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At least 163 records · Page 9

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DOE OSTI2026

Alumina Priming-Mediated Enhanced Binding of Diethylzinc with Carbonyl Groups in Poly(Methyl Methacrylate) during Vapor-Phase Infiltration

Vapor-phase infiltration (VPI) of inorganic materials in polymers is increasingly becoming popular for synthesizing various functional hybrid materials. While AlO x infiltration using trimethylaluminum (TMA) has been extensively studied, the mechanism of diethylzinc (DEZ)-based ZnO x infiltration, especially one that is initiated by AlO x priming, has not received much attention because highly reactive hydroxyl groups generated by AlO x -priming are expected to dominate the initial binding of DEZ, thus enabling the overall ZnO x VPI. Here, we interrogate the ZnO x infiltration mechanism in AlO x -primed poly(methyl methacrylate) (PMMA) in comparison to the control AlO x -only infiltration by utilizing a suite of complementary characterizations, including quartz crystal microbalance mass gain measurement, transmission electron microscopy, infrared reflection–absorption spectroscopy (IRRAS), and synchrotron X-ray absorption spectroscopy (XAS). The multivalent TMA precursor and associated hyperbranched AlO x network can quickly saturate the AlO x infiltration by clogging the polymer-free volume near the top. On the contrary, the ZnO x infiltration using divalent DEZ precursor, once activated via AlO x -priming, can lead to accelerated ZnOx infiltration. With the help of IRRAS, XAS, and density functional theory (DFT) simulations, we uncover that the AlO x -priming enhances the reactivity of neighboring carbonyl groups toward DEZ and opens up simultaneous reaction pathways, leading to accelerated high-fidelity infiltration of ZnO x .

36 MATERIALS SCIENCE↗

DOE OSTI2021

Polymer intercalation synthesis of glycoboehmite nanosheets

In this work, novel materials based on the aluminum oxyhydroxide boehmite phase were prepared using a glycothermal reaction in 1,4-butanediol. Under the synthesis conditions, the atomic structure of the boehmite phase is altered by the glycol solvent in place of the interlayer hydroxyl groups, creating glycoboehmite. The structure of glycoboehmite was examined in detail to determine that glycol molecules are intercalated in a bilayer structure, which would suggest that there is twice the expansion identified previously in the literature. This precursor phase enables synthesis of two new phases that incorporate either polyvinylpyrrolidone or hydroxylpropyl cellulose nonionic polymers. These new materials exhibit changes in morphology, thermal properties, and surface chemistry. All the intercalated phases were investigated using PXRD, HRSTEM, SEM, FT-IR, TGA/DSC, zeta potential titrations, and specific surface area measurement. These intercalation polymers are non-ionic and interact through wetting interactions and hydrogen bonding, rather than by chemisorption or chelation with the aluminum ions in the structure.

36 MATERIALS SCIENCE↗

DOE OSTI2025

Microwave-Assisted Production of Polycarbonate Diols using Carbon Dioxide

Carbon dioxide (CO2) is a cheap and readily available resource that can be converted to value-added chemicals including fuels, polymers, and other products. One lucrative option is polycarbonate diols, which are the precursor to polyurethanes that find wide applications in automotive and aerospace industries. The traditional process for the synthesis of polycarbonate diols involves using hazardous phosgene and alcohols in a strongly basic medium that generates significant amounts of salt. Alternately, CO2 can be reacted with alkanediols over CeO2 catalysts to produce polycarbonate diols. For the current work, a microwave-assisted atmospheric flow system was investigated for converting CO2 into polycarbonate diols and was compared against a thermal system. Various parameters such as type and ratio of solvents, and the addition of dehydrating agents for the microwave system was tested. The different CeO2 catalysts used were characterized using Brunauer–Emmett–Teller (BET) surface area analysis, Raman spectroscopy, X-ray diffraction, and temperature programmed desorption (NH3-TPD and CO2-TPD).

CO2 utilization↗

DOE OSTI2022

iNovo479: Metabolic Modeling Provides a Roadmap to Optimize Bioproduct Yield from Deconstructed Lignin Aromatics by Novosphingobium aromaticivorans

Lignin is an abundant renewable source of aromatics and precursors for the production of other organic chemicals. However, lignin is a heterogeneous polymer, so the mixture of aromatics released during its depolymerization can make its conversion to chemicals challenging. Microbes are a potential solution to this challenge, as some can catabolize multiple aromatic substrates into one product. Novosphingobium aromaticivorans has this ability, and its use as a bacterial chassis for lignin valorization could be improved by the ability to predict product yields based on thermodynamic and metabolic inputs. In this work, we built a genome-scale metabolic model of N. aromaticivorans, iNovo479, to guide the engineering of strains for aromatic conversion into products. iNovo479 predicted product yields from single or multiple aromatics, and the impact of combinations of aromatic and non-aromatic substrates on product yields. We show that enzyme reactions from other organisms can be added to iNovo479 to predict the feasibility and profitability of producing additional products by engineered strains. Thus, we conclude that iNovo479 can help guide the design of bacteria to convert lignin aromatics into valuable chemicals.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2021

Effect of Polymer Removal on the Morphology and Phase of the Nanoparticles in All-Inorganic Heterostructures Synthesized via Two-Step Polymer Infiltration

Polymer templates play an essential role in the robust infiltration-based synthesis of functional multicomponent heterostructures with controlled structure, porosity, and composition. Such heterostructures are be used as hybrid organic–inorganic composites or as all-inorganic systems once the polymer templates are removed. Using iron oxide/alumina heterostructures formed by two-step infiltration of polystyrene-block-polyvinyl pyridine block copolymer with iron and aluminum precursors from the solution and vapor-phases, respectively, we show that the phase and morphology of iron oxide nanoparticles dramatically depend on the approach used to remove the polymer. We demonstrate that thermal and plasma oxidative treatments result in iron oxide nanoparticles with either solid or hollow morphologies, respectively, that lead to different magnetic properties of the resulting materials. Our study extends the boundaries of structure manipulations in multicomponent heterostructures synthesized using polymer infiltration synthesis, and hence their properties.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

DOE OSTI2024

Developmental assembly of multi-component polymer systems through interconnected synthetic gene networks in vitro

Abstract Living cells regulate the dynamics of developmental events through interconnected signaling systems that activate and deactivate inert precursors. This suggests that similarly, synthetic biomaterials could be designed to develop over time by using chemical reaction networks to regulate the availability of assembling components. Here we demonstrate how the sequential activation or deactivation of distinct DNA building blocks can be modularly coordinated to form distinct populations of self-assembling polymers using a transcriptional signaling cascade of synthetic genes. Our building blocks are DNA tiles that polymerize into nanotubes, and whose assembly can be controlled by RNA molecules produced by synthetic genes that target the tile interaction domains. To achieve different RNA production rates, we use a strategy based on promoter “nicking” and strand displacement. By changing the way the genes are cascaded and the RNA levels, we demonstrate that we can obtain spatially and temporally different outcomes in nanotube assembly, including random DNA polymers, block polymers, and as well as distinct autonomous formation and dissolution of distinct polymer populations. Our work demonstrates a way to construct autonomous supramolecular materials whose properties depend on the timing of molecular instructions for self-assembly, and can be immediately extended to a variety of other nucleic acid circuits and assemblies.

Science & Technology - Other Topics↗

DOE OSTI2026

Polymer-iron oxide hybrid films for controlling electrokinetic properties

Electrokinetic phenomena at polymer-water interfaces are central to technologies for water purification, ion separations, and energy conversion, yet the ability to systematically control polymer surface charge and associated electrokinetic processes remains limited. Here, we demonstrate a simple liquid-phase infiltration (LPI) method to synthesize polymer–metal oxide hybrid films with controllable interfacial properties. Hydroxy-terminated poly(2-vinylpyridine) (P2VP-OH) brushes grafted to silicon substrates were infiltrated with iron nitrate from ethanolic solution, followed by low-temperature thermal treatment to convert the infiltrated precursor into iron oxide. Spectroscopic ellipsometry, X-ray photoelectron spectroscopy, and thermogravimetric analysis confirmed oxide incorporation and hybrid film formation without polymer degradation. Electrokinetic measurements reveal that the hybrid films acquire the electrokinetic properties of the infiltrated oxide, with concentration-dependent streaming potentials and surface conductivities closely matching those of pure iron oxide films. These results establish metal oxide infiltration as a scalable and low-cost strategy for controlling interfacial charge in polymer surfaces. The approach introduces new materials and design parameters for tailoring ion selectivity, transport, and energy conversion, with broad implications for the development of advanced membranes, electrokinetic harvesting devices, and polymer-supported oxide electrodes.

36 MATERIALS SCIENCE↗

DOE OSTI2025

Mechanical and Light Activation of Materials for Chemical Production

Abstract Mechanical expansion and contraction of pores within photosynthetic organisms regulate a series of processes that are necessary to manage light absorption, control gas exchange, and regulate water loss. These pores, known as stoma, allow the plant to maximize photosynthetic output depending on environmental conditions such as light intensity, humidity, and temperature by actively changing the size of the stomal opening. Despite advances in artificial photosynthetic systems, little is known about the effect of such mechanical actuation in synthetic materials where chemical reactions occur. It is reported here on a hybrid hydrogel that combines light‐activated supramolecular polymers for superoxide production with thermal mechanical actuation of a covalent polymer. Superoxide production is important in organic synthesis and environmental remediation, and is a potential precursor to hydrogen peroxide liquid fuel. It is shown that the closing of pores in the hybrid hydrogel results in a substantial decrease in photocatalysis, but cycles of swollen and contracted states enhance photocatalysis. The observations motivate the development of biomimetic photosynthetic materials that integrate large scale motion and chemical reactions.

Đorđević, Luka [Department of Chemical Sciences Un↗

DOE OSTI2020

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↗

DOE OSTI2025

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↗

DOE OSTI2020

Polymer principles behind solubilizing lignin with organic cosolvents for bioenergy

Lignin solubilization is key to a viable biorefinery because its removal leads to facile deconstruction of biomass and because the isolated lignin can serve to derive precursors of novel high-value materials. The mixing of organic solvents with water has been shown to improve biomass fractionation and lignin conversion reactions. However, generally-applicable solubilization strategies are lacking because of the remarkable variability of lignin across plant feedstocks. Here, to obtain a predictive understanding of lignin solvation, we perform molecular dynamics simulations of model lignin polymers in two mixtures of water with polar aprotic solvents: tetrahydrofuran (THF) : water and γ-valerolactone (GVL) : water. The model lignins include H-, G- and S-only homopolymers and lignins with an S : G 1 : 1 ratio. We find that a well-established theory of self-avoiding polymers in a “good” solvent describes accurately the physical conformations of all types of lignin in both solvents. As the degree of methoxy substitution increases in the homopolymers, the distributions of the lignin radius of gyration and the Flory exponent ν , which describes the lignin-solvent interactions, do not change in THF : water, while ν shifts to slightly higher values in GVL : water. We attribute this increase to the interaction between the methyl group of GVL with the lignin methoxy groups. We also find that the reduction in the lignin radius of gyration due to branching is accurately described by the Zimm–Stockmayer theory for both THF : water and GVL : water. The above findings validate the applicability of polymer physics concepts to lignin and suggest that GVL : water may have the most favorable interaction with S-lignin, whereas the interactions of THF : water with lignin are independent of lignin monomeric content.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Computationally guided synthesis of carbon coated mesoporous silica materials

Mesoporous silica materials (MSMs) are well-suited for biomedical applications due to their unique features, including a large surface area and tunable pore size. To enhance their durability, the small pores in MSMs are filled with carbon precursors and then carbonized to prevent them from interacting with unreacted silicic acid. Here, in this study, we synthesized and healed MSMs using a combination of non-reactive and reactive molecular dynamics (MD) simulations. The non-reactive MD simulation revealed that the self-assembly of Pluronic® L64 polymers in water resulted in nearly 80 % hydrogen bonds between the hydrophilic sections of the micelle and water. In the bond-boosted ReaxFF MD simulations, silicic acid precursors were condensed on the micelle surface, with over 60 % of them leading to the creation of periodic mesoporous silica within the system. Condensation of silicic acid precursors at 300 K with bond-boosting and at 1500 K without it both significantly promoted the polymerization of Si(OH) 4 , with the latter doubling the rate compared to the former. Subsequently, we healed the MSM surface by carbonizing carbon precursors inside an MSM pore. Polyethylene (PE) and high-rank lignite were identified as the most suitable precursors due to their ability to form turbostratic graphene structures. High-rank lignite exhibited the highest carbon conversion ratio to 6-membered rings, closely followed by PE, in the carbon ring formation analysis. Additionally, the production of gases, such as H 2 , increased significantly for PE at both 2200 K and 2600 K, indicating the conversion of a considerable portion of carbon into graphitic or turbostratic structures. The carbonization of PE primarily led to the formation of planar (sp 2 ) structures, while sucrose yielded the least planar structures. Finally, we studied the protective blocking of unreacted silicic acid precursor by considering a PET turbostratic graphene structure in a silica mesopore formed at 2600 K. The trajectory analysis showed that the surface of the silica was effectively coated with PET tar, preventing unreacted silicic acid from interacting with the inner silica pore surface. These findings offer valuable insights into the synthesis and carbonization-based healing processes of MSMs, enhancing their potential for various biomedical applications.

36 MATERIALS SCIENCE↗

DOE OSTI2025

Fabrication of nanoporous doped metal oxide coatings via selective infiltration of a block copolymer template: The case of Al-doped zinc oxide

Conductive nanoporous conformal coatings are important for various applications including touchscreens, displays, and electrochromic windows, though design of such coating with controlled porosity and composition remains challenging. We propose a sequential infiltration synthesis (SIS) method for the fabrication of nanoporous conductive aluminum-doped zinc oxide (AZO) films by infiltrating block copolymer (BCP) templates, specifically polystyrene-block-polyvinyl pyridine (PS-b-P4VP), with diethyl zinc and trimethyl aluminum precursors. Tunability of both porosity and electrical conductivity is achieved by precisely controlling the swelling behavior of the polymer templates and adjusting the number of SIS cycles. Further, our results reveal that porosity levels can reach up to 80 %, with resistivity as low as ~7.83 Ωcm. Using conductive atomic force microscopy (C-AFM) and Hall effect measurements, we show that lower concentrations of aluminum doping relative to zinc (around 1: 17) results in higher conductivity of the AZO films. Additionally, AZO is based on zinc oxide (ZnO) which is cost-efficient, abundant and less toxic than commonly used transparent conductive oxides such as indium tin oxide (ITO) and fluorine-doped tin oxide (FTO). Therefore, this novel approach opens new possibilities for creating highly porous, conformal, conductive AZO coatings with customizable porosity and composition, making them ideal candidates for diverse optoelectronic applications.

36 MATERIALS SCIENCE↗

DOE OSTI2026

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↗

DOE OSTI2024

Visualization of lignification in flax stem cell walls with novel click-compatible monolignol analogs

As an essential part of plant cell walls, lignin provides mechanical support for plant growth, enhances water transport, and helps to defend against pathogens. As the most abundant natural aromatic-based renewable resource on earth, its biosynthesis has always been a research focus, and it is still currently under study. In this study, the p-coumaryl alcohol analog (H ALK ) and the coniferyl alcohol analog (G ALK ) containing an alkyne group at the ortho position were synthesized and applied to lignification in vivo and in vitro. The incorporation of these novel lignin monomers was observed via fluorescence imaging. It was found that the two monolignol analogs could be incorporated in dehydrogenated polymers (DHPs) in vitro and in flax cell walls in vivo. The results showed that as the cultivation time and precursor concentration varied, the deposition of H and G-type lignin exhibited differences in deposition mode. At the subcellular scale, the deposited lignin first appears in the cell corner and the middle lamella, and then gradually appears on the cell walls. Furthermore, lignin was also found in bast fiber. It was demonstrated that these new molecules could provide high-resolution localization of lignin during polymerization.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2021

Renewable Polyurethanes from Sustainable Biological Precursors

Due to the depletion of fossil fuels, higher oil prices, and greenhouse gas emissions, the scientific community has been conducting an ongoing search for viable renewable alternatives to petroleum-based products, with the anticipation of increased adaptation in the coming years. New academic and industrial developments have encouraged the utilization of renewable resources for the development of ecofriendly and sustainable materials, and here, we focus on those advances that impact polyurethane (PU) materials. Vegetable oils, algae oils, and polysaccharides are included among the major renewable resources that have supported the development of sustainable PU precursors to date. Renewable feedstocks such as algae have the benefit of requiring only sunshine, carbon dioxide, and trace minerals to generate a sustainable biomass source, offering an improved carbon footprint to lessen environmental impacts. Incorporation of renewable content into commercially viable polymer materials, particularly PUs, has increasing and realistic potential. Biobased polyols can currently be purchased, and the potential to expand into new monomers offers exciting possibilities for new product development. This Review highlights the latest developments in PU chemistry from renewable raw materials, as well as the various biological precursors being employed in the synthesis of thermoset and thermoplastic PUs. We also provide an overview of literature reports that focus on biobased polyols and isocyanates, the two major precursors to PUs.

09 BIOMASS FUELS↗

DOE OSTI2024

Driving macro-scale transformations in three-dimensional-printed biopolymers through controlled induction of molecular anisotropy at the nanoscale

Motivated by the need to harness the properties of renewable and biodegradable polymers for the design and manufacturing of multi-scale structures with complex geometries, we have employed our additive manufacturing platform that leverages molecular self-assembly for the production of metre-scale structures characterized by complex geometries and heterogeneous material composition. As a precursor material, we used chitosan, a chemically modified form of chitin, an abundant and sustainable structural polysaccharide. We demonstrate the ability to control concentration-dependent crystallization as well as the induction of the preferred orientation of the polymer chains through the combination of extrusion-based robotic fabrication and directional toolpathing. Anisotropy is demonstrated and assessed through high-resolution micro-X-ray diffraction in conjunction with finite element simulations. Using this approach, we can leverage controlled and user-defined small-scale propagation of residual stresses to induce large-scale folding of the resulting structures.

36 MATERIALS SCIENCE↗

DOE OSTI2026

Siloxane-modified polycarbosilane flexible Prepregs for fabrication of ceramic matrix composites via compression molding and PIP densification

For this work, the development of ceramic matrix composites (CMCs) using 5 harness satin carbon fiber fabric impregnated with commercial polycarbosilane precursor plasticized by siloxane copolymer was investigated aiming to improve wetting behavior and shape conformability. The polycarbosilane precursor and polysiloxane plasticizer were mixed at varying weight ratios to obtain flexible preceramic resin prepreg cloths. 13 plies of preceramic polymer prepreg cloths were stacked in 0/90° layup and cured by compression molding, followed by densified via PIP process. The CMCs were densified with eight PIP cycles followed by final crystallization at 1600 °C. The CMCs made with 10 wt% polysiloxane loading showed lower viscosity of the prepreg resin as well as higher strength and displacement to failure compared to those fabricated from unplasticized polycarbosilane prepolymer. In contrast, at higher concentration of plasticizer, viscosity of the prepreg resin increased, and the CMC became more brittle; however, it exhibited considerably higher thermal conductivity.

Carbosilane↗