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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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29 records · Page 2

Complementary Semiconducting Polymer Blends: Influence of Side Chains of Matrix Polymers

The concept of complementary semiconducting polymer blends (c-SPBs) has been recently proposed to achieve enhanced solution processability and/or melt-processing capability for organic electronics. In the previous study, we demonstrated the impact of conjugation-break spacers of matrix polymers. In the current work, we explore the influence of the side chains of the matrix polymer on the physical properties of the pure polymers and their corresponding c-SPBs, including electrical properties and phase transition behaviors. Specifically, six diketopyrrolopyrrole (DPP)-based polymers with pentamethylene conjugation-break spacers (CBSs) and various side chains, including branched-alkyl, triethylene glycol (TEG), and siloxaneterminated side chains, were synthesized and characterized. The UV–vis spectra show that the side chains have a noticeable impact on the intermolecular interactions in the solid states. In addition, side chains also have a significant influence on the thermal behaviors of the polymers. Polymers with asymmetric side chains attached to the same DPP unit exhibit lower melting points compared to the congeners with symmetric side chains. The polymer with both branched-alkyl and TEG side chain exhibits the lowest melting point of 104 °C. As for charge transport properties, polymers with branched-alkyl and/or siloxaneterminated side chains give hole mobilities on the same order of magnitude, whereas the polymers with TEG side chains exhibits much lower mobilities. When c-SPBs with a fully conjugated polymer with branched-alkyl side chains are concerned, the c-SPBs of all polymers, except for the polymer with only TEG side chains (TEG-DPP-C5), show hole mobilities 2 orders of magnitude higher than the corresponding pure matrix polymers. In contrast, TEG-DPP-C5 merely presents an improvement of 20 times, which resulted from the incompatibility of TEG side chains from the matrix polymer and the alkyl side chains from the tie chain polymer. These results provide new insights into structural design for semiconducting materials with both high performance and better processability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Manufacturing of Continuous Microporous Polymeric Fibers for Separation Applications

Polyolefin plastic waste, particularly polypropylene, is one of the most prevalent components in the plastic waste stream generated globally. However, only a small fraction of this waste is recycled and reintegrated into second applications. These materials have significant embedded energy that could be used for additional productivity if recycled properly. Therefore, there is a critical need to develop scalable processing techniques with high throughput to effectively recycle it. We report the continuous manufacturing of microporous fibers using waste polypropylene plastic and melt-processable lignin, a plant biomass constituent produced as a byproduct in paper mills or biorefineries, as a template to create pores. Further, these filaments with hierarchical porosity─created by controlled microphase separation during high-speed extensional flow followed by removal of lignin─exhibit exceptional capillary action for hydrophobic liquids. The resulting porous fibers can be used for various separation applications. For example, the oil uptake of the fibers is 9.59 ± 0.82 g/g for applications in oil recovery in bodies of water. In addition, polyethylenimine infiltration within these nanoporous fibers introduces cyclic room temperature sorption and thermal desorption potential of acidic gases such as CO 2 in a bench-scale experiment. The fibers exhibit multiple cycles of CO 2 absorption, with a range of 0.15 to 0.17 mmol/g. Thus, these polyethylenimine-infiltered nanoporous polypropylene fibers can also be used in removing acidic gases from a gas mixture.

36 MATERIALS SCIENCE↗

Amplifying Nanoparticle Reinforcement through Low Volume Topologically Controlled Chemical Coupling

Here, we present a streamlined method to covalently bond hydroxylated carbon nanotubes (CNOH) within a polyphenol matrix, all achieved through a direct, solvent-free process. Employing an extremely small concentration of CNOH (0.01% w/w) along with topologically contrasting linkers led to a maximum of 5-fold increase in modulus and a 25% enhancement in tensile strength compared to the unaltered matrix, an order of magnitude greater reinforcement (w/w) compared to state-of-the-art melt-processed nanocomposites. Through dynamic mechanical analysis, low field solid-state nuclear magnetic resonance spectroscopy, and molecular dynamics simulations, we uncovered the profound influence of linker’s conformational degrees of freedom on the segmental dynamics and therefore the material’s properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hybrid Bismuth Halide with Rich Polymorphism and Second Harmonic Generation Response

Hybrid structures have emerged as a promising class of optical materials, due to their ability to couple the robustness of inorganic and the tunability of organic compounds. However, their application in nonlinear optics (NLO) remains limited, largely due to underexplored factors that drive the formation of noncentrosymmetric structures and NLO property characterization. In this work, we explore the formation, structural and temperature polymorphism, and optical properties of the (Et 3 NH) 3 Bi 2 Br 9 composition, which crystallizes as either noncentrosymmetric or centrosymmetric polymorph. Structural analysis showed that the alignment of [Bi 2 Br 9 ] 3– units dictates the symmetry of phases, as well as the nonlinear optical properties, with the triclinic polymorph exhibiting a second harmonic generation (SHG) response both in visible and IR regions (1.29 × KH 2 PO 4 and 0.08 × AgGaS 2 ). Thermal analysis reveals polymorphic phase transitions and low melting points, making them melt-processable and ionic liquid candidates.

36 MATERIALS SCIENCE↗

Redesigned Hybrid Nylons with Optical Clarity and Chemical Recyclability

Aliphatic polyamides, or nylons, are typically highly crystalline and thermally robust polymers used in high-performance applications. Nylon 6, a high-ceiling-temperature (HCT) polyamide from e-caprolactam, lacks expedient chemical recyclability, while low-ceiling temperature (LCT) nylon 4 from pyrrolidone exhibits complete chemical recyclability, but it is thermally unstable and not melt-processable. Here, we introduce a hybrid nylon, nylon 4/6, based on a bicyclic lactam composed of both HCT ..epsilon..-caprolactam and LCT pyrrolidone motifs in a hybridized offspring structure. Hybrid nylon 4/6 overcomes trade-offs in (de)polymerizability and performance properties of the parent nylons, exhibiting both excellent polymerization and facile depolymerization characteristics. This stereoregular polyamide forms nanocrystalline domains, allowing optical clarity and high thermal stability, however, without displaying a melting transition before decomposition. Of a series of statistical copolymers comprising nylon 4/6 and nylon 4, a 50/50 copolymer achieves the greatest synergy in both reactivity and polymer properties of each homopolymer, offering an amorphous nylon with favorable properties, including optical clarity, a high glass transition temperature, melt processability, and full chemical recyclability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

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↗

Microstructure and thermomechanical properties relationship of segmented thermoplastic polyurethane (TPU)

Thermoplastic polyurethanes (TPU) are important polymeric materials for seals. In competition with Acrylonitrile butadiene rubbers (NBR), TPU exhibits higher strength and a considerable better abrasion resistance. The advantage of NBR over TPU is a smaller compression set but however TPU excels in its much shorter processing cycle times. Generally a TPU is a block copolymer composed of hard and soft segments, which plays an important role in determining the material properties. TPU can be processed either to ready moulded parts or can be incorporated by multi component moulding, in both cases it shows decent mechanical properties. In the present work, the relationship between melt-process induced TPU morphology and resultant thermo mechanical properties were examined and determined by means of quasi-static tensile test, creep experiment, tension test and dynamical mechanical analysis (DMA). Scanning electron beam microscope (SEM) and differential scanning calorimeter (DSC) were used to study the morphology of the samples. A significant mathematical description of the stress-strain behaviour of TPU was found using a 3 term approach. Moreover it became evident that processing conditions such as processing temperature have crucial influence on morphology as well as short and long-term performance. To be more precise, samples processed at higher temperatures showed a lack of large hard segment agglomerates, a smaller strength for strains up to 250% and higher creep compliance.

36 MATERIALS SCIENCE↗

FY16 Annual Accomplishments - Waste Form Development and Performance: Evaluation Of Ceramic Waste Forms - Comparison Of Hot Isostatic Pressed And Melt Processed Fabrication Methods

FY16 efforts were focused on direct comparison of multi-phase ceramic waste forms produced via melt processing and HIP methods. Based on promising waste form compositions previously devised at SRNL, simulant material was prepared at SRNL and a portion was sent to the Australian Nuclear Science and Technology Organization (ANSTO) for HIP treatments, while the remainder of the material was melt processed at SRNL. The microstructure, phase formation, elemental speciation, and leach behavior, and radiation stability of the fabricated ceramics was performed. In addition, melt-processed ceramics designed with different fractions of hollandite, zirconolite, perovskite, and pyrochlore phases were investigated. for performance and properties.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Characterization of Covetic Materials for Process Control. Final CRADA report

GDC Industries LLC has been performing process research on covetic materials since its formation in February 2015. With assistance from DOE and the Air Force via SBIR projects, GDC focused on the enhancement of aluminum alloys to covetics to replicate a previously reported electrical conductivity of about 67% IACS (International Annealed Copper Standard). GDC has established a joint development agreement with General Cable Corporation, wherein General Cable agreed to perform numerous extrusions of as cast covetics and subsequent tensile and electrical conductivity tests on the resultant wire. Covetics conversion was proven but the significant improvement is yet to be replicated. To control the experiments towards enhanced process control, a series of designed experiments was created by an expert in process control from the automotive industry. Six process variables were identified and a designed experiment matrix requiring 18 independent conversions was created at GDC. The result of those designed experiments has now allowed GDC to focus on two process variables, namely, residence time and DC current in the conversions with the other four variable held constant. While this work is useful in replicating the earlier enhancements, GDC feels it will not be sufficient for the necessary process knowhow for scale up required by industry as GDC still does not have a direct correlation of the process variables to the actual carbon in the finished covetics. Since 2015, GDC has been aware of the capabilities existing at Argonne National Laboratory for performing carbon analysis that exceeds the precision commonly available to Industry. GDC and ANL submitted a proposal in response to the DOE-EERE – Small Business Vouchers Pliot Program announcement and the proposal was selected for funding. GDC will melt-process covetic aluminum samples following their design of experiment criteria and have the as-casted samples extruded by their partner, General Cable. Argonne will measure the conductivity, analyze carbon content, perform X-ray diffraction, and examine the microstructural features of the samples. Careful process variable measurements will be recorded by each party such that correlations can be developed indicating process parameters that yield the best carbon concentration in covetics.

36 MATERIALS SCIENCE↗

Lignin-derived thermoplastic co-polymers and methods of preparation

The present invention relates to a crosslinked lignin comprising a lignin structure having methylene or ethylene linking groups therein crosslinking between phenyl ring carbon atoms, wherein said crosslinked lignin is crosslinked to an extent that it has a number-average molecular weight of at least 10,000 g/mol, is melt-processible, and has either a glass transition temperature of at least 100.degree. C., or is substantially soluble in a polar organic solvent or aqueous alkaline solution. Thermoplastic copolymers containing the crosslinked lignin are also described. Methods for producing the crosslinked lignin and thermoplastic copolymers are also described.

36 MATERIALS SCIENCE↗