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At least 595 records · Page 33

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DOE OSTI2024

Nanoengineered Shape-Memory Hemostat

Uncontrolled hemorrhage is the predominant cause of preventable combat deaths. Various biomaterials serve as hemostatic agents due to their procoagulant or absorptive activity. However, these biomaterials often lack expansion capabilities, which severely limits use in noncompressible wounds. This study combines a hemostatic nanocomposite with a shape-memory polymer foam to design a composite material with both hemostatic and physical expansion properties. This composite is fabricated in two formulations: a foam externally coated in a highly concentrated nanocomposite (“coated composite”) and a foam containing a diluted nanocomposite infused throughout its pores (“infused composite”). Both formulations retain the shape-memory foam's expansion property. Further, the coated composite shows improved fluid uptake (>2-fold) versus infused composites or foam. The nanocomposite component dissociates from the foam under degradative conditions, with the foam remaining stable for 30 days. Hemostatic studies illustrate that the coated composite reduces the clotting time by ≈20%. Alternatively, the infused composite improves clotting over a larger distance (up to ≈2× distance from the composite). These results signify a modular hemostatic ability: the coated composite reduces clotting and improves fluid uptake, while the infused composite achieves diffuse clotting and maintains mechanical properties. Thus, these materials pose a strong potential for use in noncompressible wounds.

60 APPLIED LIFE SCIENCES↗

DOE OSTI2021

Durable and Highly Selective Ion Transport of a Sulfonated Diels Alder Poly(phenylene) for Vanadium Redox Flow Batteries

In order to improve the durability and ion selectivity of a hydrocarbon membrane for vanadium redox flow batteries (VRFBs) a polymer was rationally designed with an external hydrophobic shell and internal hydrophilic core. The polymer was designed to prevent hydrophilic polymer chain aggregation by functionalizing the external polymer shell with hydrophobic side chains and attaching acid moieties onto the polymer backbone. The hydrophobic shell is the result of pentafluorobenzoyl group functionalization on the pendent aryl rings in a Diels Alder poly(phenylene) backbone. The internal polymer chain contains sulfonic acid moieties to impart hydrophilic character. The physical and electrochemical characteristics of the membrane were systematically studied and compared with widely used Nafion-212. The synthesized membranes were found to be superior to Nafion-212 not only in terms of lower vanadium ion permeability (4.25 x 10 -8 vs. Nafion-212: 6.0 x 10 -6 cm 2 min -1 ) but also in higher VRFB performance (EE = 89% and vs. Nafion-212: 85.5% at 40 mA/cm 2 ). The membrane also showed over three times higher capacity retention than Nafion-212 (0.075 % vs. 0.25 % capacity loss per cycle respectively) and excellent ex situ and in situ chemical stability.

25 ENERGY STORAGE↗

NASA NTRS1978

Flame retardant spandex type polyurethanes

Flame retardant elastomeric compositions were developed, comprised of: (1) spandex type polyurethane having incorporated into the polymer chain, halogen containing polyols; (2) conventional spandex type polyurethanes in physical admixture flame retardant additives; and (3) fluoroelastomeric resins in physical admixture with flame retardant additives. Methods of preparing fibers of the flame retardant elastomeric materials are presented and articles of manufacture comprised of the elastomeric materials are mentioned.

Howarth, J. T.↗

NASA NTRS1984

Polyimide adhesives - Modified with ATBN and silicone elastomers

A series of studies evaluating the effects of added elastomers on the properties of a high-temperature addition polyimide adhesive is reviewed. First, thermoset polyimides containing various butadiene/acrylonitrile and silicone elastomers were synthesized either as physical polybends or by chemically reacting the elastomers directly onto the polymer backbone. The modified adhesive resins were characterized for thermomechanical properties, fracture toughness and adhesive strength. A second series of elastomer-containing polyimides was also prepared in order to study the effects of the elastomer chain length on polymer properties. Aromatic amine-terminated silicone rubbers with repeat units varying from n = 10 to 105 were reacted onto the polyimide backbone, and the resulting polymers were characterized for their adhesive properties.

St. Clair, A. K.↗

NASA NTRS1987

Ceramic matrix and resin matrix composites: A comparison

The underlying theory of continuous fiber reinforcement of ceramic matrix and resin matrix composites, their fabrication, microstructure, physical and mechanical properties are contrasted. The growing use of organometallic polymers as precursors to ceramic matrices is discussed as a means of providing low temperature processing capability without the fiber degradation encountered with more conventional ceramic processing techniques. Examples of ceramic matrix composites derived from particulate-filled, high char yield polymers and silsesquioxane precursors are provided.

Hurwitz, Frances I.↗

NASA NTRS1987

Ceramic matrix and resin matrix composites - A comparison

Hurwitz, Frances I.↗

NASA NTRS1990

Chemistry and properties of new poly(arylene ether imidazoles)

As part of a program to develop high-temperature high-performance structural resins for aerospace applications, the chemistry and properties of new poly(arylene ether imidazoles) were investigated. The polymers were prepared by the nucleophilic displacement reaction of aromatic bis(imidazolephenols) with activated aromatic difluoro compounds. The amorphous thermoplastic polymers exhibited glass transition temperatures from 230 to 301 C, inherent viscosities from 0.46 to 1.46 dL/g, and number-average molecular weights as high as 59,300 g/mole. The polymers exhibit good toughness, adhesive, composite, and film properties. The chemical, physical, and mechanical properties of these materials are discussed.

Connell, J. W.↗

NASA NTRS1992

Progressive fracture of polymer matrix composite structures: A new approach

A new approach independent of stress intensity factors and fracture toughness parameters has been developed and is described for the computational simulation of progressive fracture of polymer matrix composite structures. The damage stages are quantified based on physics via composite mechanics while the degradation of the structural behavior is quantified via the finite element method. The approach account for all types of composite behavior, structures, load conditions, and fracture processes starting from damage initiation, to unstable propagation and to global structural collapse. Results of structural fracture in composite beams, panels, plates, and shells are presented to demonstrate the effectiveness and versatility of this new approach. Parameters and guidelines are identified which can be used as criteria for structural fracture, inspection intervals, and retirement for cause. Generalization to structures made of monolithic metallic materials are outlined and lessons learned in undertaking the development of new approaches, in general, are summarized.

Chamis, C. C.↗

NASA NTRS1992

Progressive delamination in polymer matrix composite laminates: A new approach

A new approach independent of stress intensity factors and fracture toughness parameters has been developed and is described for the computational simulation of progressive delamination in polymer matrix composite laminates. The damage stages are quantified based on physics via composite mechanics while the degradation of the laminate behavior is quantified via the finite element method. The approach accounts for all types of composite behavior, laminate configuration, load conditions, and delamination processes starting from damage initiation, to unstable propagation, and to laminate fracture. Results of laminate fracture in composite beams, panels, plates, and shells are presented to demonstrate the effectiveness and versatility of this new approach.

Chamis, C. C.↗

NASA NTRS2008

New Materials for the Repair of Polyimide Electrical Wire Insulation

Two viable polyimide backbone materials have been identified that will allow the repair of polyimide electrical wire insulation found on the Space Shuttle and other aging aircraft. This identification is the outcome of ongoing efforts to assess the viability of using such polyimides and polyimide precursors (polyamic acids [PAAs]) as repair materials for aging polyimide electrical wire insulation. These repair materials were selected because they match the chemical makeup of the underlying wire insulation as closely as possible. This similarity allows for maximum compatibility, coupled with the outstanding physical properties of polyimides. The two polyimide backbone materials allow the polymer to be extremely flexible and to melt at low temperatures. A polymer chain end capping group that allows the polymer to crosslink into a nonflowable repair upon curing at around 200 C was also identified.

Source record↗

NASA NTRS2015

Nanotubular Toughening Inclusions

Conventional toughening agents are typically rubbery materials or small molecular weight molecules, which mostly sacrifice the intrinsic properties of a matrix such as modulus, strength, and thermal stability as side effects. On the other hand, high modulus inclusions tend to reinforce elastic modulus very efficiently, but not the strength very well. For example, mechanical reinforcement with inorganic inclusions often degrades the composite toughness, encountering a frequent catastrophic brittle failure triggered by minute chips and cracks. Thus, toughening generally conflicts with mechanical reinforcement. Carbon nanotubes have been used as efficient reinforcing agents in various applications due to their combination of extraordinary mechanical, electrical, and thermal properties. Moreover, nanotubes can elongate more than 20% without yielding or breaking, and absorb significant amounts of energy during deformation, which enables them to also be an efficient toughening agent, as well as excellent reinforcing inclusion. Accordingly, an improved toughening method is provided by incorporating nanotubular inclusions into a host matrix, such as thermoset and thermoplastic polymers or ceramics without detrimental effects on the matrix's intrinsic physical properties.

Park, Cheol↗

DOE OSTI2024

Coupling and Decoupling between Stickers and Backbones in Associating Polymers with Terminally Functionalized Side Chains

Associating polymers have recently attracted tremendous attention as self-healing polymers due to the dynamic reversibility of sticker association–dissociation processes. These sticker dynamics inevitably slow significantly as segmental dynamics decelerate below the glass transition temperature that limits the operational temperatures of associating polymers. Using broadband dielectric spectroscopy on a new set of associating polymers composed side chains of various lengths and terminal carboxylic-acid sticker functionality, we discovered an unexpected decoupling near the glass transition (T g ) between the slower backbone and fast sticker motions. These two motions have distinct activation energies for the motion of the sulfur linkage adjacent to the backbone (~22 to 26 kJ/mol) and the carboxylic acid groups (~5 to 8 kJ/mol). A second decoupling appears in the polymer with the longest side chain length at T g – 20 K, reflecting the dynamics of various carboxylic acid binding configurations. Furthermore, our findings open the door to design associating polymers with the capability of sticker association/dissociation at low temperatures.

36 MATERIALS SCIENCE↗

DOE OSTI2020

Determining population densities in bimodal micellar solutions using contrast-variation small angle neutron scattering

Self-assembly of amphiphilic polymers in water is of fundamental and practical importance. Significant amounts of free unimers and associated micellar aggregates often coexist over a wide range of phase regions. The thermodynamic and kinetic properties of the microphase separation are closely related to the relative population density of unimers and micelles. Although the scattering technique has been employed to identify the structure of micellar aggregates as well as their time-evolution, the determination of the population ratio of micelles to unimers remains a challenging problem due to their difference in scattering power. In this work, using small-angle neutron scattering (SANS), we present a comprehensive structural study of amphiphilic n-dodecyl-PNIPAm polymers, which shows a bimodal size distribution in water. By adjusting the deuterium/hydrogen ratio of water, the intra-micellar polymer and water distributions are obtained from the SANS spectra. The micellar size and number density are further determined, and the population densities of micelles and unimers are calculated to quantitatively address the degree of micellization at different temperatures. Our method can be used to provide an in-depth insight into the solution properties of microphase separation, which are present in many amphiphilic systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Selective Depolymerization for Sculpting Polymethacrylate Molecular Weight Distributions

Chain-end reactivation of polymethacrylates generated by reversible-deactivation radical polymerization (RDRP) has emerged as a powerful tool for triggering depolymerization at significantly milder temperatures than those traditionally employed. In this study, we demonstrate how the facile depolymerization of poly(butyl methacrylate) (PBMA) can be leveraged to selectively skew the molecular weight distribution (MWD) and predictably alter the viscoelastic properties of blended PBMA mixtures. By mixing polymers with thermally active chain ends with polymers of different molecular weights and inactive chain ends, the MWD of the blends can be skewed to be high or low by selective depolymerization. This approach leads to the counterintuitive principle of the “destructive strengthening” of a material. As a result, we demonstrate, as a proof of concept, the encryption of information within polymer mixtures by linking Morse code with the MWDs before and after selective depolymerization, allowing for the encoding of data within blends of synthetic macromolecules.

36 MATERIALS SCIENCE↗

NASA NTRS2018

Associative Polymers to Control Formation of Particulate Matter from Ignitable Compositions and Related Compositions, Methods and Systems

Described herein are associative polymers capable of controlling formation of particulate matter from a non-polar ignitable composition upon ignition of the non-polar ignitable composition, alone or in combination with control of a physical and/or chemical property of the non-polar compositions and related compositions, methods and systems. Associative polymers herein described have a non-polar backbone and functional groups presented at ends of the non-polar backbone, with a number of the functional groups presented at the ends of the non-polar backbone formed by associative functional groups capable of undergoing an associative interaction with another associative functional group with an association constant (k) such that the strength of each associative interaction is less than the strength of a covalent bond between atoms and in particular less than the strength of a covalent bond between backbone atoms.

Kornfield, Julia A.↗

NASA NTRS2017

Development of an Unstructured, Three-Dimensional Material Response Design Tool

A preliminary verification and validation of a new material response model is presented. This model, Icarus, is intended to serve as a design tool for the thermal protection systems of re-entry vehicles. Currently, the capability of the model is limited to simulating the pyrolysis of a material as a result of the radiative and convective surface heating imposed on the material from the surrounding high enthalpy gas. Since the major focus behind the development of Icarus has been model extensibility, the hope is that additional physics can be quickly added. The extensibility is critical since thermal protection systems are becoming increasing complex, e.g. woven carbon polymers. Additionally, as a three-dimensional, unstructured, finite-volume model, Icarus is capable of modeling complex geometries as well as multi-dimensional physics, which have been shown to be important in some scenarios and are not captured by one-dimensional models. In this paper, the mathematical and numerical formulation is presented followed by a discussion of the software architecture and some preliminary verification and validation studies.

Material Response Model↗

DOE OSTI2022

Tunable polyvinyl chloride (PVC) and thermoplastic polyurethane (TPU)-based soft polymer gel sensors

Abstract Polyvinyl chloride (PVC) gels have recently been found to exhibit mechanoelectrical transduction under mechanical deformation. These mechanoelectrical properties of PVC gels are largely uncharacterized and the underlying transduction mechanisms are currently unknown. These soft electroactive polymers have tunable properties such as modulus and response voltage based on physical dimensions and the amount of plasticizer content within the material making them ideal candidates for complaint sensors. This study aims to investigate PVC gels comprised of various plasticizers to further investigate underlying mechanisms of mechanoelectrical transduction and broaden possible sensing applications. Plasticizers used in this study include dibutyl adipate, dibutyl phthalate, dioctyl phthalate, otherwise known as bis(2-ethylhexyl) phthalate, diisodecyl adipate, and the environmentally friendly biodegradable plasticizer acetyl tributyl citrate (ATBC). ATBC is often used in cosmetics and food packaging applications and is even used as a food additive which may lead to future biocompatibility for these gel sensors. These plasticizers are used to produce PVC gel sensors that are experimentally tested for mechanoelectrical transduction properties and sensing performance. In this study, a Langmuir adsorptive model is fit to the collected mechanoelectrical transduction data. These results are also nondimensionalized and compared to the characteristic dimensionless Langmuir adsorptive model. This simple model agrees very well with the experimental data. Additionally, a study on the mechanoelectrical transduction of an alternative polymer lattice structure, thermoplastic polyurethane (TPU), is discussed. This is a novel electroactive polymer investigated for mechanoelectrical transduction properties. This portion of the study aims to further knowledge of underlying mechanisms of mechanoelectrical transduction as well as show feasibility of additional lattices for soft polymer gel sensors. These TPU gel sensors show strikingly similar mechanoelectrical transduction properties to analogous PVC gels, insinuating that the polymer structure has a limited role in the underlying sensing mechanism and PVC itself is not unique to polymer gel sensing. The TPU-based soft polymer gel sensors however do display some level of mechanoelectrical hysteresis which may be attributed to viscoelastic properties and display a small amount of fatigue possibly due to exudation of liquid plasticizer. This study provides further characterization of mechanoelectrical response for varying plasticizers, provides a theoretical framework for underlying mechanisms, and displays the potential for further polymeric gel sensors.

Instruments & Instrumentation↗

DOE OSTI2025

Bottom-Up Simulation, Reconstruction, and Quantification of Macromolecule Sequences from Experimental Polymerizations

Motivated by the canonical sequence–structure–function paradigm, tools to characterize chemical patterning in natural biomacromolecules, from proteins to nucleic acids, have grown exponentially in recent years. However, analogous strategies for synthetic macromolecules remain in nascent stages, complicated by sequence polydispersity and analytical limitations. To address this, we have developed a comprehensive and open-source Python package, PRISM (polymer rate insights and sequence modeling), an end-to-end workflow that provides a path from experimental kinetics measurements to quantitative and qualitative metrics for describing chemical patterning in stochastic polymers. First, a numerical integration strategy was constructed to simulate and fit experimental data from reversible addition–fragmentation chain transfer (RAFT) polymerization kinetics, enabling the facile estimation of relevant reactivity ratios. These ratios were then used in a mechanism-specific stochastic kinetic simulation strategy to simulate sequence ensembles corresponding to model systems spanning experimental copolymers, classes of statistical polymers (e.g., alternating, block, and gradient), and multiblock copolymers. Lastly, inspired by sequence homology metrics from bioinformatics, we introduce visualization strategies and quantitative metrics to facilitate comparisons of different sequence ensembles. As the sequence–structure–function paradigm becomes increasingly central in de novo design of synthetic macromolecules, this toolkit provides a first step toward accurate and representative sequence description and featurization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗