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Dimensional and conformational properties of pullulan tris(alkylcarbamate)s in tetrahydrofuran

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2025-04-16 DOI: 10.1016/j.polymer.2025.128417

Yuki Matsumoto , Shinichi Kitamura , Rintaro Takahashi , Ken Terao

Pullulan tris(n-butylcarbamate) (PTBC) and pullulan tris(ethylcarbamate) (PTEC) samples with different weight-average molar masses M_w were prepared from pullulan samples with varying chain lengths. Size-exclusion chromatography equipped with multi-angle light scattering detectors (SEC-MALS), small-angle X-ray scattering (SAXS), and viscometry were performed on the samples in tetrahydrofuran (THF) at 25 °C to determine M_w, form factor P(q), radius of gyration R_g, second virial coefficient, and intrinsic viscosity [η]. Infrared absorption measurements were also conducted to investigate the intramolecular hydrogen bonding between the CO and NH groups on adjacent monomer units. The obtained P(q), R_g, and [η] data were analyzed using the wormlike chain model with excluded volume effects, primarily to determine the contour length per monomer unit and the Kuhn segment length L_K, a measure of chain stiffness. The latter parameter L_K values were found to be 10 nm and 8 nm for PTBC and PTEC, respectively. The resulting chain stiffness was significantly lower than that of the corresponding amylose derivatives. Notably, PTBC and PTEC exhibited few intramolecular hydrogen bonding, in contrast to previously investigated amylose derivatives. This characteristic feature suggests that the free polar groups in pullulan derivatives could offer potential applications as macromolecular recognition materials.

{"title":"Dimensional and conformational properties of pullulan tris(alkylcarbamate)s in tetrahydrofuran","authors":"Yuki Matsumoto , Shinichi Kitamura , Rintaro Takahashi , Ken Terao","doi":"10.1016/j.polymer.2025.128417","DOIUrl":"10.1016/j.polymer.2025.128417","url":null,"abstract":"<div><div>Pullulan tris(<em>n</em>-butylcarbamate) (PTBC) and pullulan tris(ethylcarbamate) (PTEC) samples with different weight-average molar masses <em>M</em><sub>w</sub> were prepared from pullulan samples with varying chain lengths. Size-exclusion chromatography equipped with multi-angle light scattering detectors (SEC-MALS), small-angle X-ray scattering (SAXS), and viscometry were performed on the samples in tetrahydrofuran (THF) at 25 °C to determine <em>M</em><sub>w</sub>, form factor <em>P</em>(<em>q</em>), radius of gyration <em>R</em><sub>g</sub>, second virial coefficient, and intrinsic viscosity [<em>η</em>]. Infrared absorption measurements were also conducted to investigate the intramolecular hydrogen bonding between the C<img>O and NH groups on adjacent monomer units. The obtained <em>P</em>(<em>q</em>), <em>R</em><sub>g</sub>, and [<em>η</em>] data were analyzed using the wormlike chain model with excluded volume effects, primarily to determine the contour length per monomer unit and the Kuhn segment length <em>L</em><sub>K</sub>, a measure of chain stiffness. The latter parameter <em>L</em><sub>K</sub> values were found to be 10 nm and 8 nm for PTBC and PTEC, respectively. The resulting chain stiffness was significantly lower than that of the corresponding amylose derivatives. Notably, PTBC and PTEC exhibited few intramolecular hydrogen bonding, in contrast to previously investigated amylose derivatives. This characteristic feature suggests that the free polar groups in pullulan derivatives could offer potential applications as macromolecular recognition materials.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"327 ","pages":"Article 128417"},"PeriodicalIF":4.1,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143837322","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}

引用次数: 0

The effect of diamine structure on the thermomechanical properties of epoxy resin thermosets

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2025-04-16 DOI: 10.1016/j.polymer.2025.128408

Romina Keshavarz , Marlene A. Velazco-Medel , Matthew D. Green

Structure and composition are two essential components that affect the properties of the polymeric thermoset. In this paper, we studied the effect of the diamine structure on thermoset properties by synthesizing a series of epoxy-based thermosets composed of hardeners with almost equivalent molecular weights, including diaminooctane (DAO), Jeffamine-EDR, para-xylylenediamine (p-XDA), and meta-xylylenediamine (m-XDA). The structural and thermomechanical properties of the cured thermosets were characterized by attenuated total reflectance Fourier-transform infrared spectroscopy (ATR-FTIR), x-ray diffraction (XRD), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and dynamic mechanical analysis (DMA). These thermosets with amorphous structures, confirmed by XRD, were fully cured and crosslinked according to FTIR results. All thermosets demonstrated high thermal stability above 376 °C, with aromatic thermosets showing the highest char yield. The sample cured with m-XDA exhibited the highest glass transition temperature according to the DMA results, which were in agreement with the DSC results.

{"title":"The effect of diamine structure on the thermomechanical properties of epoxy resin thermosets","authors":"Romina Keshavarz , Marlene A. Velazco-Medel , Matthew D. Green","doi":"10.1016/j.polymer.2025.128408","DOIUrl":"10.1016/j.polymer.2025.128408","url":null,"abstract":"<div><div>Structure and composition are two essential components that affect the properties of the polymeric thermoset. In this paper, we studied the effect of the diamine structure on thermoset properties by synthesizing a series of epoxy-based thermosets composed of hardeners with almost equivalent molecular weights, including diaminooctane (DAO), Jeffamine-EDR, <em>para</em>-xylylenediamine (<em>p</em>-XDA), and <em>meta</em>-xylylenediamine (<em>m</em>-XDA). The structural and thermomechanical properties of the cured thermosets were characterized by attenuated total reflectance Fourier-transform infrared spectroscopy (ATR-FTIR), x-ray diffraction (XRD), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and dynamic mechanical analysis (DMA). These thermosets with amorphous structures, confirmed by XRD, were fully cured and crosslinked according to FTIR results. All thermosets demonstrated high thermal stability above 376 °C, with aromatic thermosets showing the highest char yield. The sample cured with <em>m</em>-XDA exhibited the highest glass transition temperature according to the DMA results, which were in agreement with the DSC results.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"328 ","pages":"Article 128408"},"PeriodicalIF":4.1,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143837329","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}

引用次数: 0

Hollow fiber with hierarchical loose cellular pores for treating textile wastewater

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2025-04-15 DOI: 10.1016/j.polymer.2025.128412

Chuanyong Liu , Liang Wang , Yong Liu

Hollow fiber membrane (HFM) has been widely used to purify waste dye water. The nanoporous skin of HFM usually provided high rejection to dye molecules, however, it suffered from the problem of conflict between high flux and rejection. In this study, a foaming layer was constructed in hollow spongy fiber (HPF) via coupling the non-solvent induced phase separation (NIPS) with polymer foaming. The boundary condition of cavity appearance was closely related with generated CO₂ diffusion. Based on theoretical analysis of phase-diagrams, the increased gas diffusion promoted instantaneous demixing. The enhanced thermodynamic instability would benefit CO₂ nucleation and growth, resulting in hierarchical cellular structure. CO₂ bubble diffusion broke the free barrier of gel rich-phase, achieving interconnected nanopores on each cell wall. This spongy nanopores located on foaming layers provided absorption sites for dye molecules, generating a layer by layer absorption and interception effect to dye. The as-prepared HPF membranes exhibited a high dye rejection (<98.2 %) and a high flux (24.4 L m⁻²h⁻¹) to Rhodamine B. This proposed coupling principles of bubble nucleation and phase-separation would help to design high-performance HFM with pores optimization.

{"title":"Hollow fiber with hierarchical loose cellular pores for treating textile wastewater","authors":"Chuanyong Liu , Liang Wang , Yong Liu","doi":"10.1016/j.polymer.2025.128412","DOIUrl":"10.1016/j.polymer.2025.128412","url":null,"abstract":"<div><div>Hollow fiber membrane (HFM) has been widely used to purify waste dye water. The nanoporous skin of HFM usually provided high rejection to dye molecules, however, it suffered from the problem of conflict between high flux and rejection. In this study, a foaming layer was constructed in hollow spongy fiber (HPF) via coupling the non-solvent induced phase separation (NIPS) with polymer foaming. The boundary condition of cavity appearance was closely related with generated CO<sub>2</sub> diffusion. Based on theoretical analysis of phase-diagrams, the increased gas diffusion promoted instantaneous demixing. The enhanced thermodynamic instability would benefit CO<sub>2</sub> nucleation and growth, resulting in hierarchical cellular structure. CO<sub>2</sub> bubble diffusion broke the free barrier of gel rich-phase, achieving interconnected nanopores on each cell wall. This spongy nanopores located on foaming layers provided absorption sites for dye molecules, generating a layer by layer absorption and interception effect to dye. The as-prepared HPF membranes exhibited a high dye rejection (<98.2 %) and a high flux (24.4 L m<sup>−2</sup>h<sup>−1</sup>) to Rhodamine B. This proposed coupling principles of bubble nucleation and phase-separation would help to design high-performance HFM with pores optimization.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"327 ","pages":"Article 128412"},"PeriodicalIF":4.1,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143833431","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}

引用次数: 0

Antioxidant-enhanced interfacial adhesion and mechanical properties of polyetheretherketone–carbon fiber composites

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2025-04-15 DOI: 10.1016/j.polymer.2025.128415

Hideyuki Uematsu , Toumu Aratama , Ken Sudo , Yukino Ito , Ayaka Yamaguchi , Akinori Fukushima , Shinji Sugihara , Fumihiro Nishimura , Masachika Yamane , Shuichi Tanoue

The effects of antioxidants on the interfacial adhesion between polyetheretherketone (PEEK) and carbon fiber (CF) and the mechanical properties of PEEK/CF were investigated. The interfacial shear strength of PEEK/CF was improved 30–50 % by adding phosphorus and phenolic antioxidants to PEEK. Its elastic modulus was increased by 40 %, and cohesive failure occurred with the addition of the antioxidants. Electron spin resonance spectroscopy and rheological property analysis of the molten state assumed that the antioxidants helped enhance the interfacial interaction owing to an increase in phenoxy radicals and the generation of phenyl radicals. Micro-Raman spectroscopy indicated that the improved interfacial interactions suppressed the formation of PEEK crystals at the interphase, resulting in cohesive failure. The addition of antioxidants not only improved the interfacial adhesion of PEEK/CF but also suppressed the interfacial fracture of PEEK/CF.

{"title":"Antioxidant-enhanced interfacial adhesion and mechanical properties of polyetheretherketone–carbon fiber composites","authors":"Hideyuki Uematsu , Toumu Aratama , Ken Sudo , Yukino Ito , Ayaka Yamaguchi , Akinori Fukushima , Shinji Sugihara , Fumihiro Nishimura , Masachika Yamane , Shuichi Tanoue","doi":"10.1016/j.polymer.2025.128415","DOIUrl":"10.1016/j.polymer.2025.128415","url":null,"abstract":"<div><div>The effects of antioxidants on the interfacial adhesion between polyetheretherketone (PEEK) and carbon fiber (CF) and the mechanical properties of PEEK/CF were investigated. The interfacial shear strength of PEEK/CF was improved 30–50 % by adding phosphorus and phenolic antioxidants to PEEK. Its elastic modulus was increased by 40 %, and cohesive failure occurred with the addition of the antioxidants. Electron spin resonance spectroscopy and rheological property analysis of the molten state assumed that the antioxidants helped enhance the interfacial interaction owing to an increase in phenoxy radicals and the generation of phenyl radicals. Micro-Raman spectroscopy indicated that the improved interfacial interactions suppressed the formation of PEEK crystals at the interphase, resulting in cohesive failure. The addition of antioxidants not only improved the interfacial adhesion of PEEK/CF but also suppressed the interfacial fracture of PEEK/CF.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"328 ","pages":"Article 128415"},"PeriodicalIF":4.1,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143837328","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}

引用次数: 0

Processability of poly(amic acid) gel films

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2025-04-15 DOI: 10.1016/j.polymer.2025.128414

Jianhua Wang, Guofeng Tian, Shengli Qi, Dezhen Wu

During the high-temperature drawing process of polyimide (PI) films, simultaneously changing the physicochemical structure of the films and implementing intricate process control is a complex problem. In this study, the PI precursor poly(amic acid) (PAA) was condensed from pyromellitic dianhydride (PMDA) and 4,4′-diaminodiphenyl ether (ODA) and its transformation from solution to gel and then to the glassy state was investigated using isothermal thermogravimetry, isothermal dynamic mechanical analysis, and differential scanning calorimetry. The experimental results were combined with molecular simulation results to determine the diffusion behaviors and related mechanisms of the solvents and chain segments. After investigating the effects of the solvent system, temperature, and solid content on the processability of PAA gel films, the processing window was identified on a two-dimensional parameter map (temperature versus solid content), which was divided into three regions with distinct processabilities. Both N,N′-dimethylacetamide (DMAc) and N-methylpyrrolidone (NMP) solvent systems exhibited a highly elastic gel state within a broad range of solid contents and temperatures but the NMP system demonstrated better processability, with an elongation rate exceeding 120 % within the 110°C-135 °C range and no chemical structural transformation from PAA to PI. This study successfully realizes a high-elastic gel state of PAA without relying on other chemical reagents. The proposed research idea and technical approach is expected to realize low-temperature drawing processing of PI films.

{"title":"Processability of poly(amic acid) gel films","authors":"Jianhua Wang, Guofeng Tian, Shengli Qi, Dezhen Wu","doi":"10.1016/j.polymer.2025.128414","DOIUrl":"10.1016/j.polymer.2025.128414","url":null,"abstract":"<div><div>During the high-temperature drawing process of polyimide (PI) films, simultaneously changing the physicochemical structure of the films and implementing intricate process control is a complex problem. In this study, the PI precursor poly(amic acid) (PAA) was condensed from pyromellitic dianhydride (PMDA) and 4,4′-diaminodiphenyl ether (ODA) and its transformation from solution to gel and then to the glassy state was investigated using isothermal thermogravimetry, isothermal dynamic mechanical analysis, and differential scanning calorimetry. The experimental results were combined with molecular simulation results to determine the diffusion behaviors and related mechanisms of the solvents and chain segments. After investigating the effects of the solvent system, temperature, and solid content on the processability of PAA gel films, the processing window was identified on a two-dimensional parameter map (temperature versus solid content), which was divided into three regions with distinct processabilities. Both N,N′-dimethylacetamide (DMAc) and N-methylpyrrolidone (NMP) solvent systems exhibited a highly elastic gel state within a broad range of solid contents and temperatures but the NMP system demonstrated better processability, with an elongation rate exceeding 120 % within the 110°C-135 °C range and no chemical structural transformation from PAA to PI. This study successfully realizes a high-elastic gel state of PAA without relying on other chemical reagents. The proposed research idea and technical approach is expected to realize low-temperature drawing processing of PI films.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"327 ","pages":"Article 128414"},"PeriodicalIF":4.1,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143837324","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}

引用次数: 0

Single-step fabrication of high-performance chlorinated polyethylene /CuO nanocomposites for energy storage applications

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2025-04-15 DOI: 10.1016/j.polymer.2025.128399

M. Shini , M.T. Ramesan

The development of flexible dielectric materials with superior energy storage capabilities is essential for electronic applications and the next generation electric power systems. This study employed a one-step two-roll mill mixing technique to fabricate chlorinated polyethylene (CPE) nanocomposites reinforced with copper oxide (CuO) nanoparticles, specifically engineered for energy storage applications. UV–visible spectroscopy indicated a redshift in absorbance, with the nanocomposite containing 7 wt% CuO displaying the highest refractive index and the lowest optical bandgap energy. FTIR analysis confirmed the bonding interactions between CuO and CPE while XRD verified the presence of crystalline CuO phase. FE-SEM and HR-TEM images demonstrated a uniform surface morphology and homogeneous nanoparticle dispersion of CuO nanoparticles at a 7 wt% loading, while agglomeration became apparent at higher concentrations. Thermal analysis using DSC and TGA revealed enhanced glass transition temperature and thermal stability upon incorporation of nanoparticles. The AC conductivity, dielectric constant, and modulus of the nanocomposites were evaluated across varying temperatures and frequencies, showing a consistent increase with rising nanofiller content. These properties reached their peak at 7 wt% CuO loading, where AC conductivity and dielectric constant values were approximately 13.4 and 3 times higher, respectively than those of pristine CPE. Additionally, mechanical properties were also significantly improved with CuO reinforcement. The nanocomposite containing 7 wt% CuO exhibited outstanding mechanical performance, with tensile strength increasing by 106.7 %, impact strength by 48.9 %, and hardness by 15.6 %. These results underscore the potential of CPE/CuO nanocomposites as advanced electroactive materials for future energy storage applications.

{"title":"Single-step fabrication of high-performance chlorinated polyethylene /CuO nanocomposites for energy storage applications","authors":"M. Shini , M.T. Ramesan","doi":"10.1016/j.polymer.2025.128399","DOIUrl":"10.1016/j.polymer.2025.128399","url":null,"abstract":"<div><div>The development of flexible dielectric materials with superior energy storage capabilities is essential for electronic applications and the next generation electric power systems. This study employed a one-step two-roll mill mixing technique to fabricate chlorinated polyethylene (CPE) nanocomposites reinforced with copper oxide (CuO) nanoparticles, specifically engineered for energy storage applications. UV–visible spectroscopy indicated a redshift in absorbance, with the nanocomposite containing 7 wt% CuO displaying the highest refractive index and the lowest optical bandgap energy. FTIR analysis confirmed the bonding interactions between CuO and CPE while XRD verified the presence of crystalline CuO phase. FE-SEM and HR-TEM images demonstrated a uniform surface morphology and homogeneous nanoparticle dispersion of CuO nanoparticles at a 7 wt% loading, while agglomeration became apparent at higher concentrations. Thermal analysis using DSC and TGA revealed enhanced glass transition temperature and thermal stability upon incorporation of nanoparticles. The AC conductivity, dielectric constant, and modulus of the nanocomposites were evaluated across varying temperatures and frequencies, showing a consistent increase with rising nanofiller content. These properties reached their peak at 7 wt% CuO loading, where AC conductivity and dielectric constant values were approximately 13.4 and 3 times higher, respectively than those of pristine CPE. Additionally, mechanical properties were also significantly improved with CuO reinforcement. The nanocomposite containing 7 wt% CuO exhibited outstanding mechanical performance, with tensile strength increasing by 106.7 %, impact strength by 48.9 %, and hardness by 15.6 %. These results underscore the potential of CPE/CuO nanocomposites as advanced electroactive materials for future energy storage applications.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"327 ","pages":"Article 128399"},"PeriodicalIF":4.1,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143837323","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}

引用次数: 0

Effects of additives and pre-heating temperature on interlayer shrinkage of polyamide-12 parts in Additive Manufacturing

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2025-04-15 DOI: 10.1016/j.polymer.2025.128409

Benjamin H.W. Teo , Van Thai Tran , Chao Tang , Kaijuan Chen , Jun Zeng , Hejun Du

Additive manufacturing (AM) processes, which require additives, fabricate polyamide-12 (PA12) parts. These additives can affect its physical appearance and mechanical properties in a single print job due to variations in thermal distribution. These properties are influenced by its crystallization behavior, which in turn is affected by the presence of additives of solvent due to low pre-heat temperature. From the Differential Scanning Calorimetry experiment, the remained DI-water affects the crystallization behavior of PA12. At low pre-heat temperature, the remained water vapor lowered the crystallization temperature and overall crystallinity of the PA12. The Thermomechanical Analysis results also suggested that samples with low pre-heat temperature exhibited higher shrinkage during the cooling process. Real-time optical images showed that the presence of additives reduced spherulite size and increased initiation rate. This investigation provided deeper insights into the influence of additives on the crystallization of PA12 for additive manufacturing.

{"title":"Effects of additives and pre-heating temperature on interlayer shrinkage of polyamide-12 parts in Additive Manufacturing","authors":"Benjamin H.W. Teo , Van Thai Tran , Chao Tang , Kaijuan Chen , Jun Zeng , Hejun Du","doi":"10.1016/j.polymer.2025.128409","DOIUrl":"10.1016/j.polymer.2025.128409","url":null,"abstract":"<div><div>Additive manufacturing (AM) processes, which require additives, fabricate polyamide-12 (PA12) parts. These additives can affect its physical appearance and mechanical properties in a single print job due to variations in thermal distribution. These properties are influenced by its crystallization behavior, which in turn is affected by the presence of additives of solvent due to low pre-heat temperature. From the Differential Scanning Calorimetry experiment, the remained DI-water affects the crystallization behavior of PA12. At low pre-heat temperature, the remained water vapor lowered the crystallization temperature and overall crystallinity of the PA12. The Thermomechanical Analysis results also suggested that samples with low pre-heat temperature exhibited higher shrinkage during the cooling process. Real-time optical images showed that the presence of additives reduced spherulite size and increased initiation rate. This investigation provided deeper insights into the influence of additives on the crystallization of PA12 for additive manufacturing.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"327 ","pages":"Article 128409"},"PeriodicalIF":4.1,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143837442","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}

引用次数: 0

Effect of chain length of α,ω-aliphatic diacid on melt crystallization and optical, mechanical and gas barrier properties of aliphatic-aromatic PBXT copolyesters

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2025-04-15 DOI: 10.1016/j.polymer.2025.128402

Pengkai Qin , Linbo Wu , Suyun Jie

Two series of high molecular weight aliphatic-aromatic random copolyesters: PBXT, where X represents the carbon atom number of the aliphatic α,ω-diacids, PBXT₄₈ and PBXT_50w (X = 4–14, even), with molar and mass copolymer compositions (48 mol% and 50 wt%) equal to those of commercial poly(butylene adipate-co-terephthalate) (PBAT) were synthesized from butanediol, terephthalic acid and various aliphatic α,ω-diacids. They were characterized with ¹H NMR, and their melt crystallization, optical, mechanical and gas barrier properties were assessed. In these copolyesters, the melt crystallization of butylene terephthalate (BT) sequence is dominant, while the butylene adipate (BX) sequences can also crystallize from melt when the BX content is high enough, the chain length of α,ω-diacid unit or the crystallization time is long enough. Long enough chain length of α,ω-diacid unit (X ≥ 6) endows PBXT with sufficient chain flexibility/mobility and, therefore, excellent melt crystallizability at rapid cooling. For PBXTs with X ≥ 6, the effect of X on BT crystallization is not monotonic. In particular, both PB6T and PB12T displayed a higher melt crystallization temperature than the adjacent PBXTs. Compared to PB6T, PB4T has higher transparency and gas barrier properties; with increasing X from 6 to 14, the PBXTs show increased transparency and water vapor barrier, but decreased oxygen barrier performance. The tensile modulus and strength of PBXT decrease, and the elongation at break increases with increasing X. But the effect of X is clearly weakened for PBXTs with the same mass composition of 50 wt%.

{"title":"Effect of chain length of α,ω-aliphatic diacid on melt crystallization and optical, mechanical and gas barrier properties of aliphatic-aromatic PBXT copolyesters","authors":"Pengkai Qin , Linbo Wu , Suyun Jie","doi":"10.1016/j.polymer.2025.128402","DOIUrl":"10.1016/j.polymer.2025.128402","url":null,"abstract":"<div><div>Two series of high molecular weight aliphatic-aromatic random copolyesters: PBXT, where X represents the carbon atom number of the aliphatic <em>α,ω</em>-diacids, PBXT<sub>48</sub> and PBXT<sub>50w</sub> (X = 4–14, even), with molar and mass copolymer compositions (48 mol% and 50 wt%) equal to those of commercial poly(butylene adipate-co-terephthalate) (PBAT) were synthesized from butanediol, terephthalic acid and various aliphatic <em>α</em>,<em>ω</em>-diacids. They were characterized with <sup>1</sup>H NMR, and their melt crystallization, optical, mechanical and gas barrier properties were assessed. In these copolyesters, the melt crystallization of butylene terephthalate (BT) sequence is dominant, while the butylene adipate (BX) sequences can also crystallize from melt when the BX content is high enough, the chain length of <em>α</em>,<em>ω</em>-diacid unit or the crystallization time is long enough. Long enough chain length of <em>α</em>,<em>ω</em>-diacid unit (<strong>X</strong> ≥ 6) endows PBXT with sufficient chain flexibility/mobility and, therefore, excellent melt crystallizability at rapid cooling. For PBXTs with <strong>X</strong> ≥ 6, the effect of <strong>X</strong> on BT crystallization is not monotonic. In particular, both PB6T and PB12T displayed a higher melt crystallization temperature than the adjacent PBXTs. Compared to PB6T, PB4T has higher transparency and gas barrier properties; with increasing <strong>X</strong> from 6 to 14, the PBXTs show increased transparency and water vapor barrier, but decreased oxygen barrier performance. The tensile modulus and strength of PBXT decrease, and the elongation at break increases with increasing <strong>X</strong>. But the effect of <strong>X</strong> is clearly weakened for PBXTs with the same mass composition of 50 wt%.</div></div>","PeriodicalId":405,"journal":{"name":"Polymer","volume":"327 ","pages":"Article 128402"},"PeriodicalIF":4.1,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143837326","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}

引用次数: 0

Structure and performance evolution of polybutylene succinate foams with lightweight and high-strength wood-like material under solid-state stretching

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2025-04-15 DOI: 10.1016/j.polymer.2025.128413

Jiajun Luo , Zhiqing Liu , Shuangqiao Yang , Shibing Bai , Weijun Zhen

Wood possesses a unique structure, characterized by "longitudinal tubular cells and aligned fibers" on its radial section, which current polymer processing techniques find challenging to replicate. In this study, polybutylene succinate (PBS) material, foamed with supercritical carbon dioxide (ScCO₂) at a foaming ratio of 3.56 times, was subjected to forced solid-state stretching. This stretching was conducted above the glass transition temperature (T_g) and below the melting point (T_m), resulting in a transformation of the spherical cells into a "tubular cell" structure. During this process, the polymer material aligned along the height of the tubular cells, undergoing crystalline reordering and growth. Consequently, the tensile strength of the resulting foam material increased significantly from 7.3 MPa to 30.7 MPa, and the tensile modulus rose from 67.3 MPa to 178.8 MPa. Scanning electron microscopy results confirm that the cell structure of the PBS foam transitions from spherical to a regularly arranged tubular configuration. Furthermore, differential scanning calorimetry and small-angle X-ray scattering tests reveal a substantial enhancement in the crystallinity and orientation of the PBS foam cell walls. Complementary static structural simulations conducted in ANSYS Workbench demonstrate that circular cells can indeed transform into a tubular lattice-like structure, akin to that of wood.

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引用次数: 0

Unraveling the biaxial deformation mechanism of isotactic polypropylene film via in-situ synchrotron radiation X-ray scattering

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer

Pub Date : 2025-04-15 DOI: 10.1016/j.polymer.2025.128411

Jianhe Zhu , Xueqing Han , Hong Cheng , Hang Guo , Jungen Chen , Wancheng Yu , Liangbin Li , Kunpeng Cui

The structure evolution of polymers during biaxial stretching presents a complex, critical challenge in both polymer industry processing and polymer physics. Despite its significance, biaxial deformation of polymers at high temperature has been less studied due to experimental difficulties, leaving underlying mechanism poorly understood. Here we employ a self-developed in-situ biaxial stretching device combined with synchrotron radiation small and wide-angle X-ray scattering (SAXS and WAXS) to track the real-time structural evolution of isotactic polypropylene (iPP) films under sequential (SEQ) and simultaneous (SIM) biaxial stretching. Our results reveal distinct deformation pathways. In the first step of SEQ stretching, the initial linear deformation is governed by lamellar separation, interlamellar shear, and lamellar rotation, followed by coarse slip-induced yielding. Subsequent melting-recrystallization equilibration maintains constant crystallinity while forming fibrous crystals. During the second SEQ stage, stretch-induced melting dominates initially, and the chain reorganization drives the formation of new crystals. In contrast, SIM stretching primarily involves crystal melting. Lamellae undergo separation, shear, and slip, followed by progressive melting, first in thinner lamellae, then within lamellar clusters. Notably, recrystallization is suppressed in SIM due to the absence of in-plane orientation, underscoring chain alignment, rather than entropy reduction, as the primary driving force for recrystallization.

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