Interdisciplinary Materials Research Program Semiannual Progress Report, 1 Mar. - 31 Aug. 1967
Materials science research on inorganic nonmetallic materials, metallic solids, polymers, and solid state physics
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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.
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Utilizing Conjugated Imine Polymers to Stabilize Nanoparticle Silicon Anodes
Silicon anodes provide a compelling route towards delivering high-capacity lithium-ion batteries, however they are notoriously difficult to stabilize in conventional liquid electrolytes that are compatible with high performance cathodes. Furthermore, the drastic changes in volume that occur as silicon is lithiated and delithiated can lead to rapid cell failure and novel polymeric binders are known to help mitigate mechanical issues. We have recently developed a novel method to synthesize the conjugated polymer phenylmethylimine (polyPMI) using an imine metathesis reaction. We have demonstrated that this polymer can be used to stabilize silicon nanoparticles to produce a composite lithium-ion battery anode that is electrochemically stable for hundreds of lithiation and delithiation cycles with a Coulombic efficiency that is greater than 99.95% in a traditional carbonate liquid electrolyte. This work covers the structure and properties of polyPMI within the context of the unique mechanical and electrochemical requirements of nanoparticle silicon anodes. The electrochemical behavior of this polymer also offers new opportunities as an organic lithium-coordinating material that can be used to stabilize a variety of other battery electrodes. More broadly, we posit that this solution-processed, ionically conductive, and electronically conductive polymer is applicable for a variety of energy storage and conversion technologies. Finally, this work demonstrates how this novel polymer chemistry provides additional opportunities for tuning electrode architecture to target high energy full cells.
conjugated polymers↗
SBIR Phase I Final Technical Report LOW-COST, LIGHTWEIGHT DOPED POLYMER COATINGS FOR MICROELECTRONICS VIA 3D PRINTING Award Number DE-SC0025167 Prepared for U.S. Department of Energy, Office of Science, SC-1 For the Period July 22, 2024 – April 21, 2025 Report Date May 5, 2025 Submitted by Jun Wang, Ph.D., Principal Investigator Report Contributors Dr. Jun Wang, Dr. Charles Sosa
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Wang, Jun [Radiation Monitoring Devices, Inc., Wat↗
Effects of Salt on Phase Behavior and Rheological Properties of Alginate–Chitosan Polyelectrolyte Complexes
Oppositely charged polyelectrolytes often form polyelectrolyte complexes (PECs) due to the association through electrostatic interactions. Obtaining PECs using natural, biocompatible polyelectrolytes is of interest in the food, pharmaceutical, and biomedical industries. In this work, PECs were prepared from two biopolymers, positively charged chitosan and negatively charged alginate. We investigate the changes in the structure and properties of PECs by adding sodium chloride (salt doping) to the system. The shear modulus of PECs can be tuned from ~10 to 10 4 Pa by changing the salt concentration. The addition of salt led to a decrease in the water content of the complex phase with increasing shear modulus. However, at a very high salt concentration, the shear modulus of the complex phase decreased but did not lead to the liquid coacervate formation, typical of synthetic polyelectrolytes. This difference in phase behavior has likely been attributed to the hydrophobicity of chitosan and long semiflexible alginate and chitosan chains that restrict the conformational changes. Large amplitude oscillatory shear experiments captured nonlinear responses of PECs. The compositions of the PECs, determined as a function of salt concentration, signify the preferential partitioning of salt into the complex phase. Small-angle X-ray scattering of the salt-doped PECs indicates that the Kuhn length and radius of the alginate–chitosan associated structure qualitatively agree with the captured phase behavior and rheological data. This study provides insights into the structure–property as a function of salt concentration of natural polymer-based PECs necessary for developing functional materials from natural polyelectrolytes.
59 BASIC BIOLOGICAL SCIENCES↗
Macroscale Fabrication of Lightweight and Strong Porous Carbon Foams through Template-Coating Pair Design
Manufacturing of low-density-high-strength carbon foams can benefit the construction, transportation, and packaging industries. One successful route to lightweight and mechanically strong carbon foams involves pyrolysis of polymeric architectures, which is inevitably accompanied by drastic volumetric shrinkage (usually >98%). As such, a challenge of these materials lies in maintaining bulk dimensions of building struts that span orders of magnitude difference in length scale from centimeters to nanometers. Here, this work demonstrates fabrication of macroscale low-density-high-strength carbon foams that feature exceptional dimensional stability through pyrolysis of robust template-coating pairs. The template serves as the architectural blueprint and contains strength-imparting properties (e.g., high node density and small strut dimensions); it is composed of a low char-yielding porous polystyrene backbone with a high carbonization-onset temperature. The coating serves to imprint and transcribe the template architecture into pyrolytic carbon; it is composed of a high char-yielding conjugated polymer with a relatively low carbonization-onset temperature. The designed carbonization mismatch enables structural inheritance, while the decomposition mismatch affords hollow struts, minimizing density. The carbons synthesized through this new framework exhibit remarkable dimensional stability (≈80% dimension retention; ≈50% volume retention) and some of the highest specific strengths (≈0.13 GPa g -1 cm 3 ) among reported carbon foams derived from porous polymer templates.
36 MATERIALS SCIENCE↗
Evaluating sealability of blended smart polymer and fiber additive for geothermal drilling with the effect of fracture opening size
Geothermal formations often contain extensive fracture networks. These fracture networks contribute to the significant loss of drilling fluids during geothermal drilling. Multiple loss circulation materials (LCM) such as fiber, granules, and pills have been proposed to tackle this problem but with only limited success. Recent advances in materials science have led to the development of thermoset shape memory polymers (SMP) to address the lost circulation problem. In this paper, we evaluate a thermoset SMP performance in sealing near wellbore fractures of different sizes in geothermal wells. The SMP performance was assessed using granite disks and cylindrical granite cores having fracture sizes of 1000 μm and 3000 μm. A static filtration test was performed using cedar fiber, CaCO 3 , and SMP. Results showed cedar fiber performed better than the CaCO 3 ., reducing fluid loss by 89% and improving sealing pressure by 200 psi. A novel dynamic testing unit that allows for high-temperature testing under flowing conditions was used in this study. The analysis showed that 3% by weight SMP and fiber blends could bridge and plug the 1000 μm fracture. For a larger fracture of 3000 μm width, there was a need to increase the weight concentration of the SMP to 6% to plug the fracture opening effectively. We showed the influence of key parameters such as the type of LCM, concentration, and particle size distribution in optimizing the performance of drilling fluid loss treatment.
02 PETROLEUM↗
Creating Novel Gas Separation Constructs by Manipulating Free-Volume Distributions in Polymer-Grafted Nanoparticles
Polymer membranes are critical to many sustainability applications that require gas separation primarily based on differences in the sizes of the constituent molecules (“sieving”). The important figures of merit in this context are the rate at which the gas permeates through the membrane (or flux) and the resulting gas purity (as characterized by its selectivity). The overall goal is to maximize both gas permeability and selectivity. Currently, the ability to a priori design polymeric materials (either pure polymers or mixed matrix membranes where polymers are mixed with inorganic nanoparticles) with required permeability and selectivity remains an open challenge.
03 NATURAL GAS↗
Comparing Zwitterionic and PEG Exteriors of Polyelectrolyte Complex Micelles
A series of model polyelectrolyte complex micelles (PCMs) was prepared to investigate the consequences of neutral and zwitterionic chemistries and distinct charged cores on the size and stability of nanocarriers. Using aqueous reversible addition-fragmentation chain transfer (RAFT) polymerization, we synthesized a well-defined diblock polyelectrolyte system, poly(2-methacryloyloxyethyl phosphorylcholine methacrylate)-block-poly((vinylbenzyl) trimethylammonium) (PMPC-PVBTMA), at various neutral and charged block lengths to compare directly against PCM structure–property relationships centered on poly(ethylene glycol)-block-poly((vinylbenzyl) trimethylammonium) (PEG-PVBTMA) and poly(ethylene glycol)-block-poly(l-lysine) (PEG-PLK). After complexation with a common polyanion, poly(sodium acrylate), the resulting PCMs were characterized by dynamic light scattering (DLS) and small angle X-ray scattering (SAXS). We observed uniform assemblies of spherical micelles with a diameter ~1.5–2× larger when PMPC-PVBTMA was used compared to PEG-PLK and PEG-PVBTMA via SAXS and DLS. In addition, PEG-PLK PCMs proved most resistant to dissolution by both monovalent and divalent salt, followed by PEG-PVBTMA then PMPC-PVBTMA. All micelle systems were serum stable in 100% fetal bovine serum over the course of 8 h by time-resolved DLS, demonstrating minimal interactions with serum proteins and potential as in vivo drug delivery vehicles. This thorough study of the synthesis, assembly, and characterization of zwitterionic polymers in PCMs advances the design space for charge-driven micelle assemblies.
59 BASIC BIOLOGICAL SCIENCES↗
On the 3D printing of polypropylene and post-processing optimization of thermomechanical properties
Polypropylene (PP) is a highly desirable polyolefin in various plastic industries due to its outstanding thermomechanical properties and chemical resistance. Therefore, the 3D printing of PP is an interesting avenue to explore in digitized manufacturing, where more freedom in structural designs is available for new and extended applications, such as high-performance engineering parts. Here, in this work, we 3D printed PP and studied the effect of printing parameters and post-processing conditions on the printed polymer’s thermomechanical behavior. Results showed that nozzle and bed temperatures of 220 and 100°C produced a high printing quality. Infill percentages between 80 and 90%, coupled with a 4-h annealing at 110ºC, also resulted in optimal printed properties. It is thought that PP can be potentially blended with polyethylene or other vinyl polymers for a more extended 3D printing utility and practical applications in rapid tooling and prototyping.
36 MATERIALS SCIENCE↗
Monomer-scale design of functional protein polymers using consensus repeat sequences
Protein-based polymers possess chemically defined sequences that can encode diverse properties and functions into a new class of biopolymeric materials. However, sequence variation that emerges from evolution can obscure the sequence–function relationships of naturally derived polymers. One strategy to clarify these relationships is to identify common sequences between proteins with similar functions. These conserved sequences often emerge from repeat proteins, and “consensus repeat sequences” provide a convenient platform for systematic investigations of biopolymer sequence–property relationships. In this review, we highlight recent approaches to engineer tunable polymeric materials using monomer-scale design of consensus repeat proteins. Here, we explore established and emerging protein-based materials with mechanical resilience, thermodynamic phase behavior, chemical responsiveness, biomolecular transport, and hierarchical structure. Overall, recent advances in the monomer-scale design of repetitive protein polymers present exciting fundamental and translational opportunities for polymer scientists and engineers.
36 MATERIALS SCIENCE↗
Multiscale porosity characterization in additively manufactured polymer nanocomposites using micro-computed tomography
Extrusion-based additive manufacturing (AM) of polymer composites exhibits complex thermally driven phenomena that introduce severe discontinuities in the internal structure across length scales, especially voids or porosity. This study utilizes a high-throughput porosity characterization technique to analyze large datasets from numerous micro-computed tomography (mu CT) scans to capture the influence of AM print parameters on the size, shape, and location of porosity across multiple print layers (up to a few cm) on fused granular fabrication (FGF) printers. The materials investigated include nanocomposite formulations based on commercially relevant nylon-12 and polyether ketone ketone (PEKK) materials comprising nano- or micro- sized fillers. The estimated global porosity follows an inverse linear correlation against the bulk density of the printed samples. Increasing the extrusion multiplier (EM) and the nozzle temperature while decreasing the print speeds reduces the global porosity. Outlier analyses (local porosity morphology) show that faster print speeds and higher extrusion rates result in long, slender inter-layer voids, while lower nozzle temperatures lead to large, symmetrical, inter-bead voids (at the bead junction). Lack of active chamber temperature increases inter-layer and intra-bead voids with a two-fold increase in global porosity. Overall, the micro filler-reinforced composites exhibit higher global porosity than nanofiller-reinforced composites, which is attributed to the increased mismatch in the thermal expansion coefficient between the filler and the polymers used in the study.
36 MATERIALS SCIENCE↗
Smectic C Self‐Assembly in Mesogen‐Free Liquid Crystalline Chiral Polyethers with Sulfonylated Methyl‐Branched Side Chains
Abstract To realize advanced electrical applications for ferroelectric liquid crystalline polymers, high spontaneous polarization ( P s ) is highly desired. However, current ferroelectric liquid crystalline polymers usually exhibit a low P s . In this work, mesogen‐free, chiral polyethers containing sulfonylated methyl‐branched alkyl side chains with a (CH 2 ) 3 O spacer between the sulfonyl and the branched alkyl groups are designed and synthesized. In contrast to the linear n ‐alkyl side chains, the methyl‐branched alkyl side chains induce chain tilting in the smectic layers. When double chirality exists in both the main chain and the side chains, a crystalline structure is observed after mechanical stretching. Intriguingly, when single chirality exists in either the backbone or the side chains, a liquid crystalline smectic C phase is obtained. The electric displacement–electric field study, however, does not show typical ferroelectric switching, although the dielectric constants are relatively high for these liquid crystalline polymers. This is likely because the dipole–dipole interactions among neighboring sulfonyl groups along the main chain are so strong that the ferroelectric switching is hindered in the samples. For the future work, it is desired to weaken the dipole–dipole interaction to achieve ferroelectricity in these mesogen‐free liquid crystalline polymers.
36 MATERIALS SCIENCE↗
Controlling swelling in mixed transport polymers through alkyl side-chain physical cross-linking
Semiconducting conjugated polymers bearing glycol side chains can simultaneously transport both electronic and ionic charges with high charge mobilities, making them ideal electrode materials for a range of bioelectronic devices. However, heavily glycolated conjugated polymer films have been observed to swell irreversibly when subjected to an electrochemical bias in an aqueous electrolyte. The excessive swelling can lead to the degradation of their microstructure, and subsequently reduced device performance. An effective strategy to control polymer film swelling is to copolymerize glycolated repeat units with a fraction of monomers bearing alkyl side chains, although the microscopic mechanism that constrains swelling is unknown. Here we investigate, experimentally and computationally, a series of archetypal mixed transporting copolymers with varying ratios of glycolated and alkylated repeat units. Experimentally we observe that exchanging 10% of the glycol side chains for alkyl leads to significantly reduced film swelling and an increase in electrochemical stability. Through molecular dynamics simulation of the amorphous phase of the materials, we observe the formation of polymer networks mediated by alkyl side-chain interactions. When in the presence of water, the network becomes increasingly connected, counteracting the volumetric expansion of the polymer film.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Dynamics of polymer segments, polymer chains, and nanoparticles in polymer nanocomposite melts: A review
The addition of nanoparticles (NPs) to a polymer matrix, forming a polymer nanocomposite (PNC), is known to alter the microscopic dynamic processes of both species which leads to unique macroscopic material properties of the PNC. Because the NPs and polymers have overlapping characteristic length, time, and energy scales, the interactions within these materials are complex and the dynamics are interrelated. In this review, we present an overview of experimental, simulation, and theoretical results that probe multi-scale polymer and nanoparticle dynamics in polymer nanocomposites and navigate the dense parameter space presented by these multicomponent systems. Although a variety of PNC systems are mentioned, we focus this discussion on linear thermoplastics filled with hard spherical or cylindrical NPs in the melt state. We begin by introducing PNCs, the dynamic processes within them, and the importance of dynamics for properties and processing. At the smallest length and time scales, we discuss segmental dynamics in PNCs, including the role of polymer attributes, NP attributes, and NP-polymer interactions. Then, we present measurements of collective motions and intermediate (Rouse) dynamics in various PNC materials. At longer length and time scales, we discuss polymer center-of-mass diffusion in PNCs with either spherical or anisotropic NPs. We then explore the dynamics of the NPs in PNCs and polymer melts, including theoretical predictions, simulation results, and experimental observations. Lastly, we note some of the remaining challenges in probing dynamics in PNC materials and fundamentally studying PNCs more generally.
36 MATERIALS SCIENCE↗
Quantum Simulations of Radiation Damage in a Molecular Polyethylene Analog
Abstract An atomic‐level understanding of radiation‐induced damage in simple polymers like polyethylene is essential for determining how these chemical changes can alter the physical and mechanical properties of important technological materials such as plastics. Ensembles of quantum simulations of radiation damage in a polyethylene analog are performed using the Density Functional Tight Binding method to help bind its radiolysis and subsequent degradation as a function of radiation dose. Chemical degradation products are categorized with a graph theory approach, and occurrence rates of unsaturated carbon bond formation, crosslinking, cycle formation, chain scission reactions, and out‐gassing products are computed. Statistical correlations between product pairs show significant correlations between chain scission reactions, unsaturated carbon bond formation, and out‐gassing products, though these correlations decrease with increasing atom recoil energy. The results present relatively simple chemical descriptors as possible indications of network rearrangements in the middle range of excitation energies. Ultimately, the work provides a computational framework for determining the coupling between nonequilibrium chemistry in polymers and potential changes to macro‐scale properties that can aid in the interpretation of future radiation damage experiments on plastic materials.
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
Hydrogen-Bonding Bottlebrush Networks: Self-Healing Materials from Super-Soft to Stiff
The impact of polymer architecture on network dynamics and self-healing is presented using bottlebrushes containing side chains that are end-functionalized with 2-ureido-4[1H]-pyrimidinone (UPy). The synthesis of these materials is straightforward through a three-step process: (1) synthesizing rubbery poly(4-methylcaprolactone) macromonomers (p4MCL–OH) with a norbornene-based initiator, (2) functionalizing the terminal hydroxyl group with UPy–isocyanate (p4MCL–UPy), and (3) statistically copolymerizing p4MCL–OH and p4MCL–UPy via ring-opening metathesis polymerization (ROMP) to form hydrogen-bonding bottlebrushes having a fraction (p) of side chains functionalized with UPy. Attaching UPy to the free end of bottlebrush side chains dilutes the impact of friction from complementary UPy interactions on segmental dynamics, leading to a much weaker dependence of the glass-transition temperature (T g ) on p than observed in linear analogues, while the activation energy to dissociate UPy–UPy bonds (41–47 kJ/mol) remains mostly unchanged. Longer side chains result in a competition between reducing T g and inducing entanglements that influence hydrogen-bonded network dynamics. Increasing the backbone length extends the sticky Rouse region without affecting the network modulus (G x ) or UPy–UPy dissociation time (τ s ). Gx scales linearly with p and ranges from 27 kPa to 1.6 MPa, while τs remains nearly constant in contrast to linear telechelic ionomers, implying a similar self-healability across bottlebrush networks containing different amounts of UPy. Furthermore, these stretchable networks with p ≤ 0.25 undergo self-healing upon repeated rupture and melt pressing at ≤100 °C while retaining similar tensile properties. In summary, decorating bottlebrush polymers with hydrogen bonds creates opportunities to independently manipulate associative network dynamics and mechanical moduli.
36 MATERIALS SCIENCE↗
Microwave assisted heating of plastic waste: Effect of plastic/susceptor (SiC) contacting patterns
We discuss plastic accumulation as a growing sustainability challenge. Most plastics are thermally inert at room temperature, requiring high temperatures for depolymerization. In the quest for developing sustainable plastic upcycling, we investigate silicon carbide (SiC) as microwave absorbing susceptors for reaching depolymerization temperatures. We utilize three SiC topologies – particles, hot-pressed plastic films containing SiC particles, and monoliths. SiC particles of >0.5 mm in diameter can provide heating rates approaching ~200 °C/min at modest powers. Still, physically mixed plastic-susceptor beds suffer from density differences, causing non-uniform contact during plastic softening and melting. Hot-pressed plastic films containing SiC particles allow uniform plastic-susceptor contact but suffer from slow heating as only a single layer of susceptors exists between polymer layers. SiC monoliths mitigate these challenges by preferentially dissipating the microwaves and rapidly heating the plastics independently of polymeric properties.
36 MATERIALS SCIENCE↗