Polymer Degradation and Stability最新文献

{"title":"Effect of different structured epoxy-type reactive rejuvenators on recycling performance and repair mechanism of the aged styrene-butadiene-styrene (SBS) modified bitumen","authors":"Qingyuan Ma ,&nbsp;Hongwei He ,&nbsp;Wenwen Yu ,&nbsp;Jianjun Xu ,&nbsp;Quanxin Xu ,&nbsp;Jiaqi Xue ,&nbsp;Yushi Jin ,&nbsp;Rong Zhu ,&nbsp;Chen Han ,&nbsp;Bo Wang ,&nbsp;Chen Cui ,&nbsp;Jie Ma ,&nbsp;Fuyong Liu ,&nbsp;Heng Zhang","doi":"10.1016/j.polymdegradstab.2025.111331","DOIUrl":"10.1016/j.polymdegradstab.2025.111331","url":null,"abstract":"<div><div>The styrene-butadiene-styrene (SBS) modified bitumen (SMB) has gained worldwide popularity due to its exceptional performance. However, the waste SMB generated by its maintenance and resurfacing urgently needs to be rejuvenated with good performance for the prolonged service life of asphalt roads. In this study, the epoxy-type reactive rejuvenators, trimethylmethylpropane triglycidyl ether (TMPTE) and polyethylene glycol diglycidyl ether (PEGDGE), combined with vegetable oil (VO) were employed to reconstruct the aged SBS modified bitumen. Mild-moderate thermo-oxidative aging and pressure aging methods were applied, and regeneration experiments were conducted subsequently. FTIR indicates the occurrence of the SBS repair reaction or/and epoxy homo-polymerization. GPC demonstrates the restoration of characteristic peaks for both SBS and bitumen in aged SMB after the regeneration, while FM images show a reconstructed network structure of SBS. From a macroscopic perspective, the regeneration of aged SMB was assessed from four aspects, i.e. high/low temperature performance, elasticity and stiffness. It is found that the PEGDGE regenerated SMB exhibits the best high-temperature performance in the thermo-oxidative aging system, while the TMPTE regenerated SMB demonstrates the best high-temperature performance in the pressure aging system. And TMPTE regenerated SMB exhibits the best low temperature performance and elasticity in the thermo-oxidative aging system, and PEGDGE regenerated SMB exhibits the excellent low temperature performance and recovery performance in the pressure aging system. Meanwhile, in the thermo-oxidative aging system, PEGDGE regenerated SMB demonstrates superior deformation resistance. In the pressure-aging system, TMPTE regenerated SMB exhibits exceptional deformation resistance. The mechanism for the varying regeneration effects of different aging methods and regeneration systems were analyzed, suggesting a possible correlation with the molecular structures (e.g. functionality, chain flexibility) of the epoxy-type reactive rejuvenators. This study offers a theoretical guidance for regenerating aged SMB pavements with varying degrees of aging and a reference for selection or synthesis of reactive rejuvenators.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"237 ","pages":"Article 111331"},"PeriodicalIF":6.3,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143679858","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}

{"title":"Zinc oxide nanoparticles and sage (Salvia officinalis) essential oil as active components of alginate films for food packaging","authors":"Jolanta Kowalonek ,&nbsp;Natalia Stachowiak‒Trojanowska ,&nbsp;Zuzanna Cieciurska ,&nbsp;Agnieszka Richert","doi":"10.1016/j.polymdegradstab.2025.111328","DOIUrl":"10.1016/j.polymdegradstab.2025.111328","url":null,"abstract":"<div><div>Antioxidant and antibacterial packaging based on natural polymers have been the subject of interest in recent years. Such functional materials aim to prolong food's shelf life and reduce food waste. Therefore, alginate films enriched with zinc oxide nanoparticles (ZnONPs) and sage essential oil (SEO) were obtained. ZnONPs were produced by means of green synthesis using tansy (<em>Tanacetum vulgare</em>) extract. XRD and SEM results proved the formation of inorganic nanoparticles, whose sizes were about 16 nm and shape was oval. The structure, mechanical properties, moisture content, water vapor transmission rate, and antimicrobial and antioxidant properties of the biopolymeric films with ZnONPs and/or SEO were investigated. ATR-FTIR spectra showed a lack of interactions between polymeric film components. SEM images exhibited uniform distribution of ZnONPs in the alginate film, while SEO formed an emulsion with this biopolymer. Alginate film with both additives exhibited higher values of tensile strength (7.76 ± 0.75 MPa) and elongation at the break (64.98 ± 2.27 %), lower moisture content (19.61 ± 0.20 %), better barrier properties (257.50 ± 4 g•m^‒2•day^‒1), and enhanced antioxidant (91.64 ± 3.62 μmol Trolox/100 <em>g</em>) and antibacterial properties compared to alginate films with ZnONPs or SEO separately. Combining ZnONPs and SEO was advantageous due to the meaningful synergistic effect, which is especially pronounced in the enhanced antioxidant and antimicrobial features. Such properties are highly needed in the case of active food packaging. Improved properties of the modified alginate film made it suitable for packing applications for fruits and vegetables.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"237 ","pages":"Article 111328"},"PeriodicalIF":6.3,"publicationDate":"2025-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143654882","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}

{"title":"Investigation of biodegradable microparticle release and environmental accumulation in Poly(butylene succinate) degradation under UV and non-UV aging conditions","authors":"Peng Cui ,&nbsp;Jiamin Wang ,&nbsp;Lu Mao ,&nbsp;Yuan Gao ,&nbsp;Shuang Li ,&nbsp;Yan Liu ,&nbsp;Haimei Mao ,&nbsp;Munan Qiu ,&nbsp;Wenqi Zou ,&nbsp;Xia Gao","doi":"10.1016/j.polymdegradstab.2025.111323","DOIUrl":"10.1016/j.polymdegradstab.2025.111323","url":null,"abstract":"<div><div>This study investigates the release behavior of biodegradable microparticles and their environmental accumulation during the degradation of poly(butylene succinate) (PBS) through enzymatic hydrolysis and UV aging. By employing laser diffraction and image counting techniques, we monitored the real-time release of biodegradable microparticles during PBS degradation. The findings reveal that during enzymatic degradation, non-UV-aged PBS releases a significant number of microparticles, peaking at 4569 particles per 50 µL on the fifth day, with 97% of these particles subsequently degraded. In contrast, UV-aged PBS shows a markedly slower degradation rate. For samples pretreated with UV for 30 days, the number of released microparticles peaks at 1856 particles per 50 µL, and even after the complete disintegration of the primary material, approximately 52% of these microparticles remain undegraded. UV aging initially accelerated surface degradation due to photochemical reactions but ultimately reduced overall degradation efficiency by inducing crosslinking, resulting in persistent microparticle accumulation. Analytical techniques such as Scanning Electron Microscopy (SEM), Gel Permeation Chromatography (GPC), Nuclear Magnetic Resonance (¹HNMR ), and X-ray Photoelectron Spectroscopy (XPS) were used to analyze structural changes and degradation products, revealing surface chemical transformations and their impact on microparticle release. This research underscores the importance of comprehensive environmental assessments of biodegradable plastics, particularly focusing on the dynamic release of microparticles during degradation. The findings provide a critical scientific basis for developing safer biodegradable materials and contribute to effectively addressing plastic pollution issues.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"237 ","pages":"Article 111323"},"PeriodicalIF":6.3,"publicationDate":"2025-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143679856","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}

{"title":"Enhancing α- and β-glucan esters’ material selection through machine learning: An empirical study","authors":"Misuzu Kumagai ,&nbsp;Taizo Kabe ,&nbsp;Kiichi Obuchi ,&nbsp;Kiyohiko Toyama ,&nbsp;Tadahisa Iwata ,&nbsp;Shukichi Tanaka ,&nbsp;Daniel Oñoro-Rubio","doi":"10.1016/j.polymdegradstab.2025.111293","DOIUrl":"10.1016/j.polymdegradstab.2025.111293","url":null,"abstract":"<div><div>Polysaccharide esters, with their potential as biomass plastics, represent sustainable alternatives to oil-based plastics. This study contributes to the optimization of material design by demonstrating that Materials Informatics (MI), combined with machine learning, can be effectively utilized to predict and enhance the properties of polysaccharide esters. The research methodology involved generating Simplified Molecular Input Line Entry System (SMILES) representations for polysaccharide esters, creating a novel dataset from scratch. By employing fourteen distinct machine learning models, the research successfully constructed a Quantitative Structure-Property Relationship (QSPR) model that accurately predicts <span><math><msub><mrow><mi>T</mi></mrow><mrow><mi>g</mi></mrow></msub></math></span> and Elongation at Break of the given esters. Additionally, the study applied multiobjective optimization to these models, optimizing for both <span><math><msub><mrow><mi>T</mi></mrow><mrow><mi>g</mi></mrow></msub></math></span> and Elongation at Break. This approach enables the efficient achievement of new material properties by significantly reducing the number of required experiments. The practical application of these models was further validated through laboratory experiments involving the synthesis and testing of proposed polysaccharide ester structures.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"238 ","pages":"Article 111293"},"PeriodicalIF":6.3,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143685961","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}

{"title":"Pyrolysis mechanism of spent LIBs separator and catalytic effect of metal foils: Insights from combined experimental and DFT studies","authors":"Ran Tao ,&nbsp;Yufeng Wu ,&nbsp;Lijuan Zhao ,&nbsp;Bin Li ,&nbsp;Haoran Yuan ,&nbsp;Jing Gu ,&nbsp;Yong Chen","doi":"10.1016/j.polymdegradstab.2025.111326","DOIUrl":"10.1016/j.polymdegradstab.2025.111326","url":null,"abstract":"<div><div>The rapid development of new energy technologies has facilitated the widespread adoption of electric vehicles, but has also led to a significant increase in the generation of spent lithium-ion batteries (LIBs). Extensive research has been conducted on the recycling of spent LIBs with most studies focusing on the recovery of the anode and cathode materials, electrolytes, and current collectors. Research on the recycling of battery separators remains limited. Pyrolysis technology has been shown to enable the efficient recovery of organic components and has already been applied in the recycling of spent LIB separators. However, existing studies reveal that the mechanisms underlying separator pyrolysis are not well understood, and the role of endogenous metals (Cu and Al foil) in the pyrolysis process remains unclear. Density Functional Theory (DFT) calculations have been extensively employed in mechanistic investigations of organic compound pyrolysis and metal-catalyzed reactions. In this context, the commonly used polypropylene (PP) separator was selected as the subject of this study. Various thermal analysis devices and kinetic methods were employed to investigate the pyrolysis characteristics, pyrolysis kinetics, distribution of pyrolysis products, and the influence of metal foils on the pyrolysis process of PP separators. Through DFT calculations and wave function analysis, the pyrolysis mechanism of PP separators and the catalytic role of metal foils in the PP pyrolysis process were elucidated.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"237 ","pages":"Article 111326"},"PeriodicalIF":6.3,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143654880","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}

{"title":"Solid-state modification for improved flame retardancy","authors":"Carolane Gerbehaye ,&nbsp;Katrien V. Bernaerts ,&nbsp;Gaelle Fontaine ,&nbsp;Serge Bourbigot ,&nbsp;Rosica Mincheva ,&nbsp;Jean-Marie Raquez","doi":"10.1016/j.polymdegradstab.2025.111327","DOIUrl":"10.1016/j.polymdegradstab.2025.111327","url":null,"abstract":"<div><div>The European Union's regulations on halogenated flame retardants have led to investigations of alternatives. Poly(butylene terephthalate) (PBT), commonly used for its attractive properties in terms of use in electrical and electronics applications, is one of the polymers at risk under these guidelines. Indeed, its poor fire resistance often restricts its use or requires the addition of potentially toxic elements. The improvement of its flammability properties is thus crucial, and solid-state modification (SSM) is an ideal method to achieve this while preserving its crystalline structure and thermomechanical characteristics. Therefore, an intumescent copolyester made by SSM using a biobased co-monomer has been prepared. First, PBT was modified with a carbonizing agent, 2,3:4,5-di-O-isopropylidene-galactarate (GalX). The optimization of this process involved study of the effects of temperature, time, and pressure. The thermal properties of P(BT-<em>co</em>-GalXT) demonstrates that the positive qualities of PBT are retained reflecting the preservation of the crystalline phases during the solid-state reactions. Finally, pure PBT may be combined with the copolyester and ammonium polyphosphate to obtain an intumescence system which exhibits V-0 rating in the UL 94 test. This composition displays the desirable properties of the homopolymer as well as improved fire behavior.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"237 ","pages":"Article 111327"},"PeriodicalIF":6.3,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143642061","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}

{"title":"Phosphorus-derived imidazolium salts with varied oxidation states: Tailoring latency, mechanical properties, and flame retardancy in single-component epoxy resins","authors":"Jingsheng Wang ,&nbsp;Jun Wang ,&nbsp;Shuang Yang ,&nbsp;Guoping Ding ,&nbsp;Renxin Xu ,&nbsp;Wei Liu ,&nbsp;Jiuxiao Sun ,&nbsp;Kaiwen Chen ,&nbsp;Liu Duan ,&nbsp;Jiaqi Wang ,&nbsp;Hao Wang ,&nbsp;Siqi Huo","doi":"10.1016/j.polymdegradstab.2025.111325","DOIUrl":"10.1016/j.polymdegradstab.2025.111325","url":null,"abstract":"<div><div>Single-component epoxy resin (EP) is the premix of EP and latent curing agent, which is highly demanded in industries. However, current single-component EPs struggle to balance storage stability with mechanical properties and flame retardancy. To address this issue, three phosphorus-derived imidazolium salts (MPOx, x = 2, 3, 4) were synthesized using 2-ethyl-4-methylimidazole (EMI) and phosphorus-containing acids with different oxidation states (diphenylphosphinic acid, phenyl hydrogen phenylphosphonate, and diphenyl phosphate). The oxidation state of phosphorus significantly influenced thermal latency of MPOx, with higher oxidation states leading to improved latency. EP/MPO4 achieved the longest shelf life of 42 d at 25 °C. EP/MPO3 and EP/MPO4 exhibited enhanced tensile strength, modulus, and impact resistance compared to EP/EMI, but EP/MPO2 showed poor mechanical properties due to phase separation. All EP/MPOx achieved limiting oxygen index (LOI) exceeding 30 %, with EP/MPO3 showing the highest LOI of 34.0 % and significant reductions in heat release and smoke production. Flame-retardant mechanistic studies revealed a shift from gaseous-phase flame inhibition to condensed-phase promoting carbonization with increasing phosphorus oxidation state. Obviously, MPOx provides a tailored balance of latency, mechanical strength, and flame retardancy, making it a promising solution for advanced single-component EPs in aerospace, electronics, and optical applications.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"237 ","pages":"Article 111325"},"PeriodicalIF":6.3,"publicationDate":"2025-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143629255","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}

{"title":"High performance polyurethanes with extraordinary hydrolytic resistance prepared from bio-renewable alkyl-δ-lactones: Synthesis, properties and chemical recycling","authors":"Min Zhang ,&nbsp;Qin Yan ,&nbsp;Xinxin Yu ,&nbsp;Yong Shen ,&nbsp;Zhibo Li","doi":"10.1016/j.polymdegradstab.2025.111322","DOIUrl":"10.1016/j.polymdegradstab.2025.111322","url":null,"abstract":"<div><div>Despite the great advancements achieved for the chemically recyclable polymers in recent years, it remains as a challenge to develop chemically recyclable polyurethanes from bio-renewable monomers with thermal and mechanical properties that compare with petroleum-based polyurethanes. In this contribution, we present the successful preparation of a series of chemically recyclable polyurethanes from the ring-opening polymerization of bio-renewable alkyl-δ-lactones followed by the tandem polycondensation with diisocyanate and a chain extender. The thermal and mechanical properties of the obtained polyurethanes can be easily tailored by adjusting the molar mass of soft segment, the hard segment content as well as the length of the pendent alkyl group of the poly(alkyl-δ-lactone) polyol precursor. The obtained polyurethanes behave as thermoplastic elastomers with excellent tensile strength and elasticity that compare with commodity petroleum-based polyurethanes. Remarkably, the obtained polyurethanes exhibit extraordinary hydrolytic resistance and remain intact up to 5 months in acidic or basic aqueous solution. The chemical recycling of polyurethanes to recover clean alkyl-δ-lactones with high yield (&gt; 95 %) can be easily achieved by simple heating the materials in bulk under reduced pressure.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"237 ","pages":"Article 111322"},"PeriodicalIF":6.3,"publicationDate":"2025-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143621205","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}

{"title":"A novel P-N structure modified halloysite nanotube for simultaneously enhancing flame retardancy and mechanical properties of unsaturated polyester resin","authors":"Hang-Ping Fang ,&nbsp;Ying-Ming Li ,&nbsp;Dan-Ping Zhu ,&nbsp;Yao Deng ,&nbsp;De-Yi Wang","doi":"10.1016/j.polymdegradstab.2025.111324","DOIUrl":"10.1016/j.polymdegradstab.2025.111324","url":null,"abstract":"<div><div>Unsaturated polyester resin (UPR) is highly flammable due to its long-chain polymer structure composed of hydrocarbon elements, which significantly restricts its application. In this study, an organic-inorganic hybrid flame retardant was developed by using siloxane (KH-560) as a bridging agent to graft bio-based P-N structure (the salt formation of diphenyl phosphoric acid and cytosine) onto the surface of halloysite nanotubes (HNT), resulting in the synthesis of HNT-Si-DC. Experimental results demonstrated that the UPR composite containing 15 wt% HNT-Si-DC achieved a UL-94 V-0 rating, with a limiting oxygen index (LOI) of 33.2 %. Compared to pure UPR, the peak of heat release rate (PHRR) of the composite decreased by 49.8 %. Furthermore, the mechanical properties of the UPR/HNT-Si-DC₁₅ composite were significantly enhanced, with the tensile modulus increasing by 38.7 % and the flexural strength improving by 21.3 % compared to those of pure UPR, indicating high mechanical performance. Additionally, the dense and continuous carbon layer preferentially enhanced the flame retardancy. This work presents a highly efficient approach to designing organic-inorganic hybrid modified HNT for the development of UPR composites with excellent fire resistance and high mechanical properties.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"237 ","pages":"Article 111324"},"PeriodicalIF":6.3,"publicationDate":"2025-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143628939","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}

{"title":"Novel one-pot recovery and in-situ crystallization of polyhydroxybutyrate and hydroxyapatite/tricalcium phosphate biocomposite microparticles with comparative life cycle assessment","authors":"Anuchan Panaksri ,&nbsp;Pasin Kuncharin ,&nbsp;Purin Neerawong ,&nbsp;Taranuch Panthong ,&nbsp;Thanadol Thanakornkriengkrai ,&nbsp;Sani Boonyagul ,&nbsp;Woradej Pichaiaukrit ,&nbsp;Sutee Wangtueai ,&nbsp;Nuankanya Sathirapongsasuti ,&nbsp;Kittisak Jantanasakulwong ,&nbsp;Pornchai Rachtanapun ,&nbsp;Patnarin Worajittiphon ,&nbsp;Phavit Wongsirichot ,&nbsp;Nuttapol Tanadchangsaeng","doi":"10.1016/j.polymdegradstab.2025.111321","DOIUrl":"10.1016/j.polymdegradstab.2025.111321","url":null,"abstract":"<div><div>Formation of polyhydroxybutyrate (PHB) biopolymer composites with bioceramics such as hydroxyapatite (HA) and tricalcium phosphate (TCP) is essential in achieving mechanical properties needed for novel bone tissue engineering using PHB. However, composite microparticle synthesis typically requires multiple steps, including 1) PHB recovery and purification, 2) dispersion of HA and TCP particles in the melt or solvent-dissolved polymer liquid, and 3) micro-droplet drying. In this study, PHB/HA/TCP composite microparticles were successfully produced by one-pot biosynthesis. This was achieved during acid-based PHB recovery by utilizing the crystallization of native-amorphous granule PHB within <em>Cupriavidus necator</em>. In-situ PHB crystallization was successfully monitored by real-time attenuated total reflection-Fourier transform infrared (ATR-FTIR). Additionally, the in-situ crystallization behavior was elucidated by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The most suitable conditions for synthesis of the PHB/HA/TCP composite were pH 2, and 20 min of reaction time, which capitalizes on the amorphous nature of the in-situ PHB during recovery. The HA and TCP did not function as nucleating agents, thereby not impacting accumulation and homogeneity. This allows HA/TCP bioceramics to be inserted into the polymer during the PHB recovery period, and after the crystallization step is completed, the composite microparticles could facilely form. The crystallization mechanism was found to be sporadic, and the morphology was a disc with two dimensions. Additionally, the life cycle assessment (LCA) revealed that the one-pot method reduced global warming potential (GWP) emissions by 50% and non-renewable energy use (NREU) by a comparable margin, compared to the conventional multi-step method for HA/TCP (20:80) production. These findings emphasize the environmental advantages of the one-pot approach alongside its cost and process efficiency. The demonstrated one-pot synthesis method would allow for more streamlined and cost-effective production of PHB/HA/TCP biocomposites. The materials produced and insights gained will be beneficial for future development of biopolymer composite processing and biomedical applications.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"237 ","pages":"Article 111321"},"PeriodicalIF":6.3,"publicationDate":"2025-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143654881","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}