Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “biobased polymer”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 19 records

Effects of PLA/PHB Blend Ratio and Wood Flour Loading on the Melt Rheology and Thermomechanical Properties of Biobased Polymer Composites

The development of sustainable, biobased polymer composites is crucial for reducing supply chain dependence on fossil fuels. A major challenge lies in understanding and predicting the processability of these sustainable material alternatives, which directly impacts large-scale manufacturing. Here, this study systematically investigates the effect of poly(lactic acid) (PLA)/polyhydroxybutyrate (PHB) blend ratios and wood flour (WF) loadings on the thermal, rheological, and mechanical properties of the composites. Composites were prepared via melt compounding and characterized by using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), oscillatory shear melt rheology, tensile testing, and scanning electron microscopy. Results showed that increasing the PHB content lowered the glass transition temperature, while higher PHB and WF loadings decreased thermal stability. Complex viscosity decreased with increasing PHB in 0 and 10% WF, whereas it increased in 20% and 30% WF for PHB-rich blends (80/20 and 70/30 PLA/PHB) due to stronger filler interactions with flexible PHB chains. At 30% WF, PHB-containing composites also showed elastic dominance with G′ higher than G″. This behavior was confirmed by van Gurp–Palmen plots, where the phase angle decreased with increasing PHB and WF loadings. WF addition also shifted Cole–Cole plots away from semicircular terminal relaxation, while time–temperature superposition validity was maintained, confirming that polymer chain dynamics continue to dominate melt behavior. Young’s modulus increased with WF loading, while tensile strength and toughness decreased due to weaker interfacial adhesion between the matrix and the filler. Interestingly, 10% WF systems containing PHB exhibited the highest toughness among all of the filled systems, indicating synergistic reinforcement from WF fillers and PHB-induced ductility. Overall, melt rheology effectively captured the internal structure and stiffness of the composites as the formulation changed, reinforcing the concept that the PLA/PHB ratio and WF content can be tuned to adjust melt elasticity and balance mechanical property trade-offs for targeted applications.

melt rheology↗

Engineering Innovations, Challenges, and Opportunities for Lignocellulosic Biorefineries: Leveraging Biobased Polymer Production

Alternative polymer feedstocks are highly desirable to address environmental, social, and security concerns associated with petrochemical-based materials. Lignocellulosic biomass (LCB) has emerged as one critical feedstock in this regard because it is an abundant and ubiquitous renewable resource. LCB can be deconstructed to generate valuable fuels, chemicals, and small molecules/oligomers that are amenable to modification and polymerization. However, the diversity of LCB complicates the evaluation of biorefinery concepts in areas including process scale-up, production outputs, plant economics, and life-cycle management. We discuss aspects of current LCB biorefinery research with a focus on the major process stages, including feedstock selection, fractionation/deconstruction, and characterization, along with product purification, functionalization, and polymerization to manufacture valuable macromolecular materials. We highlight opportunities to valorize underutilized and complex feedstocks, leverage advanced characterization techniques to predict and manage biorefinery outputs, and increase the fraction of biomass converted into valuable products.

59 BASIC BIOLOGICAL SCIENCES↗

Biobased Semi-Interpenetrating Polymer Networks of Poly(ε-caprolactone) and Epoxidized Soybean Oil with Nanoscale Morphology, Shape-Memory Effect, and Biocompatibility

Creating biobased polymer blends with outstanding properties, nanoscale morphology, shape-memory capability, and biocompatibility is very crucial and requires a fundamental understanding of the phase behavior, macromolecular structure, and biological compatibility of the polymer blends with living cells. It is very critical to understand the complex relationships among the polymer structure, morphology, and performance of multifunctional smart materials under conditions that they are likely to encounter during use, particularly in biomedical applications. Biobased semi-interpenetrating polymer networks of poly(ε-caprolactone) and epoxidized soybean oil with nanoscale morphology have been successfully synthesized via in situ cationic polymerization and compatibilization in a homogeneous solution. Varies analytical and characterization techniques, such as Fourier transform infrared spectroscopy, differential scanning calorimetry, dynamic mechanical analysis, transmission electron microscopy, X-ray scattering, cell toxicity, and shape-memory effects (SMEs), have been employed to understand the structure–properties relationship of these smart, biobased nanostructured polymer blends. The synthesized nano blends were nontoxic or biocompatible and supported attachment of human vein endothelial cells, showing their potential use in biomedical applications. The current versatile, low-cost strategy for synthesizing the nanoscale morphology of semi-interpenetrating polymer networks with SMEs and biocompatibility should be widely applicable for polymer systems. This study is also considered as a continuation to our efforts in the area of biobased polymers to develop innovative technologies to transform natural resources into smart multifunctional materials for a wide range of applications, including coatings, adhesives, and medical devices.

36 MATERIALS SCIENCE↗

Biobased Poly(dodecylene Furanoate) with Inherent Advantages in Performance and Circularity

Biobased polymers are gaining traction toward more sustainable flexible-film packaging, yet overcoming trade-offs between their performance properties and end-of-life (EoL) options still remains a challenge. Here, it is shown that biobased poly(dodecylene 2,5-furanoate) (PDDF), synthesized via both step-growth polycondensation and chain-growth ring-opening polymerization methods, exhibits advantages not only in gas barrier properties but also in EoL options due to its biodegradability and closed-loop chemical circularity. Specifically, PDDF displays significantly lower oxygen and carbon dioxide permeability than commercial poly(butylene adipate-co-terephthalate) (PBAT) and linear low-density polyethylene , alongside a markedly higher modulus (by ≈3 ×) and reduced water vapor transmission rate compared to PBAT. This superior performance is attributed to the inherently rigid, polar, H-bonding furan rings that enhance chain interaction, packing and crystallinity and thus reduce free volume impeding gas diffusion, while the long hydrophobic dodecylene segments inhibit water permeation. Furthermore, PDDF can be recycled back to its cyclic monomer by base-catalyzed depolymerization or diester and diol monomers by simple methanolysis. These superior barrier properties, coupled with biodegradation and closed-loop circularity, highlight the potential of the biobased PDDF as a more sustainable alternative for packaging.

Poly(dodecylene 2,5-furanoate) (PDDF)↗

Designing a Block Copolymer Membrane for Selective Transport of Lactic Acid from Aqueous Mixtures

We report the design and synthesis of a triblock copolymer-based membrane for enabling selective transport of lactic acid from aqueous solutions. This is relevant to the production of polylactic acid, one of the few biodegradable and biobased polymers with sufficient mechanical strength for practical applications. The end blocks are positively charged with negatively charged lactate counterions. The middle block is polybutadiene (PBD). Due to microphase separation, the charged blocks form channels for transporting lactic acid. The mechanical integrity of the membrane is controlled by cross-linking the PBD block. Transport of lactic acid and water across the membrane was studied by placing the membrane between two chambers, a feed chamber containing aqueous lactic acid solutions, and a receiving chamber containing pure water. The lactic acid concentration in the receiving chamber was monitored as a function of time using conductivity, HPLC, and NMR. The corresponding flux of water from the receiving chamber to the feed chamber was measured using an NMR-based approach. The lactic acid and water permeabilities through our membrane were (1.12 ± 0.05) × 10–8 and (8.58 ± 0.75) × 10–9 cm2 s–1. To our knowledge, there are no reports of lactic acid permeabilities through any membrane in the literature. The separation factor of our membrane, αLA/water, 1.305 ± 0.123, is comparable to that of membranes used for selective transport of ethanol, despite the fact that lactic acid is a much larger molecule than ethanol. Selective transport of lactic acid in our membrane is governed mainly by differences in solubility; lactic acid is 18 times more soluble in the membrane than water.

Jana, Rounak↗

Lignin-Derived Methoxyterephthalates for Performance-Advantaged Polymers and Plasticizers

Lignin-derived aromatic carboxylic acids can be produced from oxidative catalytic processes and are promising building blocks for performance-advantaged bioproducts that leverage their inherent heteroatom functionalities. Here, we synthesize 2-methoxyterephthalate and 2,6-dimethoxyterephthalate derivatives by electrochemical carboxylation of guaiacyl- and syringyl-derived lignin monomers obtained from the oxidative deconstruction of lignin. These methoxylated terephthalates are evaluated as comonomers in poly(ethylene terephthalate) (PET) and as plasticizers that could replace petrochemically-derived isophthalate and phthalate, respectively. Specifically, we copolymerize 2-methoxy- and 2,6-dimethoxyterephthalate with dimethyl terephthalate to form several PET copolymers, both of which enable the properties of PET to be tuned, with an incorporation beyond 25% producing amorphous polyesters. At 10 mol % loading in the copolymers, we demonstrate that the bioderived comonomers exhibit comparable behavior to isophthalic acid, a commonly used comonomer in PET, by lowering the crystallinity and melting temperature. Moreover, methoxyterephthalate esters (2-ethylhexyl and butyl) are compared to phthalate and terephthalate ester counterparts used as poly(vinyl chloride) (PVC) plasticizers. The bioderived plasticizers are comparable to the petroleum-derived incumbents in reducing the glass transition temperature and increasing the thermal stability of PVC. Furthermore, the dimethoxyterephthalic esters are expected to have an extended lifetime in the polymer matrix due to their lower volatility and lower diffusion coefficients calculated by molecular dynamic simulations. These results demonstrate that the isophthalate and phthalate components in polyesters and plasticizers, respectively, could be substituted with biobased methoxyterephthalate derivatives.

09 BIOMASS FUELS↗

Designing Recyclable Biomass-Based Polyesters (Final Technical Report)

This project successfully demonstrated the production of sustainable polyesters from biomass-derived monomers, offering properties on par with or superior to fossil-based plastics such as LLDPE and PBAT. Using renewable chemical platforms like furfural and HMF, we synthesized over eight novel monomers and nearly 100 aliphatic-aromatic polyesters. Among these, PPeAT and PDDF emerged as highly promising candidates for flexible packaging applications, exhibiting excellent mechanical performance, tunable thermal properties, and enhanced barrier characteristics. Key advances included the development of ring-opening polymerization strategies using cyclic monomer intermediates to produce high molecular weight materials with excellent control. The resulting polymers achieved biobased content of at least 44 wt.%. We also implemented chemical recycling via catalytic methanolysis, recovering over 90% of monomers from PPeAT at semi-pilot scale. This supports a circular economy approach by enabling material reuse without performance loss. Techno-economic and life cycle assessments confirmed that these polyesters can reduce greenhouse gas emissions by up to 50% compared to petroleum-derived alternatives. Favorable mechanical properties may further reduce material demand, and cost competitiveness was demonstrated under specific market conditions. Feedstock cost and environmental footprint were identified as primary levers for future optimization. In summary, the project met or closely approached all technical targets, including biodegradability, strength, and processing compatibility. While minor issues such as color and melting point variation remain, the results strongly support continued development and scale-up of these sustainable materials.

09 BIOMASS FUELS↗

Force-Triggered, Biobased Sealants for Prefabricated Building Components: Toward Improved Efficiency and Performance

The prefabricated building construction industry has made extensive progress in expediting the manufacture of prefabricated components at off-site plants. However, the sealing of joints between these components, which is crucial to ensuring the weatherproofing of the assembly, still represents a labor-intensive, on-site effort that relies on the manual installation of tapes and caulks. Here, to reduce work at the jobsite and improve the airtightness and waterproofness of building envelopes, we developed a sealant that can be installed at the plant on prefab components and have the curing reaction triggered at the jobsite by using microencapsulation technology to separate the reactive agents. A series of force-triggered, high-strength, and fast-curing sealants derived from biobased feedstocks were developed, which consist of a biobased epoxy agent encapsulated in a polymer shell, embedded in a biobased amine curing agent. The shell of the microcapsules allows an effective separation of the reactive species in the one-part sealant, allowing shelf stability to an otherwise fast-curing system as well as improving the hydrophobicity of the whole system. When force activates and breaks the microcapsules, the highly reactive epoxy and amine mix and cure, exhibiting peel strength values of up to 143 ppi (pounds per inch). The hydrophobicity of the sealants allows them to retain up to 94% of the original peel strength after complete submersion in water for 24 h, showcasing the water resistivity of the sealant system. The open-air shelf stability of the sealant complex is demonstrated by the obtention of peel strength values of ∼16 ppi when triggering the curing reaction even after being exposed 8 months to open air and humidity. The successful on-demand triggering of curing reactions and the shelf stability provide efficacy of these force-triggered sealants for installation on prefabricated components, storage for months prior to delivery, and assembly at a jobsite. These force-triggered biobased sealants for prefabricated buildings can result in lower installation time and cost and better performance than tapes and caulks at the jobsite.

biobased↗

Biodegradable High-Molecular-Weight Poly(pentylene adipate- co -terephthalate): Synthesis, Thermo-Mechanical Properties, Microstructures, and Biodegradation

Poly(pentylene adipate-co-terephthalate) (PPAT) is a promising biobased and biodegradable polymer that can replace polyethylene in flexible packaging films where biodegradability is desired. High-molecular-weight (100K–145 KDa) aliphatic–aromatic polyester PPAT was successfully synthesized, and the effects of reaction conditions on molecular weight were reported. PPAT polyesters were characterized for polymer compositions, number-average unit length, thermal transitions, and rheological properties. PPAT compression-molded films were characterized for crystallinity and tensile properties to correlate micro- and macroproperties. PPAT compression-molded films exhibited up to a 76% higher tensile modulus than compression-molded films from poly(butylene adipate-co-terephthalate) (PBAT), making PPAT films potentially comparable with compression-molded films from linear low-density polyethylene (LLDPE). Finally, PPAT is biodegradable in soil and freshwater environments with estimated 90% biodegradation times of 504–580 and 604–845 days, respectively, while PBAT takes 971 days in soil and 395 days in freshwater.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Closed‐Loop Recycling of Poly(pentylene Adipate‐ co ‐Terephthalate) via Amine‐Catalyzed Methanolysis

Advancing circularity through effective chemical recycling strategies is essential for enabling the sustainable use of emerging biodegradable polyesters in film applications. In this context, poly(pentylene adipate-co-terephthalate) with a 40/60 adipate-to-terephthalate ratio (PPeAT60), a significantly stiffer and partially biobased copolyester recently reported by our team, offers improved mechanical performance and processability compared to commercial poly(butylene adipate-co-terephthalate), while providing a platform to evaluate advanced recycling approaches for film applications. Here, this study describes depolymerization of PPeAT60 through amine-catalyzed methanolysis, followed by the repolymerization of the recovered monomers. The resulting repolymerized material exhibited a molar mass distribution, chemical structure, and thermal stability comparable to the virgin polymer, confirming the technical feasibility of the methanolysis-based recycling route. Both polymers displayed nearly identical melting, glass transition, and decomposition temperatures, crystallinity, and modulus, demonstrating full structural and mechanical reproducibility after recycling. Variations in crystallization kinetics, elongation at break, and barrier properties likely arise from trace impurities (<1%) introduced during processing acting as nucleating and stress-inducing agents. Overall, these results demonstrate that PPeAT60 retains its key properties after chemical recycling, establishing methanolysis as a promising platform for recycling of this partially biobased polymer that may be able to replace both conventional polyolefins and PBAT in flexible packaging applications.

09 BIOMASS FUELS↗

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↗

Tunable and Degradable Dynamic Thermosets from Compatibilized Polyhydroxyalkanoate Blends

Polyhydroxyalkanoates (PHAs) are versatile, biobased polyesters that are often targeted for use as degradable thermoplastic replacements for polyolefins. Given the substantial chemical diversity of PHA, their potential as cross-linked polymers could also enable similar platforms for reversible, degradable thermosets. In this work, we genetically engineered Pseudomonas putida KT2440 to synthesize poly(3-hydroxybutyrate-co-3-hydroxyundecenoate) (PHBU), which contains both 3-hydroxybutyrate and unsaturated 3-hydroxyundecenoate components. To reduce the brittleness of this polymer, we physically blended PHBU with the soft copolymer poly(3-hydroxydecanonate-co-3-hydroxyundecenoate) in mass ratios of 1:3, 1:1, and 3:1. Upon observing varying degrees of immiscibility by scanning electron microscopy, we installed dynamic boronic ester cross-links via thiol–ene click chemistry, which resulted in compatibilized dynamic thermoset blends ranging in hard, medium, and soft rubber or elastomer thermomechanical profiles. These dynamic thermoset blends were subjected to controlled biological degradation experiments in freshwater conditions, achieving timely mass loss despite the cross-linked architectures. Overall, this work highlights a two-component platform for the production of degradable and reprocessable dynamic thermoset blends suitable for several classes of cross-linked polymer technologies from tailored, biological PHA copolymers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Analytical Tools to Assess Polymer Biodegradation: A Critical Review and Recommendations

Many petroleum-derived plastic materials are highly recalcitrant and persistent in the environment, posing significant threats to human and ecological receptors due to their accumulation in ecosystems. In recent years, research efforts have focused on advancing biological methods for polymer degradation. Enzymatic depolymerization has emerged as particularly relevant for biobased plastic recycling, potentially scalable for industrial use. Biodegradation involves adsorption to the plastic solid surface, followed by an interfacial reaction, resulting in cleavage of bonds of polymer chains exposed on the surface. Here, widely varying substrate-specific kinetics are observed, with the polymer’s properties possessing a significant impact on the rate of this interfacial catalysis. Thus, there is a critical need for sensitive and accurate characterization of the material surface during and after interfacial depolymerization to fully understand the reaction mechanisms. Here, we provide a critical review of a range of techniques used in the analysis of material surfaces to characterize the chemical, topological, and morphological features relevant to the study of enzymatic biocatalysis, including microscopy techniques, spectroscopic techniques (e.g., X-ray diffraction analysis, Fourier transform infrared attenuated total reflectance spectroscopy, and mass spectrometry detection of analytes associated with degradation). Techniques for evaluation of surface energy and topology in their relevancy for sensitive detection of biological surface modifications are also discussed. In addition, this paper provides an overview of the strengths of these techniques and compares their performance in both sensitivity and throughput, including emerging techniques, which can be useful, particularly for the rapid analysis of the surface properties of polymeric materials in high-throughput screening of candidate biocatalysts. This research serves as a starting point in selecting and applying appropriate methodologies that provide direct evidence to the ongoing biotic degradation of polymeric materials.

Colachis, Matthew↗

Enabling Partnership between South Carolina and NREL for Advancing Opportunities in Plastics Recycling Research (EPSCOR for Plastics Recycling)

Proposal Objectives: 1. Utilize depolymerization/fractionation techniques to recover highly processable and reactive feedstocks for polymer synthesis from lignin. 2. Synthesize lignin‐derived non‐isocyanate polyurethane, epoxy, and polyamide using non‐ toxic, biobased route designed for chemical recycling. Characterize resulting materials. 3. Design a high‐yielding chemical recycling process for as‐synthesized materials yielding usable building blocks for many generations of polymer synthesis. 4. Optimize chemical recycling of PET waste for the synthesis of lignin‐based polymers. Compare properties to commercial materials. 5. Optimize reaction conditions and recycling steps to facilitate enhanced sustainability of the synthetic steps and final properties of materials. 6. Complete a lifecycle assessment of lignin utilization and chemical recycling to compare their environmental performance to that of materials produced from virgin material. Identify hot spots and benefits using the chemical recycling process.

36 MATERIALS SCIENCE↗

Biobased chemical recycling: aminolysis of PET using renewable reagents and monomers to synthesize new semi-aromatic polyamides

Chemical recycling of PET is a method of depolymerizing polymer chains to monomeric components enabling the synthesis of second-generation materials with virgin-like quality. Commercial chemical recycling techniques rely upon high pressure methanolysis to create precursors capable of synthesizing a second-generation PET resin. However, despite the circular approach of methanolysis, a product with a very short lifespan and similar value is created. The approach of the current study is to utilize aminolysis as an ambient pressure technique to create precursors for higher value materials with longer lifespans to address the current crisis in plastic waste. Semi-aromatic polyamides (SAP) are desired in this circumstance because of their high melting point and heat resistance combined with good melt-processability similar to aliphatic polyamides. In this study SAPs were synthesized using precursors recovered from the aminolysis of PET employing biobased diamines and dicarboxylic acids. While aminolysis has been explored in previous studies, this work investigated the use of biobased components from castor oil: decamethylene diamine during recycling and sebacic acid during polymerization. Polymer synthesis resulted in the formation of SAPs similar to polyphthalamides (PPA) with novel structures given the aromatic portion from terephthalic acid (TPA) and aliphatic portion from the diamines and diacids. The synthesized materials exhibited excellent thermal stability with high glass transition temperatures. Novel polymers were created with varying aliphatic chain length to understand fundamental parameters needed to produce a valuable polymer from post-consumer waste.

High performance Applications↗

Thermoplastic Polymer from Lignin: Creating an Extended Polyamide Network through Reactive Kraft Lignin Derivatives

Thermoplastic polymers have many desirable properties for consumer applications and are complemented by efficient thermal processing techniques, reducing the cost of manufacturing. Lignin exists as an immense biobased carbon source but has largely been researched for its use in thermoset materials due to its own cross-linked, polyfunctional nature. In this study, a new reaction design is employed to create a thermoplastic polyamide network incorporating lignin that is tested to be 99% biobased carbon by radiocarbon analysis. Chemical analysis reveals the nature of lignin incorporation based on chain extension and cross-linking models. The thermal and rheological properties of the new polymers are thoroughly investigated to demonstrate the higher melt-strength capability of the lignin-based polymers facilitating their use in modern processing equipment. This analysis results in finding an optimal lignin loading ratio in the polymer composition reflected by improved tensile strength and stiffness. The results point to a promising polymer design for applying industrial kraft lignin in high-value thermoplastic polymer applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hemp fiber reinforced dual dynamic network vitrimer biocomposites with direct incorporation of amino silane

Natural fiber composites are inexpensive and renewable alternatives to traditional fiber reinforced polymers (FRPs). However, existing natural fiber composites primarily rely on petrochemical based thermosetting matrices, which are difficult to recycle due to their stable crosslinked network structures. To address this challenge, it is desirable to develop natural fiber composites with inherently recyclable biobased matrices. In this study, we developed a dual dynamic network vitrimer matrix from hempseed oil and limonene derivatives and demonstrated its application in hemp fiber reinforced composites. To improve the weak interface between hemp fiber and the polymer matrix, a common challenge in the realm of natural fiber composites, we directly incorporated amino silane into the vitrimer matrix. The amino silane participated in the polymer network, increasing the crosslink density and toughening the matrix, as evidenced by a significantly improved impact strength from 3.5 kJ/m 2 to 10.3 kJ/m 2 . Moreover, the incorporation of amino silane resulted in a lower water absorption by 11% in 7-day soaking for the composites, demonstrating improved fiber/matrix interfacial interaction. Furthermore, our biobased vitrimer matrix exhibits both imine and hydroxy-ester dynamic bonds, which enable the recycling of the biocomposite through a mild and cost-effective aminolysis process (100°C, 3h, ambient pressure). The decomposed polymer matrix was successfully reused as a polyol for polyurethane adhesives, and the surface morphology of recovered hemp fibers was analyzed and compared with that of the original fibers. Furthermore, these findings will help broaden the use of vitrimers for practical natural fiber composite applications, raise awareness of the problem of recycling natural fiber composite waste, and shed light on the interfacial challenge of natural fiber reinforced vitrimer composites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗