Pub Date : 2026-01-13DOI: 10.1016/j.polymer.2026.129596
Denisse Jara , Roxana Coppola , Fernando Fabris , Giuliano Basso , Diego Muraca , Jimena S. González , Pedro Mendoza Zélis , Gabriel Ybarra , Pablo Tancredi
This study presents and compares the preparation, characterization, and performance of three poly(N-isopropylacrylamide)/alginate ferrogels containing magnetic nanoparticles (NPs) incorporated through either in situ or ex situ methods, which are intended to act as nanoheaters capable of triggering the polymer's hydrophilic–hydrophobic transition. The ex situ ferrogels were fabricated with bare or citrate-coated NPs with a crystallite length of 11 nm, a size known to ensure good heating performance under alternating magnetic fields. In contrast, the in situ NPs were smaller, around 8 nm, likely due to the synthesis temperature and the restraints experienced by the precursors within the hydrogel. All three ferrogels showed strong thermoresponsive behavior, expelling over 80 % of water once the polymer transition temperature was reached. Under magnetic heating, ex situ systems displayed rapid temperature rise and fast deswelling, while the in situ system heated more slowly due to its reduced NPs size and lower heating efficiency. Nevertheless, the latter still achieved significant water expulsion, suggesting localized heating effects sufficient to induce the polymer transition without a rapid bulk temperature increase. Overall, both approaches are effective for preparing functional thermoresponsive ferrogels, but each method offers advantages and limitations that should be considered based on the intended application.
{"title":"In situ or ex situ? Choosing the best path for the synthesis of thermoresponsive ferrogels for remotely triggered controlled release applications","authors":"Denisse Jara , Roxana Coppola , Fernando Fabris , Giuliano Basso , Diego Muraca , Jimena S. González , Pedro Mendoza Zélis , Gabriel Ybarra , Pablo Tancredi","doi":"10.1016/j.polymer.2026.129596","DOIUrl":"10.1016/j.polymer.2026.129596","url":null,"abstract":"<div><div>This study presents and compares the preparation, characterization, and performance of three poly(N-isopropylacrylamide)/alginate ferrogels containing magnetic nanoparticles (NPs) incorporated through either <em>in situ</em> or <em>ex situ</em> methods, which are intended to act as nanoheaters capable of triggering the polymer's hydrophilic–hydrophobic transition. The <em>ex situ</em> ferrogels were fabricated with bare or citrate-coated NPs with a crystallite length of 11 nm, a size known to ensure good heating performance under alternating magnetic fields. In contrast, the <em>in situ</em> NPs were smaller, around 8 nm, likely due to the synthesis temperature and the restraints experienced by the precursors within the hydrogel. All three ferrogels showed strong thermoresponsive behavior, expelling over 80 % of water once the polymer transition temperature was reached. Under magnetic heating, <em>ex situ</em> systems displayed rapid temperature rise and fast deswelling, while the <em>in situ</em> system heated more slowly due to its reduced NPs size and lower heating efficiency. Nevertheless, the latter still achieved significant water expulsion, suggesting localized heating effects sufficient to induce the polymer transition without a rapid bulk temperature increase. Overall, both approaches are effective for preparing functional thermoresponsive ferrogels, but each method offers advantages and limitations that should be considered based on the intended application.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"345 ","pages":"Article 129596"},"PeriodicalIF":4.5,"publicationDate":"2026-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145962757","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 : 2026-01-13DOI: 10.1016/j.polymer.2026.129597
Su Min Oh, Yoon Chan Chung, Jang Hyun Kim, Kyung Hoon Min, Byeongseok Kim, Sang Eun Shim
Fluoro-phenyl silicone (FPS) copolymers were synthesized via anionic ring-opening polymerization of cyclic siloxane monomers containing methyltrifluoropropylsiloxane (MFS) and diphenylsiloxane (DPS) units. 1H and 29Si NMR, and ATR–FTIR confirmed random incorporation of the functional units, while GPC and viscometry related changes in molecular weight and viscosity to steric hindrance and π–π or dipole–π interactions. By varying the MFS/DPS contents, the glass-transition temperature (Tg) of the copolymers was tuned.
FPS rubbers (FPSRs) were evaluated by thermogravimetric analysis under nitrogen and air. DPS units enhanced thermal resistance by suppressing back-biting and promoting thermally induced crosslinking through phenyl-radical formation, whereas MFS units, although increasing polarity, facilitated back-biting and lowered thermal stability in both atmospheres. Morphological characterization by SEM with F EDS mapping and elemental analysis showed that FPSRs form single-phase random copolymer networks with finely dispersed silica; only the fluorine-rich, phenyl-free FPSR-F50-P0 displayed slight local clustering, which was mitigated by adding a small amount of DPS.
Chemical-resistance tests revealed that MFS markedly improves resistance owing to its low surface energy and high polarity, while excessive DPS promotes swelling in nonpolar liquids. Increasing MFS contents lower surface free energy and suppresses oil permeation, whereas higher DPS contents slightly raise surface free energy and correlate with enhanced oil uptake. The cooperative effects of MFS and DPS therefore allow tuning of morphology and structure–property relationships in FPSRs, providing guidelines for designing silicone materials with improved thermal and chemical durability for demanding applications.
{"title":"Tuning thermal and chemical stability of silicone rubbers via incorporation of diphenylsiloxane and methyltrifluoropropylsiloxane units","authors":"Su Min Oh, Yoon Chan Chung, Jang Hyun Kim, Kyung Hoon Min, Byeongseok Kim, Sang Eun Shim","doi":"10.1016/j.polymer.2026.129597","DOIUrl":"10.1016/j.polymer.2026.129597","url":null,"abstract":"<div><div>Fluoro-phenyl silicone (FPS) copolymers were synthesized via anionic ring-opening polymerization of cyclic siloxane monomers containing methyltrifluoropropylsiloxane (MFS) and diphenylsiloxane (DPS) units. <sup>1</sup>H and <sup>29</sup>Si NMR, and ATR–FTIR confirmed random incorporation of the functional units, while GPC and viscometry related changes in molecular weight and viscosity to steric hindrance and π–π or dipole–π interactions. By varying the MFS/DPS contents, the glass-transition temperature (Tg) of the copolymers was tuned.</div><div>FPS rubbers (FPSRs) were evaluated by thermogravimetric analysis under nitrogen and air. DPS units enhanced thermal resistance by suppressing back-biting and promoting thermally induced crosslinking through phenyl-radical formation, whereas MFS units, although increasing polarity, facilitated back-biting and lowered thermal stability in both atmospheres. Morphological characterization by SEM with F EDS mapping and elemental analysis showed that FPSRs form single-phase random copolymer networks with finely dispersed silica; only the fluorine-rich, phenyl-free FPSR-F50-P0 displayed slight local clustering, which was mitigated by adding a small amount of DPS.</div><div>Chemical-resistance tests revealed that MFS markedly improves resistance owing to its low surface energy and high polarity, while excessive DPS promotes swelling in nonpolar liquids. Increasing MFS contents lower surface free energy and suppresses oil permeation, whereas higher DPS contents slightly raise surface free energy and correlate with enhanced oil uptake. The cooperative effects of MFS and DPS therefore allow tuning of morphology and structure–property relationships in FPSRs, providing guidelines for designing silicone materials with improved thermal and chemical durability for demanding applications.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"345 ","pages":"Article 129597"},"PeriodicalIF":4.5,"publicationDate":"2026-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145962197","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 : 2026-01-13DOI: 10.1016/j.polymer.2026.129593
Nicholas R. Enos, Joseph P. Previte, Jeffrey S. Wiggins
Inclusion of nanomaterials and varying processing parameters can alter the crystallization rate and morphology of semi-crystalline polymers. This work investigates the influence of carbon nanotubes on PEKK crystallization rates and morphology under both quiescent (zero shear) and sheared conditions. We found that the inclusion of 0.1 wt.% and 1 wt.% carbon nanotubes accelerated crystallization in DSC, and nucleation density increased, evidenced by a transition from spherulitic to point-like morphology as observed by POM. Parallel plate rheology was used to apply shear and analyze crystallization through an increase in storage modulus. In neat PEKK, shear rates of 5 s-1 led to shear thinning in the melted material, which led to accelerated crystallization. Shearing the material at 30 s-1 and above led to a 20 °C increase in the crystallization onset temperature, and a bimodal behavior in the storage modulus evolution was observed during crystallization, which was attributed to a gradient of crystalline morphology in the sample: a transition from spherulitic, to point-like, to a highly aligned morphology in the direction of shear. Although the incorporation of CNTs hindered the relaxation of PEKK chains, crystallization rates in the nanocomposites remained largely unaffected by shear. Morphology also remained consistent under shear, indicating that heterogeneous nucleation from CNTs dominates over flow-induced crystallization. This behavior demonstrates the ability of CNTs to provide consistent morphology in PEKK nanocomposites despite variation in processing conditions.
{"title":"Flow-Induced Crystallization and Morphology in Poly (ether ketone ketone) Nanocomposites with Dominant Influence from Carbon Nanotubes","authors":"Nicholas R. Enos, Joseph P. Previte, Jeffrey S. Wiggins","doi":"10.1016/j.polymer.2026.129593","DOIUrl":"https://doi.org/10.1016/j.polymer.2026.129593","url":null,"abstract":"Inclusion of nanomaterials and varying processing parameters can alter the crystallization rate and morphology of semi-crystalline polymers. This work investigates the influence of carbon nanotubes on PEKK crystallization rates and morphology under both quiescent (zero shear) and sheared conditions. We found that the inclusion of 0.1 wt.% and 1 wt.% carbon nanotubes accelerated crystallization in DSC, and nucleation density increased, evidenced by a transition from spherulitic to point-like morphology as observed by POM. Parallel plate rheology was used to apply shear and analyze crystallization through an increase in storage modulus. In neat PEKK, shear rates of 5 s<sup>-1</sup> led to shear thinning in the melted material, which led to accelerated crystallization. Shearing the material at 30 s<sup>-1</sup> and above led to a 20 °C increase in the crystallization onset temperature, and a bimodal behavior in the storage modulus evolution was observed during crystallization, which was attributed to a gradient of crystalline morphology in the sample: a transition from spherulitic, to point-like, to a highly aligned morphology in the direction of shear. Although the incorporation of CNTs hindered the relaxation of PEKK chains, crystallization rates in the nanocomposites remained largely unaffected by shear. Morphology also remained consistent under shear, indicating that heterogeneous nucleation from CNTs dominates over flow-induced crystallization. This behavior demonstrates the ability of CNTs to provide consistent morphology in PEKK nanocomposites despite variation in processing conditions.","PeriodicalId":405,"journal":{"name":"Polymer","volume":"1 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145962759","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 : 2026-01-12DOI: 10.1016/j.polymer.2026.129590
Jose Sena-Fernández , Oscar Toledano , Gonzalo Santoro , Mikel Sanz , Oscar Gálvez , Tiberio A. Ezquerra , Esther Rebollar , Aurora Nogales
We systematically investigate the dominant role of solvent polarity in the formation of electroactive phases of poly(vinylidene fluoride) (PVDF) by combining comprehensive experimental characterization (IR spectroscopy, X-ray scattering, Atomic Force Microscopy) with molecular dynamics (MD) simulations. We demonstrate that the solvent dipole moment dictates the stabilization of polar chain conformations in the solution and, consequently, the crystallization of electroactive β and γ polymorphs (reported here jointly as β/γ) in both solvent-cast bulk deposits and water-dispersed nanoparticles (NPs). A critical dipole-moment threshold of μ ≈ 2.8 D is identified: solvents above this value consistently yield electroactive phase contents exceeding 50 %, regardless of the processing route. MD simulations reveal that polar solvents strengthen PVDF–solvent dipole coupling and increase the population of all-trans (TTT) conformers, in agreement with the experimentally determined electroactive fractions. Furthermore, the incorporation of water as a polar antisolvent during nanoprecipitation enhances the electroactive phase content of the crystallites in NPs relative to bulk samples. The combined experimental–computational approach provides a unified molecular-level understanding of solvent-driven polymorph selection in PVDF and offers practical guidelines for solvent and process design to engineer high-performance electroactive PVDF structures from the macro-to the nanoscale.
{"title":"Role of solvent polarity in controlling the formation of electroactive β/γ-phases in poly(vinylidene fluoride) nanoparticles","authors":"Jose Sena-Fernández , Oscar Toledano , Gonzalo Santoro , Mikel Sanz , Oscar Gálvez , Tiberio A. Ezquerra , Esther Rebollar , Aurora Nogales","doi":"10.1016/j.polymer.2026.129590","DOIUrl":"10.1016/j.polymer.2026.129590","url":null,"abstract":"<div><div>We systematically investigate the dominant role of solvent polarity in the formation of electroactive phases of poly(vinylidene fluoride) (PVDF) by combining comprehensive experimental characterization (IR spectroscopy, X-ray scattering, Atomic Force Microscopy) with molecular dynamics (MD) simulations. We demonstrate that the solvent dipole moment dictates the stabilization of polar chain conformations in the solution and, consequently, the crystallization of electroactive β and γ polymorphs (reported here jointly as β/γ) in both solvent-cast bulk deposits and water-dispersed nanoparticles (NPs). A critical dipole-moment threshold of μ ≈ 2.8 D is identified: solvents above this value consistently yield electroactive phase contents exceeding 50 %, regardless of the processing route. MD simulations reveal that polar solvents strengthen PVDF–solvent dipole coupling and increase the population of all-trans (TTT) conformers, in agreement with the experimentally determined electroactive fractions. Furthermore, the incorporation of water as a polar antisolvent during nanoprecipitation enhances the electroactive phase content of the crystallites in NPs relative to bulk samples. The combined experimental–computational approach provides a unified molecular-level understanding of solvent-driven polymorph selection in PVDF and offers practical guidelines for solvent and process design to engineer high-performance electroactive PVDF structures from the macro-to the nanoscale.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"345 ","pages":"Article 129590"},"PeriodicalIF":4.5,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145956725","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 : 2026-01-12DOI: 10.1016/j.polymer.2026.129588
Carl T. Furner , Jeffrey T. Wilk , Michael T. Kelly , Ethan W. Kent , Bin Zhao , Christopher Y. Li
Crystallization of molecular bottlebrushes has recently received increasing attention. In this work, a series of 3-arm star molecular bottlebrush (sMBB) polymers with varying grafting densities, ranging from 18 % to 88 %, were synthesized using a copper(I)-catalyzed azide-alkyne cycloaddition reaction. The non-isothermal and isothermal crystallization of these sMBBs was investigated using differential scanning calorimetry (DSC) and polarized light microscopy (PLM). We specifically focused on the effect of grafting density on the sMBB crystallization behavior. The Hoffman-Lauritzen model was employed to analyze the polymer crystallization kinetics. Furthermore, the sMBBs were compared with linear molecular bottlebrushes (lMBBs) with similar grafting densities. The direct comparison between star and linear bottlebrush crystallization reveals the independent effects of grafting density and backbone architecture.
{"title":"Effect of grafting density and backbone branching on crystallization of poly(ethylene oxide)-bearing star bottlebrushes","authors":"Carl T. Furner , Jeffrey T. Wilk , Michael T. Kelly , Ethan W. Kent , Bin Zhao , Christopher Y. Li","doi":"10.1016/j.polymer.2026.129588","DOIUrl":"10.1016/j.polymer.2026.129588","url":null,"abstract":"<div><div>Crystallization of molecular bottlebrushes has recently received increasing attention. In this work, a series of 3-arm star molecular bottlebrush (<em>s</em>MBB) polymers with varying grafting densities, ranging from 18 % to 88 %, were synthesized using a copper(I)-catalyzed azide-alkyne cycloaddition reaction. The non-isothermal and isothermal crystallization of these <em>s</em>MBBs was investigated using differential scanning calorimetry (DSC) and polarized light microscopy (PLM). We specifically focused on the effect of grafting density on the <em>s</em>MBB crystallization behavior. The Hoffman-Lauritzen model was employed to analyze the polymer crystallization kinetics. Furthermore, the <em>s</em>MBBs were compared with linear molecular bottlebrushes (<em>l</em>MBBs) with similar grafting densities. The direct comparison between star and linear bottlebrush crystallization reveals the independent effects of grafting density and backbone architecture.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"345 ","pages":"Article 129588"},"PeriodicalIF":4.5,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145956589","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}
Growing concerns over formaldehyde emissions from conventional melamine–formaldehyde (MF) resins have driven the search for greener alternatives in decorative laminate applications. Among potential building blocks for impregnation resins, glyoxal has emerged as a promising sustainable crosslinker, while sorbitol serves as a bio-based additive to modify the cured network structure. During resin synthesis, sorbitol (10 wt%) was incorporated at distinct synthesis stages to assess its impact on resin structure and performance. Importantly, sorbitol-modified GMF resins exhibited satisfactory processability and film formation during impregnation. In this study, the curing behavior of sorbitol-modified glyoxal-melamine-formaldehyde (GMF) resins was investigated using a complementary analytical strategy that combined attenuated total reflection Fourier-transform infrared (ATR-FTIR) spectroscopy with univariate and multivariate data evaluation, supported by differential scanning calorimetry (DSC). Univariate tracking of selected IR absorption bands resolved condensation and bridge-formation reactions, while principal component analysis (PCA) captured holistic cure trajectories. The onset of bridge formation was identified using both DSC and FTIR conversion profiles and defined a practical cure window, thereby guiding the selection of pressing times for board manufacturing. Compared to MF references, GMF variants exhibited significantly reduced formaldehyde release and altered network formation, and the timing of sorbitol addition influenced bridge formation during cure. Principal component regression (PCR) linked spectral features to performance-relevant parameters, including color stability and hydrolysis-liberated formaldehyde content, and enabled prediction of laminate properties prior to performance testing. This integrated analytical framework, combining univariate and multivariate spectroscopic methods with thermal and performance evaluation, supports the development and optimization of low-formaldehyde, high-performance alternatives that are readily implementable in industrial laminate manufacturing.
{"title":"Uni- and Multivariate FTIR analysis approaches to monitor the cure of bio-based sorbitol glyoxal melamine thermoset resins for decorative laminates","authors":"Martina Duller , Arunjunai Raj Mahendran , Olivia Moser , Edith Martha Zikulnig-Rusch","doi":"10.1016/j.polymer.2026.129561","DOIUrl":"10.1016/j.polymer.2026.129561","url":null,"abstract":"<div><div>Growing concerns over formaldehyde emissions from conventional melamine–formaldehyde (MF) resins have driven the search for greener alternatives in decorative laminate applications. Among potential building blocks for impregnation resins, glyoxal has emerged as a promising sustainable crosslinker, while sorbitol serves as a bio-based additive to modify the cured network structure. During resin synthesis, sorbitol (10 wt%) was incorporated at distinct synthesis stages to assess its impact on resin structure and performance. Importantly, sorbitol-modified GMF resins exhibited satisfactory processability and film formation during impregnation. In this study, the curing behavior of sorbitol-modified glyoxal-melamine-formaldehyde (GMF) resins was investigated using a complementary analytical strategy that combined attenuated total reflection Fourier-transform infrared (ATR-FTIR) spectroscopy with univariate and multivariate data evaluation, supported by differential scanning calorimetry (DSC). Univariate tracking of selected IR absorption bands resolved condensation and bridge-formation reactions, while principal component analysis (PCA) captured holistic cure trajectories. The onset of bridge formation was identified using both DSC and FTIR conversion profiles and defined a practical cure window, thereby guiding the selection of pressing times for board manufacturing. Compared to MF references, GMF variants exhibited significantly reduced formaldehyde release and altered network formation, and the timing of sorbitol addition influenced bridge formation during cure. Principal component regression (PCR) linked spectral features to performance-relevant parameters, including color stability and hydrolysis-liberated formaldehyde content, and enabled prediction of laminate properties prior to performance testing. This integrated analytical framework, combining univariate and multivariate spectroscopic methods with thermal and performance evaluation, supports the development and optimization of low-formaldehyde, high-performance alternatives that are readily implementable in industrial laminate manufacturing.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"345 ","pages":"Article 129561"},"PeriodicalIF":4.5,"publicationDate":"2026-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145947738","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 : 2026-01-09DOI: 10.1016/j.polymer.2026.129577
Zhiguo Hu , Yuesheng Zhang , Jiangang Zhang , Wen Cao , Xiong Liu , Hongtao Lu , Jianna Bao
The enhancement of the toughness and crystallization kinetics of PLA through a green and sustainable strategy was highly significant for improving its application potential. In this work, a bio-based degradable polyester (PLDSF) containing unsaturated double bonds was synthesized from 1,3-propanediol, succinic acid, l-lactic acid, and fumaric acid. Dynamic crosslinking of PLA/PLDSF (7:3) blends was initiated by bis(tert-butylperoxy) diisopropyl benzene (BIBP). The effects of BIBP content (0–0.5 wt%) on the morphology, mechanical properties, rheological properties, crystallization behavior, and degradation properties were investigated. The successful synthesis of PLDSF was confirmed by 1H NMR and FT-IR analyses. Gel extraction and morphological evolution further confirmed that BIBP-induced crosslinking occurred in both phases, while the reduction of voids and the progressive blurring of phase boundaries indicated an enhancement of interfacial compatibility. The mechanical properties of the blends first increased and then decreased with increasing BIBP content. At 0.3 wt% BIBP, the elongation at break and notched impact strength were enhanced by 55-fold (219 %) and 6-fold (70.4 kJ/m2), respectively, compared with the direct PLA/PLDSF blend. In addition, the crystallization rate of the blends was progressively enhanced with increasing BIBP content. At 130 °C, the half-crystallization time of the blend containing 0.5 wt% BIBP was reduced to 1.4 min, in sharp contrast to 27.9 min for the BIBP-free sample. This acceleration was attributed to the in situ formation of branched and crosslinked structures between PLA and PLDSF, which served as effective nucleation sites, thereby markedly increasing the nucleation density and facilitating PLA crystallization. This study demonstrated a green and effective strategy in which dynamic crosslinking improved both the toughness and crystallization rate of PLA, offering valuable insights into the development of high-performance biodegradable polyesters.
{"title":"Interfacial engineering of polylactic acid via dynamic vulcanization of bio-based polyester toward simultaneous toughening and accelerated crystallization","authors":"Zhiguo Hu , Yuesheng Zhang , Jiangang Zhang , Wen Cao , Xiong Liu , Hongtao Lu , Jianna Bao","doi":"10.1016/j.polymer.2026.129577","DOIUrl":"10.1016/j.polymer.2026.129577","url":null,"abstract":"<div><div>The enhancement of the toughness and crystallization kinetics of PLA through a green and sustainable strategy was highly significant for improving its application potential. In this work, a bio-based degradable polyester (PLDSF) containing unsaturated double bonds was synthesized from 1,3-propanediol, succinic acid, <span>l</span>-lactic acid, and fumaric acid. Dynamic crosslinking of PLA/PLDSF (7:3) blends was initiated by bis(tert-butylperoxy) diisopropyl benzene (BIBP). The effects of BIBP content (0–0.5 wt%) on the morphology, mechanical properties, rheological properties, crystallization behavior, and degradation properties were investigated. The successful synthesis of PLDSF was confirmed by <sup>1</sup>H NMR and FT-IR analyses. Gel extraction and morphological evolution further confirmed that BIBP-induced crosslinking occurred in both phases, while the reduction of voids and the progressive blurring of phase boundaries indicated an enhancement of interfacial compatibility. The mechanical properties of the blends first increased and then decreased with increasing BIBP content. At 0.3 wt% BIBP, the elongation at break and notched impact strength were enhanced by 55-fold (219 %) and 6-fold (70.4 kJ/m<sup>2</sup>), respectively, compared with the direct PLA/PLDSF blend. In addition, the crystallization rate of the blends was progressively enhanced with increasing BIBP content. At 130 °C, the half-crystallization time of the blend containing 0.5 wt% BIBP was reduced to 1.4 min, in sharp contrast to 27.9 min for the BIBP-free sample. This acceleration was attributed to the in situ formation of branched and crosslinked structures between PLA and PLDSF, which served as effective nucleation sites, thereby markedly increasing the nucleation density and facilitating PLA crystallization. This study demonstrated a green and effective strategy in which dynamic crosslinking improved both the toughness and crystallization rate of PLA, offering valuable insights into the development of high-performance biodegradable polyesters.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"345 ","pages":"Article 129577"},"PeriodicalIF":4.5,"publicationDate":"2026-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145956591","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 : 2026-01-09DOI: 10.1016/j.polymer.2026.129572
Xiqin Guo, Ye Liu, Bosheng Zhao, Qian Zhao, Hongli Liu, Xianggao Li, Shirong Wang
Electrophoretic display (EPD) device has garnered significant interest due to its eye protection, low energy consumption and environmental protection. However, its widespread adoption has been hindered by limitations such as poor steady state performance, low contrast ratio and slow response speed. In this study, a novel grafting-functionalizing-coating (GFC) method was developed to construct functional materials with an inorganic core, an organic functional layer, and a coating layer, using rutile TiO2 and ferromanganese black (FM) particles as raw materials. 3-(methacryloyloxy) propyl trimethoxysilane (KH570) was grafted on the surface of particles. Acrylic acid (AA), acrylamide (AM), diallyl dimethyl ammonium chloride (DMDAAC), polyoxyethylene allyloxy bonylphenoxypropyl ether ammonium sulfate (SE-10) were introduced as charge control agent. Methyl lauryl acrylate (LMA) was served as hydrophobic monomer, while divinylbenzene (DVB) was coating monomer. The target modified TiO2@ACDLD and FM@ADLSD particles have better dispersion stability, high zeta potential (29.56 mV for TiO2@ACDLD and -35.95 mV for FM@ADLSD) and low leakage current (0.0030 μA) in isopar L. The prototype device containing TiO2@ACDLD and FM@ADLSD particles shows an excellent performance, including high contrast ratio of 47.17 and rapid response time of 66 ms.
{"title":"Grafting-functionalizing-coating modified white/black electrophoretic particles for fast response and high contrast ratio electrophoretic display","authors":"Xiqin Guo, Ye Liu, Bosheng Zhao, Qian Zhao, Hongli Liu, Xianggao Li, Shirong Wang","doi":"10.1016/j.polymer.2026.129572","DOIUrl":"https://doi.org/10.1016/j.polymer.2026.129572","url":null,"abstract":"Electrophoretic display (EPD) device has garnered significant interest due to its eye protection, low energy consumption and environmental protection. However, its widespread adoption has been hindered by limitations such as poor steady state performance, low contrast ratio and slow response speed. In this study, a novel grafting-functionalizing-coating (GFC) method was developed to construct functional materials with an inorganic core, an organic functional layer, and a coating layer, using rutile TiO<ce:inf loc=\"post\">2</ce:inf> and ferromanganese black (FM) particles as raw materials. 3-(methacryloyloxy) propyl trimethoxysilane (KH570) was grafted on the surface of particles. Acrylic acid (AA), acrylamide (AM), diallyl dimethyl ammonium chloride (DMDAAC), polyoxyethylene allyloxy bonylphenoxypropyl ether ammonium sulfate (SE-10) were introduced as charge control agent. Methyl lauryl acrylate (LMA) was served as hydrophobic monomer, while divinylbenzene (DVB) was coating monomer. The target modified TiO<ce:inf loc=\"post\">2</ce:inf>@ACDLD and FM@ADLSD particles have better dispersion stability, high zeta potential (29.56 mV for TiO<ce:inf loc=\"post\">2</ce:inf>@ACDLD and -35.95 mV for FM@ADLSD) and low leakage current (0.0030 μA) in isopar L. The prototype device containing TiO<ce:inf loc=\"post\">2</ce:inf>@ACDLD and FM@ADLSD particles shows an excellent performance, including high contrast ratio of 47.17 and rapid response time of 66 ms.","PeriodicalId":405,"journal":{"name":"Polymer","volume":"37 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145956592","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 : 2026-01-08DOI: 10.1016/j.polymer.2026.129558
Haoran Peng , Xuejin Li , Qifan Yang , Yao Xue , Yongping Bai , Wei Li , Wenhui Zheng
Polyethylene terephthalate (PET) was widely utilized across diverse fields. However, its inferior hydrophobicity led to considerable practical losses and restricted its application scope. Herein, a new method was used to synthesize high-molecular-weight hydrophobic fluorinated polyester (FPET), effectively addressing the challenges of low reactivity and lengthy reaction times associated with fluorinated alcohols. By leveraging the excellent solubility of FPET, a superhydrophobic polyester material (PSPE) was prepared via solution blending of FPET with modified silica (F–SiO2) and polytetrafluoroethylene (PTFE) particles. Accordingly, the water contact angle (WCA) of the resulting polyester increased from 67° (pristine PET) to 115°, confirming a significant improvement in hydrophobicity, which provided a foundation for achieving superhydrophobic modification. Furthermore, under PTFE particles and F–SiO2, the hydrophobicity of the fluorinated polyester was further enhanced—achieving a maximum WCA of 159.5° and a minimum (SA) of 2.3°, which fully met the definition of superhydrophobicity. Even under a 100 g load, the sample maintained its superhydrophobicity after 50 abrasion cycles using sandpaper. Additionally, the incorporation of PTFE particles effectively reduced the dielectric constant of the polyester (dielectric constant ranged from 3.1 to 3.25), endowing it with favorable electrical insulation performance. This study presented an effective and viable strategy for synthesizing fluorinated polyesters with integrated superhydrophobicity, inherent self-cleaning ability, and low dielectric constant. Such multifunctional materials were expected to expand their application potential in water-repellent systems, anti-contamination coatings, and electronic packaging scenarios, addressing the key limitations of pristine PET.
{"title":"Superhydrophobic fluorinated polyester materials with low dielectric constant synthesized via facile preparation","authors":"Haoran Peng , Xuejin Li , Qifan Yang , Yao Xue , Yongping Bai , Wei Li , Wenhui Zheng","doi":"10.1016/j.polymer.2026.129558","DOIUrl":"10.1016/j.polymer.2026.129558","url":null,"abstract":"<div><div>Polyethylene terephthalate (PET) was widely utilized across diverse fields. However, its inferior hydrophobicity led to considerable practical losses and restricted its application scope. Herein, a new method was used to synthesize high-molecular-weight hydrophobic fluorinated polyester (FPET), effectively addressing the challenges of low reactivity and lengthy reaction times associated with fluorinated alcohols. By leveraging the excellent solubility of FPET, a superhydrophobic polyester material (PSPE) was prepared via solution blending of FPET with modified silica (F–SiO<sub>2</sub>) and polytetrafluoroethylene (PTFE) particles. Accordingly, the water contact angle (WCA) of the resulting polyester increased from 67° (pristine PET) to 115°, confirming a significant improvement in hydrophobicity, which provided a foundation for achieving superhydrophobic modification. Furthermore, under PTFE particles and F–SiO<sub>2</sub>, the hydrophobicity of the fluorinated polyester was further enhanced—achieving a maximum WCA of 159.5° and a minimum (SA) of 2.3°, which fully met the definition of superhydrophobicity. Even under a 100 g load, the sample maintained its superhydrophobicity after 50 abrasion cycles using sandpaper. Additionally, the incorporation of PTFE particles effectively reduced the dielectric constant of the polyester (dielectric constant ranged from 3.1 to 3.25), endowing it with favorable electrical insulation performance. This study presented an effective and viable strategy for synthesizing fluorinated polyesters with integrated superhydrophobicity, inherent self-cleaning ability, and low dielectric constant. Such multifunctional materials were expected to expand their application potential in water-repellent systems, anti-contamination coatings, and electronic packaging scenarios, addressing the key limitations of pristine PET.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"345 ","pages":"Article 129558"},"PeriodicalIF":4.5,"publicationDate":"2026-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145923912","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 : 2026-01-08DOI: 10.1016/j.polymer.2026.129575
Ricardo A. Pérez-Camargo , Alejandro J. Müller
Long-chain branches (LCBs) are primarily introduced within linear chains to enhance their melt strength and rheological performance. However, the influence of LCBs on crystallization has received comparatively little attention. This review reports recent results on isotactic polypropylene (iPP) and poly (lactic acid) (PLA) as representative semicrystalline polymers in which the effect of LCBs on nucleation and crystal growth has been extensively studied. A consistent trend emerges: LCBs accelerate nucleation, as indicated by higher nucleation densities, faster nucleation rates, and notable increases in crystallization temperatures. However, LCBs decrease spherulitic growth due to restricted chain mobility. Despite these opposing contributions, the overall crystallization kinetics are enhanced, underscoring the dominant role of primary nucleation. The long-standing belief that branching points serve as heterogeneous nuclei has recently been challenged, with fast scanning calorimetry (FSC) showing that LCBs instead promote nucleation through conformational stabilization and homogeneous nucleation pathways. While FSC has been vital in uncovering these mechanisms, further studies, using FSC and complementary techniques, are still needed to fully determine the molecular origins of LCB-induced crystallization across different polymer families.
{"title":"The introduction of long-chain branches within linear semicrystalline polymers enhances overall crystallization by promoting homogeneous nucleation","authors":"Ricardo A. Pérez-Camargo , Alejandro J. Müller","doi":"10.1016/j.polymer.2026.129575","DOIUrl":"10.1016/j.polymer.2026.129575","url":null,"abstract":"<div><div>Long-chain branches (LCBs) are primarily introduced within linear chains to enhance their melt strength and rheological performance. However, the influence of LCBs on crystallization has received comparatively little attention. This review reports recent results on isotactic polypropylene (iPP) and poly (lactic acid) (PLA) as representative semicrystalline polymers in which the effect of LCBs on nucleation and crystal growth has been extensively studied. A consistent trend emerges: LCBs accelerate nucleation, as indicated by higher nucleation densities, faster nucleation rates, and notable increases in crystallization temperatures. However, LCBs decrease spherulitic growth due to restricted chain mobility. Despite these opposing contributions, the overall crystallization kinetics are enhanced, underscoring the dominant role of primary nucleation. The long-standing belief that branching points serve as heterogeneous nuclei has recently been challenged, with fast scanning calorimetry (FSC) showing that LCBs instead promote nucleation through conformational stabilization and homogeneous nucleation pathways. While FSC has been vital in uncovering these mechanisms, further studies, using FSC and complementary techniques, are still needed to fully determine the molecular origins of LCB-induced crystallization across different polymer families.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"345 ","pages":"Article 129575"},"PeriodicalIF":4.5,"publicationDate":"2026-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145923914","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}
扫码关注我们
求助内容：
应助结果提醒方式：
京公网安备 11010802042870号