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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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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Ionic complexation of endblock-sulfonated thermoplastic elastomers and their physical gels for improved thermomechanical performance

Thermoplastic elastomers (TPEs) composed of nonpolar triblock copolymers constitute a broadly important class of (re)processable network-forming macromolecules employed in ubiquitous commercial applications. Physical gelation of these materials in the presence of a low-volatility oil that is midblock-selective yields tunably soft TPE gels (TPEGs) that are suitable for emergent technologies ranging from electroactive, phase-change and shape-memory responsive media to patternable soft substrates for flexible electronics and microfluidics. Many of the high-volume TPEs used for these purposes possess styrenic endblocks that are inherently limited by a relatively low glass transition temperature. To mitigate this shortcoming, we sulfonate and subsequently complex (and physically crosslink) the endblocks with trivalent Al3+ ions. Doing so reduces the effective hydrophilicity of the sulfonated endblocks, as evidenced by water uptake measurements, while concurrently enhancing the thermomechanical stability of the corresponding TPEGs. Chemical modification results, as well as morphological and property development, are investigated as functions of the degree of sulfonation, complexation and TPEG composition. (C) 2020 Published by Elsevier Inc.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Supersoft Norbornene–Based Thermoplastic Elastomers with High Strength and Upper Service Temperature

With over 6 million tons produced annually, thermoplastic elastomers (TPEs) have become ubiquitous in modern society, due to their unique combination of elasticity, toughness, and reprocessability. Nevertheless, industrial TPEs display a tradeoff between softness and strength, along with low upper service temperatures, typically ≤100 °C. This limits their utility, such as in bio-interfacial applications where supersoft deformation is required in tandem with strength, in addition to applications that require thermal stability (e.g., encapsulation of electronics, seals/joints for aeronautics, protective clothing for firefighting, and biomedical devices that can be subjected to steam sterilization). Thus, combining softness, strength, and high thermal resistance into a single versatile TPE has remained an unmet opportunity. Through de novo design and synthesis of novel norbornene-based ABA triblock copolymers, this gap is filled. Ring-opening metathesis polymerization is employed to prepare TPEs with an unprecedented combination of properties, including skin-like moduli (<100 kPa), strength competitive with commercial TPEs (>5 MPa), and upper service temperatures akin to high-performance plastics (≈260 °C). Here, the materials are elastic, tough, reprocessable, and shelf stable (≥2 months) without incorporation of plasticizer. Structure–property relationships identified herein inform development of next-generation TPEs that are both biologically soft yet thermomechanically durable.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Thermoplastic Elastomers and Their Physical Gels Electrospun into Tunable Microfibrous Nonwoven Mats: Structure Formation and Property Enhancement

Abstract Thermoplastic elastomers (TPEs) based on styrenic block copolymers constitute excellent examples of self‐networking macromolecules that are employed in a wide range of contemporary technologies as molded parts. In such applications, these TPEs exist as dense (nonporous) films or other shapes. Here, it is first demonstrated that a series of commercial TPEs possessing comparable compositions can be electrospun from solution to form microfibers that are arranged into nonwoven mats that are breathable. An important consideration for microfiber formation is the copolymer molecular weight, which regulates i) the viscosity of the parent solution prior to electrospinning, ii) the ability of these copolymers to self‐assemble during electrospinning, iii) the microfiber morphology, and iv) the mechanical properties of the resultant microfibers. The addition of a midblock‐selective aliphatic oil to these TPEs yields thermoplastic elastomer gels (TPEGs), wherein the copolymer morphology and mechanical properties become highly composition‐tunable. Electrospinning TPEGs from a binary oil+solvent solution introduces a micelle inversion mechanism that begins with an oil‐rich micellar core and ends with a styrene‐rich micellar core, required for network stabilization, as the solvent dries during microfiber solidification. This work has implications for the production of controllably low‐modulus microfibrous materials possessing modestly improved toughness but exceptional extensibility and enhanced optical transparency.

Shamsi, Mohammad↗
DOE OSTI2021

Morphological Studies of Solution-Crystallized Thermoplastic Elastomers with Polyethylene Endblocks and a Random-Copolymer Midblock

Styrenic thermoplastic elastomers (TPEs) in the form of triblock copolymers possessing glassy endblocks and a rubbery midblock account for the largest global market of TPEs worldwide, and typically rely on microphase separation of the endblocks and the subsequent formation of rigid microdomains to ensure satisfactory network stabilization. In this work, the morphological characteristics of a relatively new family of crystallizable TPEs that instead consist of polyethylene endblocks and a random-copolymer midblock composed of styrene and (ethylene-co-butylene) moieties are investigated. Copolymer solutions prepared at logarithmic concentrations in a slightly endblock-selective solvent are subjected to crystallization under different time and temperature conditions to ascertain if copolymer self-assembly is directed by endblock crystallization or vice versa. According to transmission electron microscopy, semicrystalline aggregates develop at the lowest solution concentration examined (0.01 wt%), and the size and population of crystals, which dominate the copolymer morphologies, are observed to increase with increasing aging time. Real-space results are correlated with small- and wide-angle X-ray scattering to elucidate the concurrent roles of endblock crystallization and self-assembly of these unique TPEs in solution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Tunable thermoplastic elastomer gels derived from controlled-distribution triblock copolymers with crystallizable endblocks

Thermoplastic elastomers (TPEs), a commercially important category of triblock copolymers, are employed alone or upon physical modification with a midblock-selective oil (to form TPE gels, TPEGs) in a broad range of contemporary technologies. While most copolymers in this class of self-networking macromolecules possess glassy polystyrene endblocks and a rubbery polydiene or polyolefin midblock, we investigate TPEGs fabricated from a novel controlled-distribution copolymer with crystallizable polyolefin endblocks and a random-copolymer midblock. According to both electron microscopy and small-angle scattering, the morphologies of these TPEGs remain largely invariant up to 40 wt% oil and then transform considerably at higher oil levels. Although reductions in endblock melting point and crystallinity measured by thermal calorimetry accompany increasing oil content, mechanical properties such as the uniaxial strain at break and fracture toughness improve in some cases by over 50% between 5 and 40 wt% oil. In fact, the strain at break can reach 2500% within this range, thereby confirming that (i) the structure–property relationships of these unique TPEGs are highly composition-tunable and (ii) these TPEGs, stabilized by crystallizable endblocks, provide an attractive alternative for ultrasoft and stretchy recyclable materials.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Revealing Deformation Mechanisms in Polymer-Grafted Thermoplastic Elastomers via In Situ Small-Angle X-ray Scattering

The tunable properties of thermoplastic elastomers (TPEs), through polymer chemistry manipulations, enable these technologically critical materials to be employed in a broad range of applications. The need to “dial-in” the mechanical properties and responses of TPEs generally requires the design and synthesis of new macromolecules. In these designs, TPEs with nonlinear macromolecular architectures outperform the mechanical properties of their linear copolymer counterparts, but the differences in the deformation mechanism providing enhanced performance are unknown. Here, in situ small-angle X-ray scattering (SAXS) measurements during uniaxial extension reveal distinct deformation mechanisms between a commercially available linear poly(styrene)–poly(butadiene)–poly(styrene) (SBS) triblock copolymer and the grafted SBS version containing grafted poly(styrene) (PS) chains from the poly(butadiene) (PBD) midblock. The neat SBS (φ SBS = 100%) sample deforms congruently with the macroscopic dimensions, with the domain spacing between spheres increasing and decreasing along and transverse to the stretch direction, respectively. At high extensions, end segment pullout from the PS-rich domains is detected, which is indicated by a disordering of SBS. Conversely, the PS-grafted SBS that is 30 vol % SBS and 70% styrene (φ SBS = 30%) exhibits a lamellar morphology, and in situ SAXS measurements reveal an unexpected deformation mechanism. During deformation, there are two simultaneous processes: significant lamellar domain rearrangement to preferentially orient the lamellae planes parallel to the stretch direction and crazing. The samples whiten at high strains as expected for crazing, which corresponds with the emergence of features in the 2D SAXS pattern during stretching consistent with fibril-like structures that bridge the voids in crazes. The significant domain rearrangement in the grafted copolymers is attributed to the new junctions formed across multiple PS domains by the grafting of a single chain. In conclusion, the in situ SAXS measurements provide insights into the enhanced mechanical properties of grafted copolymers that arise through improved physical cross-linking that leads to nanostructure domain reorientation for self-reinforcement and craze formation where fibrils help to strengthen the polymer.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Asymmetric Miktoarm Star Polymers as Polyester Thermoplastic Elastomers

A library of polyester-based A(BA') n asymmetric miktoarm star polymers was synthesized with A, A' = poly(l-lactide) (PLLA) as the semicrystalline hard blocks and B = poly(4-methylcaprolactone) (PMCL) as the soft segment using a grafting-through platform known as μSTAR. The synthetic versatility of μSTAR enabled a systematic investigation of architectural design parameters, in particular the number of BA' arms (n), while holding the A, A', and B block lengths constant. The value of n has a pronounced impact on the mechanical properties of these high-molecular-weight miktoarm materials. Tensile toughness increases with n, an effect likely related to bridging, as the modulus drops because the hard-block volume fraction decreases. Furthermore, these insights expand our understanding of architecture effects in sustainable thermoplastic elastomers.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Direct synthesis of ordered mesoporous materials from thermoplastic elastomers

Abstract The ability to manufacture ordered mesoporous materials using low-cost precursors and scalable processes is essential for unlocking their enormous potential to enable advancement in nanotechnology. While templating-based methods play a central role in the development of mesoporous materials, several limitations exist in conventional system design, including cost, volatile solvent consumption, and attainable pore sizes from commercial templating agents. This work pioneers a new manufacturing platform for producing ordered mesoporous materials through direct pyrolysis of crosslinked thermoplastic elastomer-based block copolymers. Specifically, olefinic majority phases are selectively crosslinked through sulfonation reactions and subsequently converted to carbon, while the minority block can be decomposed to form ordered mesopores. We demonstrate that this process can be extended to different polymer precursors for synthesizing mesoporous polymer, carbon, and silica. Furthermore, the obtained carbons possess large mesopores, sulfur-doped carbon framework, with tailorable pore textures upon varying the precursor identities.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Effect of Molecular Weight on the Morphology of a Polymer Semiconductor–Thermoplastic Elastomer Blend

Abstract Polymer semiconductors (PSCs) are essential active materials in mechanically stretchable electronic devices. However, many exhibit low fracture strain due to their rigid chain conformation and the presence of large crystalline domains. Here, a PSC/elastomer blend, poly[((2,6‐bis(thiophen‐2‐yl)‐3,7‐bis(9‐octylnonadecyl)thieno[3,2‐b]thieno[2′,3′:4,5]thieno[2,3‐d]thiophene)‐5,5′‐diyl)(2,5‐bis(8‐octyloctadecyl)‐3,6‐di(thiophen‐2‐yl)pyrrolo[3,4‐c]pyrrole‐1,4‐dione)‐5,5′‐diyl]] (P2TDPP2TFT4) and polystyrene‐ block ‐poly(ethylene‐ran‐butylene)‐ block ‐polystyrene (SEBS) are systematically investigated. Specifically, the effects of molecular weight of both SEBS and P2TDPP2TFT4 on the resulting blend morphology, mechanical, and electrical properties are explored. In addition to commonly used techniques, atomic force microscopy‐based nanomechanical images are used to provide additional insights into the blend film morphology. Opposing trends in SEBS‐induced aggregation are observed for the different P2TDPP2TFT4 molecular weights upon increasing the SEBS molecular weight from 87 to 276 kDa. Furthermore, these trends are seen in device performance trends for both molecular weights of P2TDPP2TFT4. SEBS molecular weight also has a substantial influence on the mesoscale phase separation. Strain at fracture increases dramatically upon blending, reaching a maximum value of 640% ± 20% in the blended films measured with film‐on‐water method. These results highlight the importance of molecular weight for electronic devices. In addition, this study provides valuable insights into appropriate polymer selections for stretchable semiconducting thin films that simultaneously possess excellent mechanical and electrical properties.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Commodity Thermoplastic Elastomer-Enabled Templated Synthesis of Large-Pore Ordered Mesoporous Materials

Fabrication of ordered mesoporous materials (OMMs) has predominantly relied on templating-based methods. However, these methods are constrained by several limitations, especially the limited pore sizes attainable with commercially available surfactants used as structure-directing agents. To unlock the full potential of the OMMs, it is essential to develop synthetic strategies that facilitate the production of large-pore OMMs using scalable processes and cost-effective precursors. This work demonstrates the use of thermoplastic elastomer (TPE)-derived carbon replicas for synthesizing ordered mesoporous silica (OMS) and metal oxides (OMMOs) via precursor infiltration and template removal. The nanostructural evolution of the resulting inorganic materials was systematically investigated. Specifically, using tetraethyl orthosilicate (TEOS) as a silica precursor, this method can produce an OMS with relatively large pores. To establish the generalizability of this process, the fabrication approach was extended to other commercially available TPEs with varied chemical compositions and molecular weights while consistently resulting in ordered structures. Additionally, this synthetic strategy can be successfully applied to the production of OMMOs, including tin and titanium oxide matrix chemistries, yielding pore sizes of 16.0 and 19.2 nm, respectively. By developing a general method and using low-cost precursors, this work presents a scalable approach for fabricating large-pore OMMs with tunable pore textures and matrix chemistries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

All-Polyhydroxyalkanoate Triblock Copolymers via a Stereoselective-Chemocatalytic Route

Biodegradable polyhydroxyalkanoate (PHA) homopolymers and statistical copolymers are ubiquitous in microbially produced PHAs, but the step-growth polycondensation mechanism the biosynthesis operates on presents a challenge to access well-defined block copolymers (BCPs), especially higher-order tri-BCP PHAs. We report a stereoselective-chemocatalytic route to produce discrete hard–soft–hard ABA all-PHA tri-BCPs based on the living chain-growth ring-opening polymerization of racemic (rac) 8-membered diolides (rac-8DL R ; R denotes the two substituents on the ring). Depending on the composition of the soft B block, originated from rac-8DL R (R = Et, n Bu), and its ratio to the semicrystalline, high-melting hard A block, derived from rac-8DL Me , the resulting all-PHA tri-BCPs with high molar mass (M n up to 238 kg mol –1 ) and low dispersity (&#208: = 1.07) exhibit tunable mechanical properties characteristic of a strong and tough thermoplastic, elastomer, or a semicrystalline thermoplastic elastomer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

All-acrylic multigraft copolymer superelastomers

Thermoplastic elastomer compositions comprising acrylic multigraft copolymers are described. The multigraft copolymers comprise a rubbery polyacrylate backbone and a plurality of randomly spaced glassy polyacrylate side chains. The multigraft copolymers can be prepared using a facile grafting through method that can provide copolymers with enhanced purity. The acrylic multigraft copolymers exhibit microphase separated morphologies and “superelastomeric” properties, including an elongation at break, stress at break, and/or strain recovery behavior that exceeds that of conventional triblock copolymer polyacrylate thermoplastic elastomers.

Mays, Jimmy W.↗