2O5 is a highly promising separator with good safety which can be used in high-performance lithium-ion batteries.
本研究通过电纺丝方法制备了含有聚偏氟乙烯-六氟丙烯（P(VdF-co-HFP)共聚物和不同量的硼酸镁 Mg2B2O5 的纤维膜复合材料。详细研究了电纺丝膜的结晶行为、热稳定性、微观结构、孔隙率、液体电解质吸收和电化学性能。X 射线衍射（XRD）和差示扫描量热法（DSC）显示，P(VdF-co-HFP)的结晶度随着 Mg2B2O5 颗粒含量的增加而降低。与商用聚丙烯（PP）或纯 P（VdF-co-HFP）分离剂相比，含有 P（VdF-co-HFP）和 2.5 wt.% Mg2B2O5 的电纺膜在 140 °C 下具有更强的抗收缩性能。由 2.5 wt.% Mg2B2O5 组成的纤维膜在室温下具有高电解质吸收率（381%）、低界面电阻和良好的孔隙率（81%），即使在 140 °C 下加热后，孔隙率也达到了 78%。此外，使用含有 2.5 wt.% Mg2B2O5 的 P（VdF-co-HFP）隔膜的 Li||LiFePO4 电池在 0.2 摄氏度和 5 摄氏度时的放电容量分别为 167.5 mAh g-1 和 146.8 mAh g-1，而使用商用 PP 隔膜的电池在 0.2 摄氏度和 5 摄氏度时的放电容量分别只有 158 mAh g-1 和 127 mAh g-1。[P(VdF-co-HFP) + 2.5 wt.% Mg2B2O5]分离器在 9 C 下循环 100 次后，放电容量保持率也达到 99.9%，而聚丙烯分离器的放电容量保持率仅为 87%。这些结果表明，含有 2.5 wt.% Mg2B2O5 的 P（VdF-co-HFP）膜是一种极具潜力的隔膜，具有良好的安全性，可用于高性能锂离子电池。
{"title":"Enhancement of physical and electrochemical properties of electrospun P(VdF-co-HFP) separators by incorporating magnesium borate for advanced lithium-ion batteries","authors":"Mohammed A.M.M. Al-Samet , Simge Kara , Engin Burgaz","doi":"10.1016/j.polymer.2024.127798","DOIUrl":"10.1016/j.polymer.2024.127798","url":null,"abstract":"<div><div>In this study, fibrous membrane composites containing poly (vinylidene fluoride-co-hexafluoropropylene) P(VdF-co-HFP) copolymer and various amounts of magnesium borate Mg<sub>2</sub>B<sub>2</sub>O<sub>5</sub> were prepared via electrospinning method. The crystallization behavior, thermal stability, microstructure, porosity, liquid electrolyte uptake and electrochemical performance of electrospun membranes were investigated in detail. X-ray diffraction (XRD) and differential scanning calorimetry (DSC) show that, the crystallinity of P(VdF-co-HFP) tends to decrease with increasing amount of Mg<sub>2</sub>B<sub>2</sub>O<sub>5</sub> particles. The electrospun membrane containing P(VdF-co-HFP) and 2.5 wt% of Mg<sub>2</sub>B<sub>2</sub>O<sub>5</sub> demonstrates stronger anti-shrinkage properties compared to those of commercial polypropylene (PP) or pure P(VdF-co-HFP) separators at 140 °C. The fibrous membrane consisting of 2.5 wt% Mg<sub>2</sub>B<sub>2</sub>O<sub>5</sub> exhibits high electrolyte uptake (381 %), low interfacial resistance and good porosity at room temperature (81 %), even after heating at 140 °C the porosity becomes 78 %. Moreover, Li||LiFePO<sub>4</sub> cell using P(VdF-co-HFP) separator with 2.5 wt% of Mg<sub>2</sub>B<sub>2</sub>O<sub>5</sub> shows better discharge capacities of 167.5 and 146.8 mAh g<sup>−1</sup> at 0.2 C and 5 C, respectively, compared to those of commercial PP separator which delivers only 158 and 127 mAh g<sup>−1</sup> at 0.2 C and 5 C, respectively. [P(VdF-co-HFP) + 2.5 wt% Mg<sub>2</sub>B<sub>2</sub>O<sub>5</sub>] separator also provides discharge capacity retention of 99.9 % after 100 cycles at 9 C, in comparison with only 87 % for polypropylene separator. Such results reveal that P(VdF-co-HFP) membrane containing 2.5 wt% Mg<sub>2</sub>B<sub>2</sub>O<sub>5</sub> is a highly promising separator with good safety which can be used in high-performance lithium-ion batteries.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"315 ","pages":"Article 127798"},"PeriodicalIF":4.1,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142594260","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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