Pub Date : 2025-03-27DOI: 10.1016/j.polymer.2025.128326
Yiming Du , Hua Wang , Xiaofei Li , Hang Li , Wei Zhang , Yanyan Liu , Xingyou Tian
Self-healing materials that can autonomously repair physical damage and restore mechanical properties have significant potential in advanced technologies, including flexible electronics and smart coatings. In this work, we synthesized poly(dimethylsiloxane)-polyurea (PDMS-IUxMU1-x) to study the effect of multiple hydrogen bonds on the mechanical and self-healing properties and found that improving the dynamics of strong hydrogen bonding is the key to breaking the trade-off between mechanical and self-healing properties. Inspired by the octopus, we introduced different solvents to improve the healing performance. Ultimately, the stiff PDMS-MU samples (1.18 MPa, 1282 %), which were difficult to heal at elevated temperatures, achieved a remarkable strength recovery (66.7 % in 10 min, 25 °C). We verified the effect of this strategy on other polymers and achieved rapid healing at ambient temperature (88 % in 10 min and 98.5 % in 3 h) and at −20 °C (98.9% in 24 h), surpassing many reported solvent-assisted healing materials. Moreover, our findings revealed that ethanol significantly improves the dynamics of hydrogen bonding, increases the mobility of polymer molecular chains, reduces the activation energy, and ultimately promotes healing. This research offers valuable insights into designing high-performance self-healing materials that are reprocessable and energy-efficient, addressing key challenges in the field and promoting the development of self-healing elastomers in flexible and wearable devices.
{"title":"Octopus-inspired solvent-assisted rapid self-healing polydimethylsiloxane-polyurea elastomers","authors":"Yiming Du , Hua Wang , Xiaofei Li , Hang Li , Wei Zhang , Yanyan Liu , Xingyou Tian","doi":"10.1016/j.polymer.2025.128326","DOIUrl":"10.1016/j.polymer.2025.128326","url":null,"abstract":"<div><div>Self-healing materials that can autonomously repair physical damage and restore mechanical properties have significant potential in advanced technologies, including flexible electronics and smart coatings. In this work, we synthesized poly(dimethylsiloxane)-polyurea (PDMS-IU<sub>x</sub>MU<sub>1-x</sub>) to study the effect of multiple hydrogen bonds on the mechanical and self-healing properties and found that improving the dynamics of strong hydrogen bonding is the key to breaking the trade-off between mechanical and self-healing properties. Inspired by the octopus, we introduced different solvents to improve the healing performance. Ultimately, the stiff PDMS-MU samples (1.18 MPa, 1282 %), which were difficult to heal at elevated temperatures, achieved a remarkable strength recovery (66.7 % in 10 min, 25 °C). We verified the effect of this strategy on other polymers and achieved rapid healing at ambient temperature (88 % in 10 min and 98.5 % in 3 h) and at −20 °C (98.9% in 24 h), surpassing many reported solvent-assisted healing materials. Moreover, our findings revealed that ethanol significantly improves the dynamics of hydrogen bonding, increases the mobility of polymer molecular chains, reduces the activation energy, and ultimately promotes healing. This research offers valuable insights into designing high-performance self-healing materials that are reprocessable and energy-efficient, addressing key challenges in the field and promoting the development of self-healing elastomers in flexible and wearable devices.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"326 ","pages":"Article 128326"},"PeriodicalIF":4.1,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723492","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-27DOI: 10.1016/j.polymer.2025.128325
Yanfang Guan , Kasolo Enock , Jiajun Su , Zhenbin Yuan , Tong Jin , Zhaoyang Xia , Yujie Li , Xihan Gao , Han Wang , Xiang Li , Song Li , Lin Zhang , Changwei Zhu , Shuai Long Zhang , Yuhan Shen , Zhai Dandan
Recent developments in new materials for healthcare and wearable electronics highlight the potential of hydrogels, renowned flexibility, biocompatibility, and adaptability. Composite hydrogels have significant capability for applications requiring multifunctional performance. However, the gas-sensitive components used in traditional gas sensors lack properties such as self-adhere, self-heal, or stretch. This paper introduces a novel composite flexible oxygen-sensitive material composed of polyanionic cellulose (PAC), which is rich in carboxyl groups, locust bean gum (LBG) enhances hydrogel adhesion, and polyacrylamide (PAM) forming a network with diverse interaction sites. The integration of the hydrogel composite with Potassium persulfate (KPS) and N, N1 methylene bis (acrylamide) AR (MBA) led to improved performance outcomes. Using the hydrogel's distinctive characteristics, the oxygen sensor demonstrates exceptional stretchability of up to 1533 %, gas selectivity, and stable performance under varying humidity conditions, the sensor performs optimally at 40 % relative humidity (RH). Resistance measurements show a sharp increase from tens of ohms to 4.8–5.3 kΩ when exposed to O2 at the 8-s mark, maintaining this level during exposure. Notably, the sensor demonstrates no significant resistance change in response to N2 over time. The proposed PAC/LBG/PAM (PLP) hydrogel offers advantages such as excellent stretchability, self-healing ability, electrical conductivity, strong adhesion to organic and inorganic materials, operation at low temperatures, adsorption of nanoparticles, operation under various humidity levels, shortening wound healing period, and selectivity and detection of oxygen gas. The novel hydrogel holds the potential for application in various fields, including flexible sensor production, water management, and wearables.
{"title":"A high sensitivity and flexibility detection sensor for oxygen concentration based on polyanionic cellulose/locust bean gum/polyacrylamide hydrogel combination","authors":"Yanfang Guan , Kasolo Enock , Jiajun Su , Zhenbin Yuan , Tong Jin , Zhaoyang Xia , Yujie Li , Xihan Gao , Han Wang , Xiang Li , Song Li , Lin Zhang , Changwei Zhu , Shuai Long Zhang , Yuhan Shen , Zhai Dandan","doi":"10.1016/j.polymer.2025.128325","DOIUrl":"10.1016/j.polymer.2025.128325","url":null,"abstract":"<div><div>Recent developments in new materials for healthcare and wearable electronics highlight the potential of hydrogels, renowned flexibility, biocompatibility, and adaptability. Composite hydrogels have significant capability for applications requiring multifunctional performance. However, the gas-sensitive components used in traditional gas sensors lack properties such as self-adhere, self-heal, or stretch. This paper introduces a novel composite flexible oxygen-sensitive material composed of polyanionic cellulose (PAC), which is rich in carboxyl groups, locust bean gum (LBG) enhances hydrogel adhesion, and polyacrylamide (PAM) forming a network with diverse interaction sites. The integration of the hydrogel composite with Potassium persulfate (KPS) and N, N<sup>1</sup> methylene bis (acrylamide) AR (MBA) led to improved performance outcomes. Using the hydrogel's distinctive characteristics, the oxygen sensor demonstrates exceptional stretchability of up to 1533 %, gas selectivity, and stable performance under varying humidity conditions, the sensor performs optimally at 40 % relative humidity (RH). Resistance measurements show a sharp increase from tens of ohms to 4.8–5.3 kΩ when exposed to O<sub>2</sub> at the 8-s mark, maintaining this level during exposure. Notably, the sensor demonstrates no significant resistance change in response to N<sub>2</sub> over time. The proposed PAC/LBG/PAM (PLP) hydrogel offers advantages such as excellent stretchability, self-healing ability, electrical conductivity, strong adhesion to organic and inorganic materials, operation at low temperatures, adsorption of nanoparticles, operation under various humidity levels, shortening wound healing period, and selectivity and detection of oxygen gas. The novel hydrogel holds the potential for application in various fields, including flexible sensor production, water management, and wearables.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"326 ","pages":"Article 128325"},"PeriodicalIF":4.1,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723493","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-26DOI: 10.1016/j.polymer.2025.128318
Thanh Van Vu, Jae Hyun Sim, Jinwoo Choi, Hokyeong Jeong, Seungjoo Park, Sangho Kim, Sangeun Baek, Hyunmin Lee, Youngjong Kang
This study investigates the conformational structure of hypocrystalline poly(methyl methacrylate) (PMMA) films (hc-PMMAs) prepared via thermal quenching with benzoic acid (BA) as an entropy diluent. FT-IR spectroscopy revealed a significant increase in the trans-gauche (tg) conformation in hc-PMMAs compared to their solution-cast PMMA counterparts. The presence of BA stretched the polymer chains, promoting crystallization. Conformational energy calculations showed that the tg conformation became more stable than the trans-trans (tt) form, contrary to natural PMMA, due to chain stress from the quenching process. Thermal analysis demonstrated a unique tg plateau below the glass transition temperature (Tg), followed by relaxation to tt above Tg. These findings highlight the potential for manipulating polymer conformation and crystallinity using entropy diluents.
{"title":"Conformational Energy Inversion in PMMA Crystals Prepared via Thermal Quenching with Entropy Diluents","authors":"Thanh Van Vu, Jae Hyun Sim, Jinwoo Choi, Hokyeong Jeong, Seungjoo Park, Sangho Kim, Sangeun Baek, Hyunmin Lee, Youngjong Kang","doi":"10.1016/j.polymer.2025.128318","DOIUrl":"https://doi.org/10.1016/j.polymer.2025.128318","url":null,"abstract":"This study investigates the conformational structure of hypocrystalline poly(methyl methacrylate) (PMMA) films (hc-PMMAs) prepared via thermal quenching with benzoic acid (BA) as an entropy diluent. FT-IR spectroscopy revealed a significant increase in the <em>trans-gauche</em> (<em>tg</em>) conformation in hc-PMMAs compared to their solution-cast PMMA counterparts. The presence of BA stretched the polymer chains, promoting crystallization. Conformational energy calculations showed that the <em>tg</em> conformation became more stable than the <em>trans-trans</em> (<em>tt</em>) form, contrary to natural PMMA, due to chain stress from the quenching process. Thermal analysis demonstrated a unique <em>tg</em> plateau below the glass transition temperature (<em>T</em><sub>g</sub>), followed by relaxation to <em>tt</em> above <em>T</em><sub>g</sub>. These findings highlight the potential for manipulating polymer conformation and crystallinity using entropy diluents.","PeriodicalId":405,"journal":{"name":"Polymer","volume":"21 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713386","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}
Boron nitride nanofibres (Cu@BNNF) flame retardants different copper doping was successfully synthesized by calcination. It was then applied to epoxy resin (EP), where uniform dispersion of Cu could be achieved by BN loading, and good flame retardant, mechanical and smoke toxicity inhibition properties were achieved at a low addition amount. Dense residual char was obtained from EP/0.6 Cu–BNNF (4 phr) composites, which could decrease the PHRR and PSPR by 63.45 % and 43.75 %, respectively, indicating that EP/Cu–BNNF composites have excellent fire protection properties. DSC analysis results showed that BNNF and Cu had a synergistic effect on the thermo-mechanical properties of EP composites, and the appropriate amount of Cu played a catalytic role in the cross-linking of EP. Thermogravimetric infrared (TG-FTIR) results showed that by controlling the doping amount of Cu, the generation of gas-phase hazardous products such as CO, aromatic compounds and flammable small molecule alkenes was significantly reduced, and the flame-retardant and smoke-eliminating properties of EP were improved. The analysis of the residual char after combustion shows that the incorporation of Cu–BNNF improves the densification. Based on the analysis of the gaseous and condensed phases to illustrate how BNNF and Cu play a role in burning EP nanocomposites.
通过煅烧成功合成了掺杂不同铜的氮化硼纳米纤维（Cu@BNNF）阻燃剂。将其应用于环氧树脂（EP）中，通过添加 BN 实现了铜的均匀分散，并在较低的添加量下获得了良好的阻燃、机械和烟毒抑制性能。EP/0.6 Cu-BNNF (4 phr) 复合材料得到了致密的残炭，使 PHRR 和 PSPR 分别降低了 63.45% 和 43.75%，表明 EP/Cu-BNNF 复合材料具有优异的防火性能。DSC 分析结果表明，BNNF 和 Cu 对 EP 复合材料的热机械性能有协同作用，适量的 Cu 对 EP 的交联起催化作用。热重红外（TG-FTIR）结果表明，通过控制 Cu 的掺杂量，可显著减少 CO、芳香族化合物和易燃小分子烯烃等气相有害产物的生成，提高 EP 的阻燃性和消烟性能。对燃烧后残炭的分析表明，Cu-BNNF 的加入提高了致密性。根据对气相和凝结相的分析，说明了 BNNF 和 Cu 在燃烧 EP 纳米复合材料中的作用。
{"title":"Optimization of Cu doping in BNNF: A new strategy to enhance the flame retardancy, mechanical properties and smoke toxicity suppression of epoxy resin","authors":"Yumeng Cui, Yunhong Jiao, Yuying Yang, Qiuting Lu, Quan Li, Jing Zhang, Hongqiang Qu, Jianzhong Xu","doi":"10.1016/j.polymer.2025.128312","DOIUrl":"10.1016/j.polymer.2025.128312","url":null,"abstract":"<div><div>Boron nitride nanofibres (Cu@BNNF) flame retardants different copper doping was successfully synthesized by calcination. It was then applied to epoxy resin (EP), where uniform dispersion of Cu could be achieved by BN loading, and good flame retardant, mechanical and smoke toxicity inhibition properties were achieved at a low addition amount. Dense residual char was obtained from EP/0.6 Cu–BNNF (4 phr) composites, which could decrease the PHRR and PSPR by 63.45 % and 43.75 %, respectively, indicating that EP/Cu–BNNF composites have excellent fire protection properties. DSC analysis results showed that BNNF and Cu had a synergistic effect on the thermo-mechanical properties of EP composites, and the appropriate amount of Cu played a catalytic role in the cross-linking of EP. Thermogravimetric infrared (TG-FTIR) results showed that by controlling the doping amount of Cu, the generation of gas-phase hazardous products such as CO, aromatic compounds and flammable small molecule alkenes was significantly reduced, and the flame-retardant and smoke-eliminating properties of EP were improved. The analysis of the residual char after combustion shows that the incorporation of Cu–BNNF improves the densification. Based on the analysis of the gaseous and condensed phases to illustrate how BNNF and Cu play a role in burning EP nanocomposites.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"326 ","pages":"Article 128312"},"PeriodicalIF":4.1,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703382","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-26DOI: 10.1016/j.polymer.2025.128317
Mélanie Girardot, Jean-François Tahon, Joël Lyskawa, Sophie Barrau
Copolymers of vinylidene fluoride (VDF) and trifluoroethylene (TrFE), P(VDF-co-TrFE), exhibit remarkable electroactive properties. More precisely, the copolymers with a molar fraction of VDF between 49 % and 55 % present high piezoelectric properties. However, the literature on P(VDF-co-TrFE) with this composition range is limited, and there are divergences regarding the attribution of crystal phases, unlike the copolymers containing around 70 %–80 % of VDF, which have been extensively studied. In this study, wide-angle X-ray scattering (WAXS) experiments were conducted on a 55/45 P(VDF-co-TrFE) film to gain a better understanding of its crystal structure in correlation to its high piezoelectric properties. For comparison, a 80/20 P(VDF-co-TrFE) film is used as a reference. The results reveal that 55/45 P(VDF-co-TrFE) is mainly composed of two defective ferroelectric (DFE) phases, unlike 80/20 P(VDF-co-TrFE), which contains a mixture of a small fraction of DFE phase and a high fraction of ferroelectric (FE) phases. The stretching of 55/45 copolymer film induces the transformation of DFE phases to FE phase to obtain a structure very similar to that of the unstretched 80/20 copolymer. After poling, the unstretched 55/45 P(VDF-co-TrFE) film exhibits a high piezoelectric coefficient d33 of −41 pC/N, compared to more classical values of −22 pC/N for both the stretched 55/45 P(VDF-co-TrFE) and the unstretched 80/20 P(VDF-co-TrFE). This result is mainly explained by the exclusive presence of DFE phases in the unstretched 55/45 P(VDF-co-TrFE), which have greater mobility and then a better ability to polarize compared to the FE phase. This study thus highlights the importance of the DFE phase presence impacted by the film elaboration process in achieving a high piezoelectric coefficient in copolymers. This investigation contributes to a better understanding of the relationships between elaboration, structure and properties of P(VDF-co-TrFE) films, which is a key issue for the design of advanced electroactive organic devices.
{"title":"New insights on the crystal structure of P(VDF-co-TrFE) copolymer (55/45 mol%) and influence on the high piezoelectric response","authors":"Mélanie Girardot, Jean-François Tahon, Joël Lyskawa, Sophie Barrau","doi":"10.1016/j.polymer.2025.128317","DOIUrl":"10.1016/j.polymer.2025.128317","url":null,"abstract":"<div><div>Copolymers of vinylidene fluoride (VDF) and trifluoroethylene (TrFE), P(VDF-co-TrFE), exhibit remarkable electroactive properties. More precisely, the copolymers with a molar fraction of VDF between 49 % and 55 % present high piezoelectric properties. However, the literature on P(VDF-co-TrFE) with this composition range is limited, and there are divergences regarding the attribution of crystal phases, unlike the copolymers containing around 70 %–80 % of VDF, which have been extensively studied. In this study, wide-angle X-ray scattering (WAXS) experiments were conducted on a 55/45 P(VDF-co-TrFE) film to gain a better understanding of its crystal structure in correlation to its high piezoelectric properties. For comparison, a 80/20 P(VDF-co-TrFE) film is used as a reference. The results reveal that 55/45 P(VDF-co-TrFE) is mainly composed of two defective ferroelectric (DFE) phases, unlike 80/20 P(VDF-co-TrFE), which contains a mixture of a small fraction of DFE phase and a high fraction of ferroelectric (FE) phases. The stretching of 55/45 copolymer film induces the transformation of DFE phases to FE phase to obtain a structure very similar to that of the unstretched 80/20 copolymer. After poling, the unstretched 55/45 P(VDF-co-TrFE) film exhibits a high piezoelectric coefficient d<sub>33</sub> of −41 pC/N, compared to more classical values of −22 pC/N for both the stretched 55/45 P(VDF-co-TrFE) and the unstretched 80/20 P(VDF-co-TrFE). This result is mainly explained by the exclusive presence of DFE phases in the unstretched 55/45 P(VDF-co-TrFE), which have greater mobility and then a better ability to polarize compared to the FE phase. This study thus highlights the importance of the DFE phase presence impacted by the film elaboration process in achieving a high piezoelectric coefficient in copolymers. This investigation contributes to a better understanding of the relationships between elaboration, structure and properties of P(VDF-co-TrFE) films, which is a key issue for the design of advanced electroactive organic devices.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"325 ","pages":"Article 128317"},"PeriodicalIF":4.1,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713385","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-26DOI: 10.1016/j.polymer.2025.128314
Xiaotao Wang , Chuan Xu , Yonggui Liao , Ruilin Wang , Zhihao Bi , Wing-Cheung Law , Chak-Yin Tang
Responsive drug transportation, release efficiency, and low toxicity of drug delivery are important factors in the controlled release area. The conventional drug release system is hard to balance all the factors in a complex environment. In this study, we present a novel approach for synthesizing rare earth upconversion nanoparticles (UCNPs) based nanocapsules with core-shell structures, capable of emitting visible light and ultraviolet (UV) light for photodegradation under irradiation with 980 nm near-infrared (NIR) light. The hydrophilicity of the UCNPs was significantly enhanced using the hydrochloric acid pickling method. We employed a sol-gel technique with tetraethoxysilane (TEOS) and bis[γ-(triethoxysilyl)propyl]-tetrasulfide (BTES) as mixed organosilicon sources to directly coat the UCNPs, forming UCNP@(s-s)mSiO2 nanocapsules. The degradation of these nanocapsules by glutathione (GSH) was systematically studied using the molybdosilicic blue method. Doxorubicin (DOX) was subsequently loaded into the nanocapsules, achieving a drug loading efficiency of 5.12 %. To prevent premature drug release, a polyethylene glycol (PEG) layer was coated onto the nanoparticle surface via modification and click chemistry, resulting in composite drug-loaded nanocapsules with dual responsiveness to light and GSH. Under neutral conditions, the nanocapsules exhibited minimal drug leakage. Upon NIR light stimulation, 1-(5-methoxy-2-nitro-4-prop-2-ynyloxy-phenyl)ethyl-N-succinimidyl carbonate (MNPSC) underwent photolysis, causing the PEG layer to detach and trigger drug release. In a simulated high concentration of intratumoral glutathione environment, the mesoporous organosilica degraded, further facilitating the drug release. The ultimate drug release rate reached an impressive 92 %. This smart dual-responsive nanocapsule system offers a promising strategy for controlled drug delivery, combining the advantages of NIR-triggered release and GSH-responsive degradation for enhanced therapeutic efficacy.
{"title":"Smart upconversion nanocapsules: Harnessing photodegradation and glutathione responsiveness of polymers for controlled release of Payloads","authors":"Xiaotao Wang , Chuan Xu , Yonggui Liao , Ruilin Wang , Zhihao Bi , Wing-Cheung Law , Chak-Yin Tang","doi":"10.1016/j.polymer.2025.128314","DOIUrl":"10.1016/j.polymer.2025.128314","url":null,"abstract":"<div><div>Responsive drug transportation, release efficiency, and low toxicity of drug delivery are important factors in the controlled release area. The conventional drug release system is hard to balance all the factors in a complex environment. In this study, we present a novel approach for synthesizing rare earth upconversion nanoparticles (UCNPs) based nanocapsules with core-shell structures, capable of emitting visible light and ultraviolet (UV) light for photodegradation under irradiation with 980 nm near-infrared (NIR) light. The hydrophilicity of the UCNPs was significantly enhanced using the hydrochloric acid pickling method. We employed a sol-gel technique with tetraethoxysilane (TEOS) and bis[γ-(triethoxysilyl)propyl]-tetrasulfide (BTES) as mixed organosilicon sources to directly coat the UCNPs, forming UCNP@(s-s)mSiO2 nanocapsules. The degradation of these nanocapsules by glutathione (GSH) was systematically studied using the molybdosilicic blue method. Doxorubicin (DOX) was subsequently loaded into the nanocapsules, achieving a drug loading efficiency of 5.12 %. To prevent premature drug release, a polyethylene glycol (PEG) layer was coated onto the nanoparticle surface via modification and click chemistry, resulting in composite drug-loaded nanocapsules with dual responsiveness to light and GSH. Under neutral conditions, the nanocapsules exhibited minimal drug leakage. Upon NIR light stimulation, 1-(5-methoxy-2-nitro-4-prop-2-ynyloxy-phenyl)ethyl-N-succinimidyl carbonate (MNPSC) underwent photolysis, causing the PEG layer to detach and trigger drug release. In a simulated high concentration of intratumoral glutathione environment, the mesoporous organosilica degraded, further facilitating the drug release. The ultimate drug release rate reached an impressive 92 %. This smart dual-responsive nanocapsule system offers a promising strategy for controlled drug delivery, combining the advantages of NIR-triggered release and GSH-responsive degradation for enhanced therapeutic efficacy.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"326 ","pages":"Article 128314"},"PeriodicalIF":4.1,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703396","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-26DOI: 10.1016/j.polymer.2025.128316
Hui Ma , Ruijing Meng , Haohao Hou , Hongfu Zhou , Xiangdong Wang , Yafeng Deng
Polyvinylidene fluoride (PVDF) foam, known for its low density, high strength, and inherent flame retardancy, has demonstrated significant advantages in various applications. Fluorinated polyhedral oligomeric silsesquioxane (F-POSS), recognized as an ideal nanofiller, contributes to the manufacture of lightweight, high-performance PVDF insulating foam. PVDF/F-POSS composite foams were successfully prepared in this work, employing melt blending and supercritical CO2 (scCO2) autoclave foaming techniques that exhibited excellent mechanical performance and thermal insulation capabilities. Crystallization behavior research findings indicated that F-POSS increased the crystallinity of PVDF, functioning as a crystallization nucleating agent. Concurrently, the use of scCO2 foaming technology promoted phase transitions, increasing the content of β-phase. Scanning electron microscopy (SEM) observations revealed that F-POSS could also serve as a cell nucleating agent, which increased cell density and formed a more uniform cell structure. At 1 wt% of F-POSS, the foams demonstrated excellent compressive mechanical properties, which compressive specific modulus and compressive specific strength increased by 76.9 % and 197.5 %, respectively. In addition, the composite foams exhibited an outstanding low thermal conductivity value of 0.0305 W m−1 K−1. This study provides a simple, efficient and green way for preparing thermal insulation foams consisting of fluorinated polymers and fluorinated nanofillers.
{"title":"F-POSS nanofillers modified PVDF foam with excellent mechanical and thermal insulation properties","authors":"Hui Ma , Ruijing Meng , Haohao Hou , Hongfu Zhou , Xiangdong Wang , Yafeng Deng","doi":"10.1016/j.polymer.2025.128316","DOIUrl":"10.1016/j.polymer.2025.128316","url":null,"abstract":"<div><div>Polyvinylidene fluoride (PVDF) foam, known for its low density, high strength, and inherent flame retardancy, has demonstrated significant advantages in various applications. Fluorinated polyhedral oligomeric silsesquioxane (F-POSS), recognized as an ideal nanofiller, contributes to the manufacture of lightweight, high-performance PVDF insulating foam. PVDF/F-POSS composite foams were successfully prepared in this work, employing melt blending and supercritical CO<sub>2</sub> (scCO<sub>2</sub>) autoclave foaming techniques that exhibited excellent mechanical performance and thermal insulation capabilities. Crystallization behavior research findings indicated that F-POSS increased the crystallinity of PVDF, functioning as a crystallization nucleating agent. Concurrently, the use of scCO<sub>2</sub> foaming technology promoted phase transitions, increasing the content of β-phase. Scanning electron microscopy (SEM) observations revealed that F-POSS could also serve as a cell nucleating agent, which increased cell density and formed a more uniform cell structure. At 1 wt% of F-POSS, the foams demonstrated excellent compressive mechanical properties, which compressive specific modulus and compressive specific strength increased by 76.9 % and 197.5 %, respectively. In addition, the composite foams exhibited an outstanding low thermal conductivity value of 0.0305 W m<sup>−1</sup> K<sup>−1</sup>. This study provides a simple, efficient and green way for preparing thermal insulation foams consisting of fluorinated polymers and fluorinated nanofillers.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"326 ","pages":"Article 128316"},"PeriodicalIF":4.1,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703381","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-25DOI: 10.1016/j.polymer.2025.128313
Xuerong Bi , Jiawei Li , Jiansheng Guo , Chongwen Yu
Improving the uniformity of phase separation in wet spinning is crucial for enhancing fiber properties. Different from traditional wet spinning methods, in this approach, the calcium source is homogeneously dispersed in the alginate spinning solution as nano-calcium carbonate. The release of calcium ions and in-situ crosslinking are regulated by adjusting the pH of the coagulation bath, thereby enhancing crosslinking uniformity. Morphology and distribution of calcium ions analysis revealed that the radial structure of the in-situ crosslinking spinning fibers is denser and more uniform, with a higher calcium ion concentration indicating a stronger degree of crosslinking. Tensile tests demonstrated that the fracture strength of in-situ crosslinking spun fibers without drawing is twice than that of traditional wet spinning fibers. This method offers a novel approach for the fabrication of wet-spun fibers with a uniform radial structure and high strength.
{"title":"A novel in-situ crosslinking wet spinning method for promoting the strength of CNC/alginate fiber","authors":"Xuerong Bi , Jiawei Li , Jiansheng Guo , Chongwen Yu","doi":"10.1016/j.polymer.2025.128313","DOIUrl":"10.1016/j.polymer.2025.128313","url":null,"abstract":"<div><div>Improving the uniformity of phase separation in wet spinning is crucial for enhancing fiber properties. Different from traditional wet spinning methods, in this approach, the calcium source is homogeneously dispersed in the alginate spinning solution as nano-calcium carbonate. The release of calcium ions and in-situ crosslinking are regulated by adjusting the pH of the coagulation bath, thereby enhancing crosslinking uniformity. Morphology and distribution of calcium ions analysis revealed that the radial structure of the in-situ crosslinking spinning fibers is denser and more uniform, with a higher calcium ion concentration indicating a stronger degree of crosslinking. Tensile tests demonstrated that the fracture strength of in-situ crosslinking spun fibers without drawing is twice than that of traditional wet spinning fibers. This method offers a novel approach for the fabrication of wet-spun fibers with a uniform radial structure and high strength.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"325 ","pages":"Article 128313"},"PeriodicalIF":4.1,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695470","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-21DOI: 10.1016/j.polymer.2025.128302
Milanta Tom , Tapas Ranjan Mohanty , Sabu Thomas , Bastien Seantier , Yves Grohens , Ramakrishnan S. , Mohamed P.K.
Alleviating the carbon footprint by utilizing bio-based fillers to develop sustainable tyre tread composites is a promising and innovative approach. Our research presents sustainable nanocomposites that utilize cellulose nanofiber (CNF) as reinforcing filler for natural rubber (NR) based truck, bus and radial tyre (TBR) tread composites. The choice of cellulose nanofibers, with their renewable nature, biodegradability, lightweight, and superior mechanical properties, to partially replace carbon black (CB) in different ratios underscores the innovative nature of our approach. Although there are a few studies focused on replacing CB with nanocellulose, a comprehensive study is necessary to optimize the loading of CB and CNF by varying the replacement ratios, thereby fully harnessing the potential of CNF. We have explored the synergism between CB and CNF and optimized CB content in the hybrid nanocomposite, demonstrating a reduction in the amount of CB in tyre tread composites. The performance of the hybrid nanocomposite is shown to be highly dependent on CNF and its concentration, as evidenced by morphological, static and dynamic mechanical properties. The increase in tensile strength and modulus (an increase of 413 % at 100 % elongation) after partially replacing CB by CNF of half the concentration of replaced CB indicates good synergism and better reinforcing ability of CNF. The remarkable decrease in rolling resistance (34 %) and the improvement in wet grip properties after partially replacing CB with CNF is quite promising for tyre tread applications to replace CB with CNF at higher ratios. The lower surface roughness values observed for 2.5 phr CNF-loaded hybrid nanocomposite from AFM analysis indicated better CNF dispersion at lower loadings. The development of these nanocellulose-based tyre tread composites not only offers a sustainable solution but also imparts bioeconomy concepts to tyre industries, reducing their dependence on non-renewable petroleum-based products and opening up new circular economic opportunities.
{"title":"Investigating the synergism and partial replacement of carbon black by cellulose nanofibers in natural rubber-based tyre tread composites","authors":"Milanta Tom , Tapas Ranjan Mohanty , Sabu Thomas , Bastien Seantier , Yves Grohens , Ramakrishnan S. , Mohamed P.K.","doi":"10.1016/j.polymer.2025.128302","DOIUrl":"10.1016/j.polymer.2025.128302","url":null,"abstract":"<div><div>Alleviating the carbon footprint by utilizing bio-based fillers to develop sustainable tyre tread composites is a promising and innovative approach. Our research presents sustainable nanocomposites that utilize cellulose nanofiber (CNF) as reinforcing filler for natural rubber (NR) based truck, bus and radial tyre (TBR) tread composites. The choice of cellulose nanofibers, with their renewable nature, biodegradability, lightweight, and superior mechanical properties, to partially replace carbon black (CB) in different ratios underscores the innovative nature of our approach. Although there are a few studies focused on replacing CB with nanocellulose, a comprehensive study is necessary to optimize the loading of CB and CNF by varying the replacement ratios, thereby fully harnessing the potential of CNF. We have explored the synergism between CB and CNF and optimized CB content in the hybrid nanocomposite, demonstrating a reduction in the amount of CB in tyre tread composites. The performance of the hybrid nanocomposite is shown to be highly dependent on CNF and its concentration, as evidenced by morphological, static and dynamic mechanical properties. The increase in tensile strength and modulus (an increase of 413 % at 100 % elongation) after partially replacing CB by CNF of half the concentration of replaced CB indicates good synergism and better reinforcing ability of CNF. The remarkable decrease in rolling resistance (34 %) and the improvement in wet grip properties after partially replacing CB with CNF is quite promising for tyre tread applications to replace CB with CNF at higher ratios. The lower surface roughness values observed for 2.5 phr CNF-loaded hybrid nanocomposite from AFM analysis indicated better CNF dispersion at lower loadings. The development of these nanocellulose-based tyre tread composites not only offers a sustainable solution but also imparts bioeconomy concepts to tyre industries, reducing their dependence on non-renewable petroleum-based products and opening up new circular economic opportunities.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"325 ","pages":"Article 128302"},"PeriodicalIF":4.1,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143666048","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-21DOI: 10.1016/j.polymer.2025.128306
Zhicheng Wang, Qiufei Chen, Tao Liu, Xudong Wang, Athar Ali Khan Gorar, Wen-bin Liu, Jun Wang, Jun-yi Wang
Tetrafuran tetramine (TFTA) was synthesized from biomass feedstock furfurylamine, and two bio-based tetrafunctional benzoxazines (BZ-satfta and BZ-mosatfta) were subsequently prepared in a three-step process with salicylaldehyde and 4-methoxysalicylaldehyde, respectively, by Mannich condensation reaction. The chemical structure was characterized with fourier transform infrared (FTIR) and nuclear magnetic resonance (NMR) spectroscopy, which showed the successful preparation of tetrafunctional benzoxazines containing a furan ring. Differential scanning calorimetry (DSC) tests and cure kinetics studies revealed that BZ-mosatfta has higher curing temperatures (234 °C) and apparent activation energies (Ek: 109.10 kJ/mol and Eo: 111.53 kJ/mol) compared to BZ-satfta due to the electron-donating effect of methoxyl. Meanwhile, the thermal properties were analyzed by the dynamic mechanical analysis (DMA) and thermal gravimetric analysis (TGA), which indicated that poly (BZ-satfta) had more excellent thermal properties and thermal stability, with glass transition temperatures (Tg) and residual carbon rates (Yc) as high as 376 °C and 58.6 %. In addition, limiting oxygen index (LOI) and microscale combustion calorimetry (MCC) tests demonstrate the outstanding flame retardant properties of both materials, which meets the standard for non-flammable materials. Furthermore, it can be extinguished within 0.5 s in the UL-94 vertical burning test. At the same time, both resins have good mechanical properties, with poly (BZ-satfta) having a flexural strength of 80 MPa. Both resins could be applied as resin matrices for high-performance heat-resistant and flame-retardant composites.
{"title":"Synthesis of bio-based tetrafunctional benzoxazines derived from furfurylamine: Excellent heat resistance and flame retardant properties","authors":"Zhicheng Wang, Qiufei Chen, Tao Liu, Xudong Wang, Athar Ali Khan Gorar, Wen-bin Liu, Jun Wang, Jun-yi Wang","doi":"10.1016/j.polymer.2025.128306","DOIUrl":"10.1016/j.polymer.2025.128306","url":null,"abstract":"<div><div>Tetrafuran tetramine (TFTA) was synthesized from biomass feedstock furfurylamine, and two bio-based tetrafunctional benzoxazines (BZ-satfta and BZ-mosatfta) were subsequently prepared in a three-step process with salicylaldehyde and 4-methoxysalicylaldehyde, respectively, by Mannich condensation reaction. The chemical structure was characterized with fourier transform infrared (FTIR) and nuclear magnetic resonance (NMR) spectroscopy, which showed the successful preparation of tetrafunctional benzoxazines containing a furan ring. Differential scanning calorimetry (DSC) tests and cure kinetics studies revealed that BZ-mosatfta has higher curing temperatures (234 °C) and apparent activation energies (<em>E</em><sub>k</sub>: 109.10 kJ/mol and <em>E</em><sub>o</sub>: 111.53 kJ/mol) compared to BZ-satfta due to the electron-donating effect of methoxyl. Meanwhile, the thermal properties were analyzed by the dynamic mechanical analysis (DMA) and thermal gravimetric analysis (TGA), which indicated that poly (BZ-satfta) had more excellent thermal properties and thermal stability, with glass transition temperatures (<em>T</em><sub>g</sub>) and residual carbon rates (<em>Y</em><sub>c</sub>) as high as 376 °C and 58.6 %. In addition, limiting oxygen index (LOI) and microscale combustion calorimetry (MCC) tests demonstrate the outstanding flame retardant properties of both materials, which meets the standard for non-flammable materials. Furthermore, it can be extinguished within 0.5 s in the UL-94 vertical burning test. At the same time, both resins have good mechanical properties, with poly (BZ-satfta) having a flexural strength of 80 MPa. Both resins could be applied as resin matrices for high-performance heat-resistant and flame-retardant composites.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"326 ","pages":"Article 128306"},"PeriodicalIF":4.1,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143672451","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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