In the pursuit of sustainable packaging to combat plastic pollution, sodium alginate, a renewable biopolymer, holds promise but demands enhancements for brittleness and moisture sensitivity. This study compares ionic crosslinking and polymer blending to develop high-performance films from a tensile strength-optimized formulation. Ionic crosslinking with CaCl2 boosts tensile strength to 41 MPa but induces brittleness (<2% elongation), reduced thermal stability and barrier trade-offs. On the contrary, compatibilizer-free blending with 30 wt% poly[(butylene adipate)-co-terephthalate] (PBAT) yields better films with 47 MPa tensile strength, 852 g m(-2) day(-1) water vapor transmission rate and improved thermal stability, driven by hydrogen bonding and 'sea-island' morphology. Based on published literature on PBAT compostability and reported degradation behavior of PBAT/alginate-type systems, the blend films are expected to be compatible with industrial composting end-of-life routes; however, biodegradation was not measured in this study. Polymer blending emerges as a superior strategy, decoupling trade-offs for multifunctional, ecofriendly packaging films.
Price variations, limited availability, non-biodegradability and environmental importance have led to an increased demand for renewable alternatives to petroleum-based counterparts. In line with the requirements, the present study focused on the preparation of mahua-oil-derived polyols for the formulation of nanocomposite polyurethane (PU) coatings. The polyol was characterized using H-1 NMR and FTIR spectroscopy, gel permeation chromatography and end group analysis. Silver-doped hydroxyapatite nanoparticles (Ag-HAPs) were also synthesized from waste chicken eggshell as another renewable alternative. These nanoparticles were incorporated into the PU matrix in varying amounts (0.4-3.2 wt%) to improve the performance of the PU coatings. The surface morphology of Ag-HAPs and their PU composites was studied by optical microscopy and SEM. The resulting nanocomposite PU coatings showed enhanced mechanical and protective properties such as pencil hardness, flexibility, adhesion, chemical resistance and corrosion protection compared with pristine PU coatings. In addition, the incorporation of Ag-HAPs increased the hydrophobicity of the composite film evidenced by higher contact angles. X-ray Diffraction (XRD) and TGA confirmed the amorphous nature of the PU matrix and that it exhibited better thermal stability with increasing nanoparticle content. Overall, the developed nanocomposite coatings offer a promising sustainable substitute to petroleum origin materials and demonstrate excellent thermal stability and anticorrosion performance.
Thermoplastic starch (TPS) is a biodegradable and cost-effective alternative to single-use plastic packaging; however, its poor mechanical strength and water resistance limit its commercial applications. This study investigated the incorporation of bio-based materials-sisal fibers (untreated and alkali-treated), sodium carboxymethyl cellulose (CMC) with different substitution levels (0.7 and 1.2) and nanoclay-into TPS to enhance its properties. Neat TPS and TPS/bio-based material films were prepared using a casting method and evaluated through tensile testing, SEM, water absorption, thermal analysis and XRD. CMC0.7 exhibited the most balanced performance, increasing the tensile modulus from 52.52 MPa (neat TPS) to 114.04 MPa and the tensile strength from 4.17 to 5.52 MPa, while reducing water absorption from 14.94% to as low as 6.70% depending on CMC0.7 content and maintaining comparable elongation at break. Untreated sisal fiber at 15 wt% provided the greatest reduction in water absorption from 14.94% (neat TPS) to 4.25%, but caused a pronounced decrease in elongation at break from 51.10% to 7.79%, while alkali treatment enhanced tensile properties, thermal stability and crystallinity. CMC1.2 increased the elongation at break up to 133.95% and enhanced crystallinity due to improved chain mobility. Nanoclay contributed to improved moisture resistance by reducing water absorption but offered limited mechanical reinforcement due to dispersion issues. Overall, CMC0.7 emerged as the most effective additive, offering a combination of mechanical enhancement and water resistance suitable for TPS-based biodegradable films with potential applications in non-barrier packaging.
Synthetic polypeptides prepared from N-carboxyanhydride (NCA) monomers are important platforms for environmental and medical applications due to their biomimetic structures which can beleveraged to deliver tunable properties. During synthesis, amino acid side chains are generally protected to prevent undesired side reactions. Following polymerization, full deprotection is typically pursued to expose the largest number of functional groups, with the expectation that greater functional group availability enhances intermolecular interactions and overall performance. While the extent of deprotection is known to impact polypeptide properties, the specific effects of partial deprotection on polypeptide functionality have not received significant attention. Here, we demonstrate that controlled acidic partial deprotection offers a straightforward and reproducible means for adjusting amphiphilicity and assembly in benzyl-protected poly(glutamic acid) and poly(glutamic acid-block-tyrosine) polypeptides. Over time, partial acidic deprotection can generate distinct morphologies which either match or outperform fully deprotected analogs. For the poly(glutamic acid) homopolymer, partial deprotection produces a population of similar to 130 nm assemblies that present more accessible surface area, leading to adsorption that matches that of fully deprotected poly(glutamic acid). These outcomes are repeatable across reactions and reproducible across 100 mg to 3 g scales, indicating that the behavior reflects inherent polymer structuring rather than anomalous effects. In the copolypeptide poly(glutamic acid-block-tyrosine), maximal drug adsorption similarly occurs at partial deprotection, correlating with the presence of small similar to 70 nm nanoassemblies which outperform more deprotected samples. These effects appear pH-dependent, with assemblies forming only when glutamic acid is deprotonated. When protonated, nanoassembly formation is suppressed, and adsorption generally correlates with particle size distribution which is influenced by the degree of deprotection and the resulting balance between hydrophobic association and chain hydration. Together, these results introduce deprotection as a functional design parameter for tuning polypeptide morphology and adsorption, extending the strategies available for controlling structure-property relationships in NCA-derived polypeptide materials. (c) 2026 The Author(s). Polymer International published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.
In this study, we synthesized a new biocomposite, chitosan-modified urea-formaldehyde resin (UF/Chi), as a potential adsorbent for removing the dye Acid Red 183 (AR183) from aqueous solutions. Characterization of chitosan and the UF/Chi composite was performed using scanning electron microscopy, X-ray diffraction, Fourier transform infrared (FTIR) spectroscopy, non-isothermal thermogravimetric analysis, differential thermal gravimetry and the Brunauer-Emmett-Teller (BET) method. The results showed that the UF/Chi composite has a rough surface and macropores, resulting in a slightly higher specific surface area (S BET) of 6 m2 g-1 compared to chitosan, which has S BET of less than 5 m2 g-1. FTIR spectroscopy validated the interaction between chitosan and UF during in situ synthesis. The UF/Chi composite showed greater thermal stability, with a degradation onset (T 5% = 92.1 degrees C) occurring later than for chitosan (T 5% = 61.1 degrees C). Thermodynamic studies revealed that the adsorption of AR183 on both chitosan and the UF/Chi composite is spontaneous. Adsorption kinetics indicated that the double exponential model best fitted the UF/Chi composite and chitosan, followed by the Elovich model. The Sips isotherm model was optimal for adsorption on both sorbents. The processes are both physical and chemical. Maximum adsorption capacities were 24.2571 mg g-1 for the UF/Chi composite (c = 50 mg dm-3, pH = 6.27, adsorbent dosage 100 mg, T = 25 degrees C) and 196.5018 mg g-1 for chitosan (c = 300 mg dm-3, pH = 6.27, adsorbent dosage 75 mg, T = 25 degrees C). These results suggest that both materials effectively remove AR183 dye from aqueous media.
A series of bio-based epoxy monomers were efficiently synthesized from di-/tri-hydroxy precursors, which were prepared via the cross-aldol condensation of vanillin with various ketone reagents. The epoxy precursors and resulting networks were thoroughly characterized and cured with different amine-based hardeners to investigate the correlation between the chemical structures of the reagents and the resulting properties. Among the tested systems, the epoxy cured with triethylenetetramine (DDN) exhibited the highest glass transition temperature (T g) and alpha-transition temperature (T alpha), along with the highest loss modulus (E '') and crosslinking density (upsilon) (145 degrees C, 157 degrees C, 126.6 MPa and 72.8 x 103 mol m-3, respectively). In contrast, the epoxy cured with 1,10-diaminodecane (DD) which has the lowest functionality in both the epoxy monomer and the curing agent showed the highest molecular weight between crosslinks (M c) (375.6 g mol-1) and the lowest crosslinking density (upsilon) (9.6 x 103 mol m-3). Furthermore, the epoxy sample cured with 1,8-diamino-3,6-dioxaoctane (DDO) demonstrated the highest ultimate tensile strength (22.90 MPa) and elongation at break (6.56%). Thermal stability analysis revealed that the DDN-cured epoxy thermoset exhibited the highest char yield (38.4%), indicating superior thermal resistance. However, the DD-based thermoset displayed the highest statistical heat-resistance index (T s), longest half-life (1311 s) and highest degradation temperature (T d = 447 degrees C), suggesting enhanced long-term thermal stability.
The increasing presence of contaminants from aqueous solutions involves significant environmental and public health risks, necessitating the development of efficient adsorbents for their removal. This study explores the potential of polyaniline-embedded montmorillonite-type clay modified titanium dioxide which was designed via an in situ polymerization technique for removal of malachite green (MG) dye from water. Characterization was conducted using XRD, Fourier transform infrared spectroscopy, X-ray fluorescence, X-ray photoelectron spectroscopy, TEM, SEM coupled with energy dispersive X-ray spectroscopy and a Brunauer-Emmett-Teller study. Significant findings for optimal conditions for MG adsorption were identified as pH 6.0, 50 mg adsorbent mass, 120 min contact time, 200 mg L-1 initial concentration and 298 K, achieving an adsorption capacity of 172.69 and 238.32 mg g-1 for Mt-TiO2 (Mt, natural montmorillonite-type clay) and PAni@Mt-TiO2 (PAni, polyaniline), respectively. Kinetic studies followed a pseudo second order model, and equilibrium data best fitted the Langmuir isotherm for PAni@Mt-TiO2 (R 2 = 0.924) and the Freundlich model for Mt-TiO2 (R 2 = 0.817). The Gibbs free energy (Delta G 0) was negative for the adsorption process in the range 298-328 K, indicating that the process was spontaneous. In addition, the enthalpy parameter (Delta H 0) was determined for the adsorption process using PAni@Mt-TiO2 and Mt-TiO2 at 1.906 kJ mol-1 and 4.506 kJ mol-1, respectively. A positive Delta H 0 indicates that the process is endothermic in the range 298-328 K using both adsorbents. The potential reusability of the adsorbent materials was confirmed for five adsorption-desorption cycles. These results highlight the potential of a conducting polymer matrix as a strategy to develop high-performance, sustainable clay-modified adsorbents for environmental uses, especially water treatment.
In this work, a high performance thermoset material was made from the natural product honokiol which is a diphenolic lignan derived from magnolia bark extract (Magnolia officinalis). Honokiol was cyanated to form the corresponding honokiol dicyanate ester (HONOCY), which was thermally cured forming honokiol polycyanurate (HONOPC) thermoset which was fully characterized. The cyanate ester resin showed excellent low temperature viscosity (0.2 Pa s at 55 degrees C), while the cured polycyanurate had char yields of 75% and 64% up to 600 degrees C in nitrogen and air atmospheres, respectively. The polycyanurate had a high decomposition temperature of 449 degrees C along with a glass transition temperature greater than 400 degrees C. HONOCY then represents a significant improvement for low temperature processing of high performance bio-based cyanate ester polymers for high temperature applications. (c) 2025 Society of Chemical Industry.
Acquiring freshwater from seawater, the solar interfacial vapor generator (SIVG) offers a passive and decentralized approach to addressing water shortage problems. However, the performance of current SIVGs is greatly restricted by the disadvantages of poor controllability and manipulation of seawater transport porous structure and the evaporation interface. To realize rapid seawater replenishment and highly efficient vaporization, we developed a novel polyethylene terephthalate (PET) SIVG with small-sized oriented pores and an ultrathin photothermal conversion layer that exhibited a highly efficient water evaporation rate under both simulated solar and outdoor sunlight illumination. The well-arranged and highly oriented pores with controllable size in PET acted as a confined mass transfer fluid pump to spontaneously transport seawater to the evaporation layer, in which a maximum height of 68 mm via the capillary rise mechanism was reached. The resultant PET layer possessed a low density of 0.08 g cm-3 that exhibited an ideal floating performance to steady the interfacial evaporation. Moreover, due to the superior dispersion structure in the photothermal conversion layer, the surface temperature of the SIVG greatly increased to 101.2 degrees C within 45 s, and the evaporation rate reached 1.26 kg m-2 h-1. This work provides a novel strategy for preparing a high performance SIVG and also paves an innovative way for obtaining fresh water. (c) 2025 Society of Chemical Industry.
Geotextiles are typically used to stabilize steep earthen structures to prevent landslides. Usually, such geotextiles are made from petrol-based polymers (such as polypropylene), but the use of biodegradable geotextiles seems to have specific benefits. Therefore, the present work investigates the mechanical and physicochemical properties of special polymer blends, made from polylactic acid, polybutylene adipate terephthalate and starch. These polymers are receiving increasing attention from industry due to their biodegradability properties and their possibility of economic production. The polymers were mixed with a laboratory extruder and the received homogeneity of the blends was characterized by SEM investigations. The ratio of the different polymers in these blends was varied to understand the relationship between the composition of the blends and the important properties for use in geotextiles. The size of the embedded particles was investigated with SEM and its relation to different mechanical properties was analyzed. The mechanical and viscoelastic properties of the prepared blends were analyzed with quasi-static tensile testing, dynamic mechanical analysis and rheology measurements. In addition, the advanced nanoIR-AFM technique was used to characterize the different prepared polymer blends. (c) 2025 The Author(s). Polymer International published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.
PolyHIPEs are porous polymer monoliths synthesized within high internal phase emulsions (HIPEs) with >74% dispersed phase. Biodegradable polyester-based poly(urethane urea) (PUU) monoliths have been synthesized within water-in-oil emulsions via simultaneous diisocyanate-polyol urethane reactions (predominant) and diisocyanate-water urea reactions (CO2 byproduct) and then used for cell culture and soft tissue engineering. Here, in contrast, an innovative sequential reaction route was used. The polycaprolactone and polylactide polyols were end-capped with diisocyanates, generating urethane groups, prior to emulsion formation. The novel monolith-forming reaction used here was the isocyanate-water urea reaction. Different diisocyanates, from relatively flexible to relatively stiff, highlighted the effects of diisocyanate stiffness on macromolecular stiffness, crystallinity and modulus. Similarly, different polyesters highlighted the effects of polyester stiffness. In addition, the novel isocyanate-water monolith formation reaction was investigated using a lysine-derived diisocyanate. The hierarchical porosity of the resulting CO2-foamed polyHIPEs contained millimeter-scale bubbles and micrometer-scale emulsion-templated porous structures. The crystalline polycaprolactone-based PUUs exhibited melting points between 50 and 80 degrees C, reflecting the unique macromolecular uniformity generated by the sequential urethane-urea reactions compared to the simultaneous urethane-urea reactions that produced amorphous PUUs. Cell growth within the resulting elastomeric polyHIPEs demonstrated potential for soft tissue engineering, with mouse skeletal muscle cells adhering, spreading, proliferating, organizing and filling the entire space. (c) 2025 The Author(s). Polymer International published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.
With the increasing demand for portable electronic devices, it is urgent to develop a flexible energy storage system with high performance and good stability. In this paper, a new kind of poly(vinyl alcohol)-polypyrrole-acidified carbon nanotube (PVA-PPy-CNT-COOH) conductive composite hydrogel was prepared using a freezing-thawing method for fabricating flexible symmetric solid-state supercapacitors. The PVA-PPy-CNT-COOH conductive composite hydrogel has a unique three-dimensional interpenetrating network structure and functional components, endowing the prepared hydrogel with softness, elasticity, compressibility and formability. Furthermore, the influence of feed mode and feeding ratio on hydrogel preparation was explored. According to the optimal experimental process, a flexible symmetric solid-state supercapacitor with high energy storage capacity and stability was fabricated using PVA-PPy-CNT-COOH as the electrode. The capacitance change of the supercapacitor was almost negligible when subjected to 50% strain. Even at 70% strain, the retention rate of volume specific capacitance was still about 88%. This study not only provides a preparation method for a new electrode material but also develops a new type of high-performance and stable flexible symmetric solid-state supercapacitor, which has potential application prospects in flexible energy devices. (c) 2025 Society of Chemical Industry.
Well-defined poly[(methyl acrylate)-co-(hydroxyethyl acrylate)]-graft-) copolymers were synthesized using a completely metal-free strategy by combining atom transfer radical polymerization (ATRP) and ring-opening polymerization (ROP) at ambient temperature. These two orthogonal, metal-free, controlled/living processes, tested in both simultaneous and sequential approaches, were employed to fine-tune grafting density and efficiency by systematically varying monomer concentration and polymerization time. Spectroscopic and chromatographic characterizations confirmed that both ATRP and ROP proceeded in a controlled fashion, yielding graft copolymers with narrowly distributed molecular weights.
This study reports the successful synthesis of bio-based polymer electrolytes (BBPEs) based on sodium alginate, incorporating varying content of lithium nitrate (LiNO3), prepared using the solution casting method. The abundant functional groups in alginate enable effective salt complexation, while LiNO3 provides mobile charge carriers, supporting the development of sustainable BBPE materials. Electrical performance, assessed via electrical impedance spectroscopy, showed an increasing trend in AC conductivity with higher salt content, peaking at similar to 10(-4) S cm(-1) at room temperature. Frequency-dependent analysis followed Jonscher's universal power law, indicating a hopping mechanism. UV-visible spectroscopy revealed a redshift in the absorption spectra and a decrease in the optical band gap from 5.41 to 5.32 eV, reflecting increased structural disorder and electronic delocalization. These results underline a strong link between ionic and optical properties, reinforcing the potential of LiNO3-doped alginate BBPEs for sustainable and transparent electrochemical systems. (c) 2025 Society of Chemical Industry.
Establishing a reliable workflow of inverse design by data‐driven machine learning (ML) models offers significant potential to accelerate molecular design of polymeric materials. Nevertheless, there exist scarcity issues of training datasets in current data‐driven models for polymers. In this contribution, we integrate the ML method with a data augmentation strategy to build upon a workflow of inverse design of polymeric materials with targeted glass transition temperature T g . Results show that the data‐augmented ML model significantly enhances the prediction accuracy of T g in spite of a small training dataset. Furthermore, the data augmentation strategy has the capability of generating the monomers of homopolymers with higher novelty and uniqueness, whose T g values are validated by the simulations of all‐atomic molecular dynamics. The ML‐assisted inverse design workflow offers significant advantages in establishing structure–property relationships and also provides an accelerated pathway for the targeted design of polymer systems. © 2025 Society of Chemical Industry.
Assembling various organic building blocks through carbon-carbon double-bond linkages is highly efficient for constructing high-performance organic semiconductors. Microporous/nanoporous structures can provide robust mass collection accommodation and reactive reaction sites. Here, we report the synthesis of a series of vinylene-linked conjugated porous polymers by Knoevenagel condensation of a tetratopic monomer tetramethyl-2,2 '-bipyridine with different ditopic monomers. The presence of the 2,2 '-bipyridine building blocks created pi-extended conjugation polymeric frameworks, substantial n-type semiconducting properties and coplanar conformation. These frameworks also exhibit strong electron-deficient characters and finely tuned energy levels. Upon visible light irradiation, they exhibited the highest activity of hydrogen peroxide generation up to 1413 mu mol h(-1) g(-1) in pure water. Their excellent recycling and reusability suggest their potential applications in green chemical transformation. (c) 2025 Society of Chemical Industry.
Polymeric photocatalysts have emerged as promising alternatives to traditional metal-based catalysts due to their tunable properties, low cost and environmental friendliness. This review highlights the significant contributions of Professor Dr Kai A. I. Zhang in advancing the field of polymeric photocatalysis. By leveraging the structural versatility of polymers, Professor Zhang's work has developed innovative strategies to enhance light absorption, charge separation and catalytic activity. The review delves into the fundamental principles underlying polymeric photocatalysis, including exciton generation, charge carrier dynamics and surface reactions. It further explores the design considerations for optimizing polymer structures to achieve efficient photocatalytic performance. Key advancements in the synthesis and characterization of polymeric photocatalysts are discussed, along with their applications in various chemical transformations. Professor Zhang's pioneering work has opened up new avenues for the development of sustainable and efficient photocatalytic systems, driving the transition towards a greener future. © 2025 The Author(s). Polymer International published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.
The production of easily separable and recoverable photocatalytic materials remains a critical challenge in achieving sustainable photocatalysis. Here, we have created a hybrid material consisting of photocatalytic polymers encapsulating magnetite nanoparticles. These nanoparticles exhibit excellent performance in oxidative hydroxylation of both boronic-acid- and boronic-acid-pinacol-ester-containing substrates. Moreover, these nanoparticles can be easily recovered and regenerated from the reaction medium via a simple magnetic separation technique. Extremely high efficiency has been maintained over multiple cycles, by recycling the magnetic photocatalyst. (c) 2025 The Author(s). Polymer International published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.
Conjugated microporous polymers (CMPs), distinguished by their extended π -conjugated backbones, nontoxicity and micropore characteristics, provide notable benefits in the development of heterogeneous catalysis systems for task-specific transformations. This review aims to summarize the up-to-date advances in the field of photocatalysis by CMPs, with a particular focus on the applications of CMPs in photocatalytic hydrogen precipitation, pollutant degradation and organic transformation in the last 5 years. Meanwhile, this review also summarizes the major challenges in this field and gives suggestions for the feasible direction of development. © 2024 Society of Chemical Industry.
This study provides a comprehensive review of the role of poly(lactic acid) (PLA) in fused deposition modeling (FDM) for biomedical additive manufacturing. PLA, a biodegradable and biocompatible polymer derived from renewable resources, has become a material of significant interest in healthcare. Its use spans orthopedic implants, including temporary plates, screws, pins and nails, which naturally degrade and eliminate the need for secondary surgeries required with nondegradable materials. In dentistry, FDM with PLA enables the fabrication of customized splints, temporary crowns, dentures and dental models, ensuring improved fit and patient comfort. PLA is also widely explored in tissue engineering scaffolds that promote bone and dental pulp regeneration. Despite these benefits, PLA has inherent limitations such as low mechanical strength and brittleness. FDM processing adds further challenges, including porous structures, weak interlayer bonding, limited resolution, warping and poor surface finish. Current research addresses these issues through fiber-reinforced PLA composites with additives like hydroxyapatite, surface modification strategies and process optimization involving parameters such as layer height and raster angle. For clinical translation, rigorous mechanical testing (tensile, impact, torsion) and biological evaluations (cytocompatibility, in vivo degradation) remain essential. Overall, PLA demonstrates immense potential for personalized biomedical solutions, although advancements in materials and process refinement are crucial for overcoming existing challenges. © 2025 Society of Chemical Industry.
