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At least 19 records

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

Marine Toxicity, Biodegradability, and Rolling-Sliding Tribological Performance of Ionic Liquid-Enhanced Environmentally-Acceptable Lubricants for Tidal Turbomachinery

Environmentally acceptable lubricants (EALs) are increasingly being recognized in many fields including waterpower, hydraulics, water transport, agricultural machinery, offshore wind turbines, etc. Specifically, high-performance EALs are demanded for tidal turbomachinery to ensure high efficiency and reliability and avoid the significant risk of direct contamination of the marine ecosystem upon leaks. Here we report a new development of ionic liquid (IL)-enhanced EALs for tidal energy. One short-chain phosphonium phosphate and one short-chain ammonium phosphate ILs were used as the candidate additives and the IL-containing EALs demonstrated significantly improved lubricating performance, much lower toxicity, and increased biodegradability compared with commercial baselines. Specifically, in a rolling-sliding test simulating the operation of a model tidal turbine gearbox bearing, an EAL containing the ILs at a 0.5 wt % concentration demonstrated 40% lower friction, 45% less wear loss, substantially reduced rolling contact fatigue-induced surface damage, and one order of magnitude lower vibration noise compared with a commercial gear oil. In an EPA standard toxicity test, 90 and 70% survival of marine biota was observed when exposed to an EAL containing 5 wt % of the short-chain phosphonium phosphate and ammonium phosphate ILs, respectively, while the selected commercial gear oil and bioderived additive killed all marine biota. In a standard biodegradability test, 2 wt % addition of the phosphonium phosphate IL not only retained the EAL’s ready biodegradability but further boosted the oil decomposition from a range of 60–80% to a higher level of 80–95%. Conversely, adding the commercial bioderived additive downgraded the EAL from readily to inherently biodegradable. Furthermore, this work offers scientific insights for development of ILs as potential EAL additives for marine energy and broader applications.

additives

Stereomicrostructure-regulated biodegradable adhesives

Commercial adhesives are petroleum-based thermoset networks or nonbiodegradable thermoplastic hot melts, making them ideal targets for replacement by biodegradable alternatives. Poly(3-hydroxybutyrate) (P3HB) is a biorenewable and biodegradable alternative to conventional plastics, but microbial P3HB, which has a stereoperfect stereomicrostructure, exhibits no adhesion. Here, in this study, by elucidating the fundamental relationship between chemocatalytically engineered P3HB stereomicrostructures and adhesion properties, we found that biodegradable syndio-rich P3HB exhibits high adhesion strength and outperforms common commercial adhesives, whereas syndiotactic, isotactic, or iso-rich P3HB shows no measurable adhesion. The syndio-rich stereomicrostructure brings about desired thermomechanical and viscoelastic properties of P3HB that enable strong adhesion to a range of substrates tested, including aluminum, steel, glass, and wood, and its performance is insensitive to molar mass and reprocessing or reuse.

36 MATERIALS SCIENCE

Polylactic acid (PLA)-based multifunctional and biodegradable nanocomposites and their applications

Polylactic acid (PLA)-based nanocomposites are emerging as multifunctional, biodegradable materials, offering sustainable alternatives to petroleum-based plastics. This review examines recent advancements in PLA nanocomposites, focusing on enhanced mechanical strength, thermal stability, and biodegradability achieved through nanofillers like metallic particles, carbon-based materials, and ceramics. Techniques such as in situ polymerization, melt mixing, and electrospinning enable application-specific improvements. PLA's limitations, including brittleness and low barrier properties, are addressed to support diverse applications: in packaging (e.g., extended shelf life), biomedicine (e.g., degradable implants), and electronics (e.g., flexible devices). Despite challenges with filler dispersion and thermal resistance, continued innovations expand PLA's potential across multiple industries, contributing to a sustainable, circular economy.

Biodegradable polymers

Biodegradable Biocomposite Development for Large Scale Additive Manufacturing

Oak Ridge National Laboratory (ORNL) worked with Mitsubishi Chemical America, Inc. to develop a highly biodegradable ~100% biobased feedstock for large format additive manufacturing (AM). Together, they developed an AM feedstock based on the biobased polyester, polybutylene succinate (PBS), that is typically used in agriculture and packaging projects. The motivation for this work was to leverage the high degradability of this polymer in AM to create a new avenue for end-of-life disposal of the product. A composite feedstock was developed from PBS, polylactic acid (PLA), and wood flour (WF). While WF improves printability, reduces feedstock cost, and can improve stiffness, it also often results in a loss in tensile strength which can inhibit/limit applications of the material. To recover the loss in tensile strength suffered by including large quantities, up to 30 wt.% WF in the composite, a chain extender was used to compatibilize the different composite constituents with each other. The feedstock was used to 3D-print a demonstration mold for precast concrete catch basins and was tested by casting 750 lbs of concrete. The mold survived the demonstration. Aerobic degradation testing of the composite feedstock showed that it was highly degradable, 40% biodegradation after 90 days, compared to other incumbent biobased feedstocks.

100% biobased feedstock for large format additive

Biodegradable Biocomposite Development for Large Scale Additive Manufacturing

Oak Ridge National Laboratory (ORNL) worked with Mitsubishi Chemical America, Inc. to develop a highly biodegradable ~100% biobased feedstock for large format additive manufacturing (AM). Together, they developed a AM feedstock based on the biobased polyester, polybutylene succinate (PBS), that is typically used in agriculture and packaging projects. The motivation for this work was to leverage the high degradability of this polymer in AM to create a new avenue for end-of-life disposal of the product. A composite feedstock was developed from PBS, polylactic acid (PLA), and wood flour (WF). While WF improves printability, reduces feedstock cost, and can improve stiffness, it also often results in a loss in tensile strength which can inhibit/limit application of the material. To recover the loss in tensile strength suffered by including large quantities, up to 30 wt%, WF in the composite a chain extender was used to compatibilze the different composite constituents with each other. The feedstock was used to 3D-print demonstration mold for precast concrete catch basins and was tested by casting 750 lbs of concrete. The mold survived the demonstration. Aerobic degradation testing of the composite feedstock showed that it was highly degradable, 40% biodegradation after 90 days, compared to other incumbent biobased feedstocks.

36 MATERIALS SCIENCE

Production of high-performance biodegradable polyurethane products made from algae precursors

We successfully developed and scaled the production of high-performance, fully biodegradable thermoplastic polyurethanes (TPUs) derived from algae-based precursors. By employing innovative flow chemistry and chemo-enzymatic methodologies, the research team produced materials with up to 100% bio-based content that match or exceed the mechanical properties of traditional petroleum-based plastics. These algae-derived TPUs were proven to be fully home-compostable, achieving over 90% decomposition within 110 to 120 days while demonstrating practical advantages such as reduced solvent requirements in fabric coating applications.

36 MATERIALS SCIENCE

The use of near-infrared photography for biodegradable pollution monitoring of tidal rivers

On October 2, 1972, a pattern of chlorophyll a containing phytoplankton (algae) was detected from 3-km altitude in a series of near-infrared photographs of the Potomac River 'Salt Wedge Area.' Densitometer traces over the film images, related to in situ measurements of chlorophyll a concentrations that varied from 4 to more than 3000 micrograms/liter, revealed a phytoplankton 'bloom' threshold in the near infrared between the concentration of 34 and 51 micrograms/liter. The photography also revealed bottom features through two meters of water and made it possible to integrate chlorophyll a concentrations over a 16 sq km area to demonstrate this remote sensing technique for biodegradable pollution monitoring.

Bressette, W. E.

Biodegradation of rocket propellent waste, ammonium perchlorate

The impact of the biodegradation rate of ammonium perchlorate on the environment was studied in terms of growth, metabolic rate, and total biomass of selected animal and plant species. Brief methodology and detailed results are presented.

Naqui, S. M. Z.

Upcycling of Waste Plastics into Carboxylic Acids for Biodegradable Surfactants

This work outlines a process for producing high‐purity (>95%) carboxylate surfactants from post‐consumer recycled high‐density polyethylene (PCR‐HDPE). The approach involves the thermal depolymerization of PCR‐HDPE via pyrolysis, followed by fractional distillation to isolate C9–C14 olefins. These olefins undergo hydroformylation using cobalt carbonyl catalysts to generate aldehydes, which are subsequently oxidized to carboxylic acids using Pinnick oxidation under mild aqueous‐phase conditions. Neutralization of the resulting carboxylic acids with sodium hydroxide produces plastic‐derived carboxylate surfactants (PDCs) in the form of sodium carboxylates. Subsequent purification steps ensure surfactant‐grade purity and enable accurate assessment of physicochemical properties. The resulting PDCs are evaluated for critical micelle concentration (CMC), foamability, surface tension reduction, and calcium ion tolerance, demonstrating competitive behavior with conventional anionic carboxylate surfactants. This route provides a sustainable alternative for surfactant production, reducing reliance on fossil‐derived feedstocks and valorizing plastic waste streams through chemical upcycling.

Biodegradable surfactants

Elucidating biodegradation of dimethyl terephthalate by two Rhodococcus strains for its valorization applications

Dimethyl terephthalate (DMT) serves as the precursor in the production of polyethylene terephthalate, polytrimethylene terephthalate, and polybutylene terephthalate. The widespread use of DMT in the polymer industry and its ubiquitous existence in end products raise alarms about its potential harm to humans and animals. DMT can enter the environment through the degradation of polymers and their end products, and cause endocrine disruption, oxidative stress, and an elevated risk of cancer. In recent years, DMT has also gained renewed interest in its potential for plastic recycling and upcycling. In this study, we identified two strains of Rhodococcus that possess DMT-degrading capabilities and utilized transcriptomic analysis and gene knockout to elucidate the mechanisms of DMT degradation. R. opacus PD630 and R. jostii RPET were found to convert up to 1 g/L DMT into mono-methyl terephthalate (MMT). A putative DMTase (RS34275) was identified for this conversion. R. jostii RPET also demonstrates the ability to convert DMT into MMT and to utilize MMT for its cellular growth via the terephthalate pathway. A putative MMTase (RS21885) as the sole enzyme was identified for the conversion of MMT into terephthalate in the RPET strain. In addition, we successfully produced lycopene and lipids from an engineered RPET strain using DMT as a substrate. Our findings will facilitate future DMT bioremediation and bio-upcycling of DMT-associated plastics, enabling the production of value-added products.

Biodegradation

Biodegradation of rocket propellant waste, ammonium perchlorate

The short term effects of ammonium perchlorate on selected organisms were studied. A long term experiment was also designed to assess the changes incurred by ammonium perchlorate on the nitrogen and chloride contents of soil within a period of 3 years. In addition, an attempt was made to produce methane gas from anaerobic fermentation of the aquatic weed, Alternanthera philoxeroides.

Naqvi, S. M. Z.

Precision Agriculture using Networks of Degradable Analytical Sensors (PANDAS) (Final Technical Report)

Precision agriculture, where sensing of soil, environment and crop conditions are used to precisely synchronize inputs (such as water and fertilizer) to crop needs enhances input use efficiency. This can improve yields and farm profitability while mitigating environmental losses, improving soil carbon content and substantially decreasing energy use for food, feed and fuel crops. Unfortunately, farmers are not yet able to harness the full potential of these management technologies as there is a lack of available management information, and there is therefore a need for sensors that are able to economically measure spatio-temporal variability in soil and crop properties of extremely heterogeneous farm fields precisely at high resolution and at low cost. Real-time, in-situ monitoring of agricultural soil conditions is today carried out using devices that limit the total number of nodes that can be used economically to typically one per acre or less. Higher spatio-temporal resolution sensing would enable more precise agricultural input optimization, with significant benefits to the farmer and the environment. In order to address this issue, this project focused on developing additively manufactured, biodegradable, soil sensors with predicted costs of < $\$$1 per unit to monitor crop inputs (such as water and fertilizer) that predictably, harmlessly degrade away into the soil when no longer needed. These sensor nodes should be easy to place, accurately and continuously monitor soil and crop conditions for an entire season, be read remotely using existing farm equipment, require no ongoing maintenance, not impede farm operations and produce no persistent waste. This approach could enable a >100× increase in information density over current solutions for precision farming of row and other crops, and lead to significant reductions in input energy use and provide increased yield for biofuel crops. Over the course of this project the team at the University of Colorado Boulder, University of California Berkeley, and Colorado State University/Kansas State University investigated a wide range of printable biodegradable electronic materials and sensor designs for determining soil moisture and soil nitrate concentration. These efforts expanded the available materials set for printed soil degradable electronic materials, particularly for conductors, enabling high conductivity and stability. Printed soil moisture and nitrate sensors with suitable sensitivity and selectivity were developed and characterized. Low power and passive wireless electronic systems were integrated with the soil sensors, and testing was carried out with completed sensors to understand their functionality under agricultural conditions. Additionally, other sensor types enabled by the biodegradable materials set created during this project, such as soil microbial activity sensors, were also developed and demonstrated. Project outputs include 10 peer reviewed publications, 4 patent applications, 21 technical presentations, 3 PhD thesis, 10 media reports, 8 additional grants worth over $\$$6M, and the formation of 3 start-up companies.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI

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