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At least 73 records · Page 4

Stent with expandable foam

A system comprising first, second, and third shape memory polymers (SMPs); wherein (a) the first SMP is a biodegradable open cell foam that includes a first channel; (b) the second SMP includes a second channel and is included in the first channel; (c) the foam is in a first state and is configured to expand to a second state, radially outward from the second foam, in response to thermal stimulus; (d) the third SMP is between the first and second SMPs and includes a stent having a first strut that includes the third SMP and a second strut that includes the third SMP; and (e) each of the first, second, and third SMPs is coupled to a wire.

Wilson, Thomas S.↗

Sustainable Polymer for Polyolefin Replacement (CRADA Final Report)

Sustainable Chemicals, LLC (Participant, Sust-Chem) develops renewable, biodegradable bioplastics for the replacement of large-volume petrochemical plastics such as polyethylene (PE) and polypropylene (PP). Participant’s patented bioplastics will find use in everyday items such as plastic bags, flexible containers, packaging, and toys and will address customers' ask for goods that are sustainable but don't cost a premium. Participants’ plastic comes from plant biomass and at the end of its lifecycle, is compostable or chemically recyclable. During the CRADA, Participant and Contractor will jointly refine the polymerization process used to make our bioplastic. Participant and Contractor will focus on technologies that are economically and industrially feasible, complete with full polymer characterization.

36 MATERIALS SCIENCE↗

Polymer-Grafted Cellulose Nanofibrils with Enhanced Interfacial Compatibility for Stronger Poly(lactic acid) Composites

Cellulose nanofibrils (CNFs) are a promising reinforcement for biodegradable composite matrices such as poly(lactic acid) (PLA), but they require commercially scalable drying methods that preserve their fibrillar morphology along with improved interfacial interactions with polymer matrices. In this work, a water-based grafting-through polymerization scheme to modify CNFs improved spray drying behavior and reinforcement capacity in PLA composites. All polymer modifications yielded CNFs with a more fibrillar morphology after spray drying, increasing specific surface area by up to 490% compared to unmodified CNFs, values similar to conventional freeze drying. Polymer-grafted CNFs in PLA composites improved the tensile strength by 16% at 20 wt % loading and stiffness by 22% at a 10 wt % loading with two different graft-polymer chemistries compared to unmodified CNF composites. Surface energy heterogeneity measurements of the reinforcements and PLA matrix were employed to understand the improvements in composite properties. Polymer modifications lowered the total surface energy of the CNFs, and calculated ratios of work of adhesion to work of cohesion suggested improved interfacial compatibility for four of the modified CNFs with PLA. Rheological oscillatory shear studies of the composites correlated solid-like melt behavior, as demonstrated by storage moduli dominance, with higher tensile strength. Thermal analysis of the composites revealed that excessive plasticization by the poly(oligoethylene glycol methyl ether methacrylate)-grafted sample potentially offset mechanical property improvements imparted by the more fibrillar morphology. This work provides an opportunity for large-scale manufacturing of CNF/PLA composites via an entirely aqueous modification scheme and industrially relevant spray drying process.

36 MATERIALS SCIENCE↗

Biodegradable waterborne polyurethane-urea dispersion adhesives with high biocontent

Non-biodegradable petroleum-based plastic wastes have become a leading environmental concern, and new efforts are underway to prepare biobased and biodegradable replacements. For this work, we have explored the preparation of adhesives suitable for use in consumer products, and here we report the development of waterborne, biodegradable adhesives from biobased monomers resulting in adhesives exceeding 70% biocontent. Using water as the polymer medium, viscosity challenges and the use of volatile organic solvents are avoided. Material properties of the polyurethane dispersions, resulting films, and laminates produced showed M w ranging between 56,000 and 124,000. Lastly, the biodegradability of films and laminates was evaluated. The resulting metrics indicate that the adhesives produced meet the desired mechanical and biodegradability targets, indicating that high renewability content solvent-free polyurethane dispersions are a viable solution for lamination adhesives.

36 MATERIALS SCIENCE↗

The developments in modifying functionality of lignin and its application in biocomposites

With the advancement of sustainable material innovations, renewable natural biopolymers are gradually replacing traditional metal and petroleum-based synthetic materials due to their environmental friendliness, biodegradability, and economic advantages. Lignin, the second most abundant natural aromatic polymer in the plant kingdom, has emerged as a key candidate raw material for the development of green polymer systems because of its unique phenylpropane unit network structure, high carbon content, and rich functional group characteristics. However, challenges such as the inherent structural complexity, chemical inertness, and uneven molecular weight distribution of lignin limit its direct application. By employing modification strategies such as chemical functionalization and physical regulation, researchers can precisely control its reactivity, thermal stability, and interfacial compatibility, enabling the preparation of high-performance lignin-based functional composites. Here, this paper systematically reviews the principles and methodological advancements in lignin's multi-dimensional modification technology. It analyzes the mechanisms by which various chemical and physical modification techniques enhance the mechanical properties, functional responsiveness, and environmental adaptability of materials, and discusses innovative applications in fields such as intelligent packaging, biomedical materials, and energy storage devices. Furthermore, this review addresses the key challenges encountered in the high-value transformation of lignin, with the aim of offering a theoretical framework and technical pathway for the transformative development of lignin from agricultural and forestry by-products to functional material platforms.

Functional composites↗

Quest for environmentally sustainable materials: A case for animal-based fillers and fibers in polymeric biocomposites

This review explores the potential of animal-based fillers and fibers as eco-friendly alternatives to conventional synthetic ones. Examining materials such as wool, silk, feather, hair and beak, the review elucidates their chemistry, structure, properties and sources, emphasizing biodegradability and renewability. It also discusses the compatibility of these materials with polymer matrices and their mechanical, acoustic and thermal performances. Further, the review critically analyzes environmental and ethical implications, presenting challenges and opportunities in the emerging field. By addressing ecological and performance aspects, it contributes to global efforts in fostering sustainability in materials science. Future research to address gaps and enhance the design, manufacture and application of animal-based reinforcements in various industries are clearly outlined at the end of the review.

36 MATERIALS SCIENCE↗

In-Silico Design of Next Generation Cellulose-Derived Packaging Materials (CRADA Final Report)

Developing sustainable solutions for single-use packaging is an important objective to combat the environmental crisis of plastics pollution. Most embodiments of cellulose-based packaging materials, including CellophaneTM, are completely biodegradable in both terrestrial and marine environments. However, petroleum-derived alternatives offer some performance advantages for metrics such as moisture barriers and mechanical properties. This project leverages molecular dynamics simulation to investigate how molecular modifications to cellulose-based polymer assemblies impact their material properties. An important performance criterion for the modified materials was to retain biodegradability; thus, modifications by naturally occurring, biodegradable additives were the focus of this study. Specifically, we developed models with xylan and lignin of varying monomeric compositions into the cellulose matrix. The mechanical properties were investigated by performing stress-strain simulations, and the water barrier and hydrophobicity were investigated by simulating the water contact angle. Our findings indicate that the incorporation of xylan into the cellulose matrix tends to increase the mechanical properties with an optimal loading of ~27 wt%. We also predict that orienting the nanoscale directionality of the xylan chains such that they are perpendicular to the cellulose fibrils will dramatically increase mechanical strength. In contrast, the incorporation of lignin tends to weaken the composite at all loadings investigated. Simulations of water contact angle predicted that coating polymers on the surface of the cellulose assembly creates a more hydrophobic surface than incorporating them throughout the matrix. Of the coatings investigated, lignin resulted in the most hydrophobic surface, followed by pectin and keratin, which both imparted modest increases in hydrophobicity. Future experimental work done by Futamura will focus on designing material prototypes to capitalize on the predictions of performance enhancement obtained from molecular modeling. While substantial progress was made by the simulations performed in this project, there still exists a vast parameter space that we were unable to investigate, including branching, functional group decoration, and degree of polymerization of polymer additives. However, the methods developed in this initial investigation will facilitate more rapid evaluation of the impact of molecular characteristics on the performance of biopolymer composite materials and thereby accelerate future materials discovery efforts in this area.

36 MATERIALS SCIENCE↗

Rapid biodegradation of microplastics generated from bio-based thermoplastic polyurethane

The accumulation of microplastics in various ecosystems has now been well documented and recent evidence suggests detrimental effects on various biological processes due to this pollution. Accumulation of microplastics in the natural environment is ultimately due to the chemical nature of widely used petroleum-based plastic polymers, which typically are inaccessible to biological processing. One way to mitigate this crisis is adoption of plastics that biodegrade if released into natural environments. In this work, we generated microplastic particles from a bio-based, biodegradable thermoplastic polyurethane (TPU-FC1) and demonstrated their rapid biodegradation via direct visualization and respirometry. Furthermore, we isolated multiple bacterial strains capable of using TPU-FC1 as a sole carbon source and characterized their depolymerization products. Finally, to visualize biodegradation of TPU materials as real-world products, we generated TPU-coated cotton fabric and an injection molded phone case and documented biodegradation by direct visualization and scanning electron microscopy (SEM), both of which indicated clear structural degradation of these materials and significant biofilm formation.

09 BIOMASS FUELS↗

Linear Viscoelastic Properties of Putative Cyclic Polymers Synthesized by Reversible Radical Recombination Polymerization (R3P)

Linear viscoelastic properties in both melt and solution states are reported for a series of poly(3,6-dioxa-1,8-octanedithiol) (polyDODT) made by reversible radical recombination polymerization (R 3 P) under conditions designed to produce linear (LDODT), cyclic (RDODT) and linear-cyclic mixtures (LRDODT). PolyDODT is amorphous (T g < -50 °C) and highly flexible (entanglement molecular weight M e,lin ≈ 1850 g/mol for LDODT). PolyDODT’s low T g and low M e,lin enable characterization over a wide dynamic range and a wide range of dimensionless weight-average molecular weight Z w = M w /M e,lin . Measurements at temperatures from -57 °C to 100 °C provide up to 18 deades of reduced frequency, which is necessary to characterize RDODT melts with Z w from 23 to 300. The two highest molecular weight polymers in the present RDODT series have such high M w (406k and 556k g/mol) that mass spectrometry, NMR spectroscopy, and even chemical assays for chain ends are unable to rule out up to 2 mol% linear contaminant. By studying the samples in solution (using dilution to reduce Z w ) we could compare their dynamics with those of previously established high-purity polystyrene (PS) rings (limited to Z w ≤ 13.6). RDODT solutions with Z w < 15 (concentrations <5wt% for RDODT-406k and 556k) have dynamic moduli G^* that accord with LCCC-purified PS rings in terms of the frequency dependence (including the absence of a plateau), the progression of shapes of G* as a function of Z w , and the linear scaling of their zero-shear viscosity η0 with M w . The shape of G* as a function of Z w for solutions of RDODT-406k and -556k also accord with lower M w RDODT melts (which have ≤ 1.3mol% linear contaminant). Thus, measurement of the linear viscoelastic properties of appropriate concentrations of high M w (>200k g/mol) putative cyclic polymers, in which linear chains evade spectroscopic detection, may provide an alternative means (though not fully proven) of validation of sample purity. When Z w > 15 (including all seven RDODT melts and eight of their solutions), G* has a rubbery plateau. This suggests that the onset of entanglement-like behavior in rings requires 4-5-fold greater Z w than is required for linear chains. Further, the plateau moduli of RDODT samples are indistinguishable from G N o of the corresponding LDODT (melt or matched-concentration solutions). In entangled linear polymers, the observation that G N o is independent of Z w follows from limitations on lateral fluctuations due to neighboring chains becoming independent of position along a given chain. The present results for RDODT suggest that this holds for sufficiently long endless chains, too. While the RDODT have the same G N o as entangled LDODT, when Z w > 60 the terminal relaxation, if reached at all, of RDODT extends to orders of magnitude lower frequency than an entangled linear polymer of the same Z w . Consequently, the viscosity of RDODT with Z w > 60 increases with Z w much more strongly than the 3.4-power observed for entangled linear polymers. Lastly, these novel polymers, with disulfide-linked backbone and broad relaxation time distribution may prove important in relation to biodegradable elastomers and materials with exceptional low-frequency dissipation, extending at least 12 decades below the onset of the rubbery plateau.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

The influence of molecular design on structure–property relationships of a supramolecular polymer prodrug

Supramolecular self-assemblies of hydrophilic macromolecules functionalized with hydrophobic, structure-directing components have long been used for drug delivery. In these systems, loading of poorly soluble compounds is typically achieved through physical encapsulation during or after formation of the supramolecular assembly, resulting in low encapsulation efficiencies and limited control over release kinetics, which are predominately governed by diffusion and carrier degradation. To overcome these limitations, amphiphilic prodrugs that leverage a hydrophobic drug as both the therapeutic and structure-directing component can be used to create supramolecular materials with higher loading and controlled-release kinetics using biodegradable or enzymatically cleavable linkers. Here, we report the design, synthesis, and characterization of a library of supramolecular polymer prodrugs based on poly(ethylene glycol) (PEG) and the proregenerative drug 1,4-dihydrophenonthrolin-4-one-3-carboxylic acid (DPCA). Structure–property relationships were elucidated through experimental characterization of prodrug behavior in both the wet and dry states using scattering techniques and electron microscopy and corroborated by coarse-grained modeling. Molecular architecture and the hydrophobic-to-hydrophilic ratio of PEG–DPCA conjugates strongly influenced their physical state in water, ranging from fully soluble to supramolecular spherical assemblies and nanofibers. Molecular design and supramolecular structure, in turn, were shown to dramatically alter hydrolytic and enzymatic release and cellular transport of DPCA. In addition to potentially expanding therapeutic options for DPCA through control of supramolecular assemblies, the design principles elaborated here may inform the development of other supramolecular prodrugs based on hydrophobic small-molecule compounds.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Mechanically robust and reprocessable imine exchange networks from modular polyester pre-polymers

Covalent adaptable networks (CANs) containing reversible cross-links impart recyclability to thermoset materials without sacrificing their desirable properties (e.g. high tensile strength and solvent resistance). In addition to thermal recycling, the sustainability of these materials may be further improved by incorporating bio-sourced monomers or by enabling alternate end-of-life fates, such as biodegradation or recovery of starting materials. The alternating ring-opening copolymerisation of epoxides and cyclic anhydrides permits the modular synthesis of polyester pre-polymers that can then be cross-linked to form dynamic imine-linked networks. In this work, we report the synthesis and characterisation of five imine exchange polyester CANs with varied cross-linking densities and pre-polymer architectures. While the materials exhibit characteristic thermoset properties at service temperatures, differences in pre-polymer architecture produce distinct dynamic mechanical effects at elevated temperatures. The networks may be thermally reprocessed with full recovery of their tensile strengths and cross-linking densities, dissociated to pre-polymer, or hydrolytically degraded.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Sandwich-structured paper composite with water and oil resistance for food packaging and tableware applications

The growing environmental challenges posed by plastic waste from disposable tableware highlight the urgent need for sustainable alternatives. Traditional plastics decompose over centuries, generating microplastics that threaten ecosystems and human health. While lignin has emerged as a promising material for plastic replacement, its inherent dark brown color and processing challenges in paper-based products have limited its application, particularly in food-contact materials. Here, to address these limitations, we have developed biodegradable sandwich-structured paper composites comprising parchment paper as surface layers and a lignin-polymer core with polyvinyl alcohol (PVA) and polylactic acid (PLA). This innovative structure eliminates the need for binders, minimizing potential food contamination, and enables direct application as packaging or molded tableware. Lignin micro- and nano-particles (LMNP) enhances durability and provides natural water and oil resistance without harmful additives, such as per- and polyfluoroalkyl substances (PFAS), while PVA and PLA improve the composite's tenacity. The resulting material, composed of 65 wt% lignin, demonstrates excellent water and oil resistance, with no penetration exceeding 1 h, and exhibits enhanced tensile strength (45 MPa), making it a viable and eco-friendly alternative for disposable tableware.

36 MATERIALS SCIENCE↗

Effect of the Lignin Structure on the Physicochemical Properties of Lignin-Grafted-Poly(ε-caprolactone) and Its Application for Water/Oil Separation

Lignin-grafted poly(ε-caprolactone) copolymers (lignin-g-PCLs) have shown wide application potentials in coatings, biocomposites, and biomedical fields. However, the structural heterogeneity of lignin affecting the structures and properties of lignin-g-PCL has been scarcely investigated. In this study, kraft lignin is fractionated into four precursors, namely, F ins , F1, F2, and F3, with declining molecular weights and increased hydroxyl contents. Lignin-g-PCLs are synthesized via ring-opening polymerization of ε-caprolactone with lignin and characterized by GPC, FTIR, 1 H and 31 P NMR, DSC, TGA, and iGC. The mechanical properties, UV barrier, and enzymatic biodegradability of the lignin-g-PCLs are evaluated. Results show that lignin with a higher molecular weight and aliphatic OH favors the copolymerization, leading to lignin-g-PCLs with longer PCL arms. Moreover, lignin incorporation improves the thermal stability, hydrophobicity, and UV-blocking ability but reduces the lipase hydrolyzability of the copolymers. We also demonstrated that the lignin-g-PCL-coated filter paper could successfully separate chloroform–, petroleum ether–, and hexane–water mixtures with an efficiency up to 99.2%. The separation efficiency remains above 90% even after 15 cycles. The structural differences of copolymers derived from the fractionation showed minimal influence on the separation efficiency. This work provides new insights into lignin-based copolymerization and the versatility of lignin valorization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Functional Filaments: Creating and Degrading pH-Indicating PLA Filaments for 3D Printing

With the rapid pace of advancements in additive manufacturing and techniques such as fused filament fabrication (FFF), the feedstocks used in these techniques should advance as well. While available filaments can be used to print highly customizable parts, the creation of the end part is often the only function of a given feedstock. In this study, novel FFF filaments with inherent environmental sensing functionalities were created by melt-blending poly(lactic acid) (PLA), poly(ethylene glycol) (PEG), and pH indicator powders (bromothymol blue, phenolphthalein, and thymol blue). The new PLA-PEG-indicator filaments were universally more crystalline than the PLA-only filaments (33–41% vs. 19% crystallinity), but changes in thermal stability and mechanical characteristics depended upon the indicator used; filaments containing bromothymol blue and thymol blue were more thermally stable, had higher tensile strength, and were less ductile than PLA-only filaments, while filaments containing phenolphthalein were less thermally stable, had lower tensile strength, and were more ductile. When the indicator-filled filaments were exposed to acidic, neutral, and basic solutions, all filaments functioned as effective pH sensors, though the bromothymol blue-containing filament was only successful as a base indicator. The biodegradability of the new filaments was evaluated by characterizing filament samples after aging in soil and soil slurry mixtures; the amount of physical deterioration and changes in filament crystallinity suggested that the bromothymol blue filament degraded faster than PLA-only filaments, while the phenolphthalein and thymol blue filaments saw decreases in degradation rates.

36 MATERIALS SCIENCE↗

PolyDODT: a macrocyclic elastomer with unusual properties

The effect of reaction conditions on the structure of poly(3,6-dioxa-1,8-octanedithiol) (polyDODT) made by Reversible Radical Recombination Polymerization (R3P) using triethylamine (TEA), H 2 O 2 and air was investigated. 800 MHz (1 and 2D) NMR was used to investigate the polymer structures. Sensitivity analysis provided direct evidence for high purity cyclic polyDODT up to M n ~ 100 000 g mol –1 . Here, comparative analysis by High Resolution Multidetector Size Exclusion Chromatography (SEC) using integrated data showed that the cycles had lower viscosity and were more compact (both for R g and R h ) than linear samples of similar molecular weight. However, differential data revealed unusual behavior. While lower molecular weight cyclic polymers eluted later and had lower intrinsic viscosity than their linear counterparts at the same molecular weight, at higher molecular weights the polymers showed strange behavior: both the diffusion coefficient measured by Quasielastic Light Scattering (QELS) and Mark–Houwink–Sakurada plots of intrinsic viscosity for linear and cyclic polyDODT were found to converge. R3P, an aqueous based “green” method is capable of producing polymers at the 10–100 g scale in the lab, which will allow more detailed studies of this new class of biodegradable elastomers so further experimentation can be performed to elucidate the reasons for the unusual findings.

36 MATERIALS SCIENCE↗

Polyhydroxyalkanoates in emerging recycling technologies for a circular materials economy

Circular polymer systems, specifically polyesters operating through chemical and biological technologies, are approaching a critical moment of industrial adoption and scale-up feasibility. At the same time, polyhydroxyalkanoate (PHA) production, scale-up, and resulting material development is converging toward commodity applications. The current PHA end-of-life philosophy, however, focalizes leveraging inherent biodegradability to circumvent plastic waste accumulation. If indeed a substantial replacement of incumbent single-use plastics with PHA alternatives is to be met in commercial manufacture, we emphasize the importance of linking PHA development with feasible polymer recycling technologies. In other words, a PHA materials economy is significantly more carbon- and cost-favorable when efficient mechanical (reprocessing), chemical (deconstruction, depolymerization), or biological (enzymatic) recycling is prioritized over biodegradation or composting. In this perspective, we discuss strategies for PHA recyclable-by-design principles, guidable by developing machine learning tools, as well as material compatibility with closed-loop recycling technologies. Additionally, we posit compelling life-cycle assessment incentives for adopting polymer reclamation over competing pathways. Ultimately, we hope this narrative further inspires the alignment between PHA design with growing calls for a circular material economy.

36 MATERIALS SCIENCE↗

Green chemistry design in polymers derived from lignin: review and perspective

The use of lignin for material and chemical applications has gained interest in recent times due to the environmental focus on using biomass for renewable materials as well as the motivation to valorize lignin as part of an integrated biorefinery. While a wealth of publications can be found for lignin-derived materials, and several reviews can be found on the topic, there are no reviews that outline and critically assess the sustainability of these protocols based on the criterion of the 12 Principles of Green Chemistry. This review assesses the literature for lignin- derived polymers over the past 20 years and highlights attempts to use biobased accompanying reagents, green solvents or solvent-less protocols, reports that replace traditionally toxic precursors (e.g. diisocyanates for polyurethanes), use mild conditions, valorize additional waste streams and prepare materials particularly biodegradable or recyclable. Here, the following work is a comprehensive and critical assessment of the green and sustainable nature of the state-of-the art of lignin-derived polymers (polyurethane, polyester, epoxy, phenolic resin, and others) utilizing actual biomass in the synthetic protocol. Each section of this review highlights and assesses published protocols that use a particularly green approach in one or more steps of the synthetic sequence. While many reports still contain traditional petroleum-derived and toxic methods along with more sustainable methods, the outline of all such green methods is able to create a landscape amidst lignin-derived polymer synthesis that points the way toward safer and more environmentally friendly materials.

36 MATERIALS SCIENCE↗

Multiscale Modeling and Experimental Insights into High-Temperature Soil Biodegradation Dynamics of Semi-Crystalline Poly(Lactic Acid) Nonwoven Fabrics

This study investigates the biodegradation of semi-crystalline poly(lactic acid) (PLA) nonwovens (NWs) in soil at 58 °C using both experimental and mathematical modeling approaches. The model utilizes a system of parabolic diffusion-reaction partial differential equations (PDEs) to elucidate chemical transformations over time and in space. It accounts for phenomena such as the diffusion of water and lactic acid monomers through the polymer matrix and into the surrounding soil, along with their microbial breakdown. It also accounts for the initial PLA crystallinity and predicts its evolution in time. The model is solved numerically for a single filament, and the results were used to shed light on PLA NW transformations observed in soil over a 180-day incubation period. Various characterization techniques, including scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and Raman spectroscopy, were employed to assess morphological changes, crystallinity, and molecular changes in the NWs throughout the experiment. By comparing the experimental data with the model predictions, the hydrolysis rate coefficient was found to be 3.37 × 10 -7 s -1 , while the rate of microbial degradation of lactic acid monomers was faster, of the order of 9.63 × 10 -7 s -1 . The findings highlight the significant role of crystallinity in the biodegradation process. The PLA degradation ceases when no amorphous material remains, and the crystallinity reaches 0.8, as observed in the experiments by day 120. Furthermore, this research contributes to a deeper understanding of PLA biodegradation dynamics and offers insights for effectively managing biodegradable materials in environmental settings.

Diffusion−reaction modeling↗