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At least 343 records · Page 19

All sources NASA NTRS DOE OSTI

NASA NTRS1984

Liquid crystal polyester-carbon fiber composites

Liquid crystal polymers (LCP) have been developed as a thermoplastic matrix for high performance composites. A successful melt impregnation method has been developed which results in the production of continuous carbon fiber (CF) reinforced LCP prepreg tape. Subsequent layup and molding of prepreg into laminates has yielded composites of good quality. Tensile and flexural properties of LCP/CF composites are comparable to those of epoxy/CF composites. The LCP/CF composites have better impact resistance than the latter, although epoxy/CF composites possess superior compression and shear strength. The LCP/CF composites have good property retention until 200 F (67 % of room temperature value). Above 200 F, mechanical properties decrease significantly. Experimental results indicate that the poor compression and shear strength may be due to the poor interfacial adhesion between the matrix and carbon fiber as adequate toughness of the LCP matrix. Low mechanical property retention at high temperatures may be attributable to the low beta-transition temperature (around 80 C) of the LCP matrix material.

Chung, T. S.↗

DOE OSTI2021

Design, synthesis, and characterization of vinyl-addition polynorbornenes with tunable thermal properties

Unfunctionalized vinyl-addition polynorbornene (VAPNB) possesses many outstanding properties such as high thermal, chemical, and oxidative stability. These features make VAPNB a promising candidate for many engineering applications. However, VAPNB has a small service window between its glass transition temperature (T g ) and decomposition temperature (T d ), and it cannot be readily processed in a melt state. In this work, we demonstrate that the service window of VAPNBs can be tailored through the use of norbornene monomers bearing alkyl, aryl, and aryl ether substituents. The vinyl addition homopolymerization and copolymerization of these functionalized norbornyl-based monomers yielded VAPNBs with high T' g s (>150 °C) and large service windows (T d –T g > 100 °C), which are comparable to other commercial engineering thermoplastics. To further establish the feasibility of melt processing, a functionalized VAPNB material with T g = 209 °C and a service window of 170 °C was successfully extruded and molded into bars. Subsequent characterization of the bars by dynamic mechanical analysis (DMA), nuclear magnetic resonance spectroscopy (NMR), and gel permeation chromatography (GPC) revealed only minor signs of polymer degradation. Furthermore, these studies suggest that substituted VAPNBs could be developed into a new class of engineering thermoplastics that is compatible with workhorse melt processing techniques such as extrusion and injection molding, as well as emerging techniques such as extrusion-based 3D printing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Effect of Graft Molecular Weight and Density on the Mechanical Properties of Polystyrene-Grafted Cellulose Nanocrystal Films

In this work, polymer-grafted nanoparticle (PGN) films were prepared from polystyrene (PS) grafted to rodlike cellulose nanocrystals (MxG-CNC-g-PS) with a controllable grafting density (0.03–0.25 chains/nm 2 ) and molecular weight (5–60 kg/mol). These nanorod-based PGNs are solution- and melt-processible, permitting access to one-component composite films with high nanofiller loadings (with up to 55 wt %). The impact of both grafted polymer density and molecular weight on the mechanical properties of the films was investigated and related to the polymer brush conformation: concentrated polymer brush (CPB), semidilute polymer brush (SDPB), or CPB core with SDPB corona (CPB/SDPB). The rubbery regime storage modulus (above $T_g$) showed 2 orders of magnitude increase, maximizing at a low degree of polymerization (N) and low grafting density (σ). Fracture toughness was maximized in samples with the grafted polymer in the SDPB or CPD/SDPB (higher N and relatively low σ) regime and showed enhancement relative to PS of molecular weight similar to the graft. In line with prior computation predictions, optimizing for both rubbery modulus and fracture toughness in such nanorod-based PGN films requires the polymers in the SDPB regime and CNC loading levels (ca. 50–60 wt %) that are difficult to attain in more traditional two-component CNC composites.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Boundary layer description of directional polymer crystallisation

Nearly fifty years ago Lovinger and Gryte suggested that the directional crystallization of a polymer was analogous to the quiescent isothermal crystallization experiment but at a supercooling where the crystal growth velocity was equal to the velocity of the moving front. Our experiments showed that this equivalence holds in a detailed manner at low directional velocities. To understand the underlying physics of these situations, we modeled the motion of a crystallization front in a liquid where the left side boundary is suddenly lowered below the melting point (Stefan's problem) but with the modification that the crystallization kinetics follow a version of the Avrami model. Our numerical results surprisingly showed that the results of the polymer analog track with the Stefan results which were derived for a simple liquid that crystallizes completely at its melting point; in particular, the position of the crystal growth-front evolved with time exactly as in the Stefan problem. The numerical solution also showed that the temperature in the immediate vicinity of the growth-front decreased with increasing front velocity, which is in line with Lovinger and Gryte's ansatz. To provide a clear theoretical understanding of these numerical results we derive a boundary layer solution to the governing coupled differential equations of the polymer problem. The analytical results are in agreement with our observations from experiments and numerical computations but show that this equivalence between the small molecule and polymer analog only holds in the limit where the crystallization enthalpy is much larger than the rate at which heat is conducted away in the polymer. In particular, in the context of the temperature profile, the enthalpy generated by the crystallisation process which is spread out over a narrow spatial region can be approximated as a point source whose location and temperature correspond to the Lovinger–Gryte ansatz.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Polymers in molten inorganic salt hydrate phase change materials: solubility and gelation

Inorganic salt hydrates are of interest as phase change materials (PCMs) for thermal energy storage because of their unique properties, such as high latent heats of fusion, moderate melting temperatures, high volumetric energy storage densities, and enhanced thermal conductivities compared to their organic counterparts. Because of the low viscosities of molten salt hydrates, the leakage and settling of solids can easily occur during their application. Polymers are promising candidates for preventing these issues. In addition, the non-flammability, non-volatility, and nontoxicity of many molten salt hydrates make them attractive options as “green” solvents for polymers. However, solutions of polymers in molten salt hydrates have rarely been studied and are poorly understood. The highly ionic environments in these materials created due to a scarcity of hydration water for ions leads to strong ionic interactions, with ramifications for polymer solubility and chain expansion. This Perspective article aims to focus on polymer solutions and gels in inorganic salt hydrates by comparing these systems with existing knowledge of polymers in traditional ionic liquids and aqueous salt solutions. To provide insight into the states of ions and water in molten salt hydrates and the degree of hydration of polymers in these solvents, infrared spectroscopy experiments have been performed, and the data are correlated with the temperature-responsive gelation of poly(vinyl alcohol), one candidate material currently used for the shape stabilization of inorganic PCMs. Finally, the thermal properties of inorganic salt hydrates and ionic liquids are compared and strategies for the shape stabilization of inorganic salt hydrates using polymers, through the formation of physical gels, are discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1994

Ceramic Tool For Preconsolidation Of Powder-Coated Towpreg

Tool converts partly formed towpreg into preconsolidated towpreg ribbon. In technique, towpreg coated with thermoplastic powder converted into preconsolidated ribbon without use of plasticizers or solvents. Relying on melt flow and proper application of tension, friction, and cooling, technique ensures both consistent distribution of polymer within, and consistent cross section of ribbon. Ceramic preconsolidation tool includes heated and cooled halves thermally insulated from each other.

Baucom, Robert M.↗

NASA NTRS2003

Research to Significantly Enhance Composites Survivability at 550 F in Oxidative Environments

Methylene dianiline (MDA) and its derivatives have been used in the synthesis of polyimides to yield polymers with characteristic low-density, high tensile strength, improved solubility in organic solvents, low-melt viscosities and high thermal stability (greater than 550 F) in air. Polyimides with such properties are desirable for use in aerospace systems, e.g., jet engines, airframe, missiles, and rockets where weight is critical. Recent research at Prairie View A&M University is focused on developing monomers to generate polyimides with enhanced performance over that of NASA s PMR-15. The objective of this work is to synthesize three ring aromatic diamines which are non-toxic and when reacted with the appropriate dianhydrides will yield polyimides with lower viscosity, improve processability, good retention of mechanical properties, and oxidative stability at high environmental temperatures. Modifications of the three ring aromatic diamines include replacing the methylene linkages with aromatic ethers by nucleophilic aromatic substitution reactions and incorporating mono- and di-substituents to the center aromatic ring. An update of current reactions involved in synthesis efforts to generate three ring aromatic monomers for polyimides with methylene, carbonyl, and ether linkages separating the aromatic moieties will be displayed.

Meador, Michael A.↗

NASA NTRS1995

Combustion of a polymer (PMMA) sphere in microgravity

Polymer combustion is a highly complicated process where chemical reactions may occur not only in the gas phase, but also in the condensed phase as well as at the solid-gas interphase. The chemistry depends strongly on the coupling between the condensed phase and gas phase phenomena. For some polymers, additional complications arise due to the formation of char layers. For others, the behavior of the condensed phase involves swelling, bubbling, melting, sputtering, and multi-stage combustion. Some of these features bear resemblance to the phenomena observed in coal particle combustion. In addition to its relevance to spacecraft fire safety, the combustion of polymeric materials is related to many applications including solid and hybrid rocket propulsion, and of recent interest, waste incineration . The burning rate is one of the most important parameters used to characterize the combustion of polymers. It has been used to rank the polymer flammability under the same experimental conditions and to evaluate various modes of inhibiting polymer flammability. The main objective of this work is to measure the burning rates of a polymeric material in low gravity. Because of inherent logistical difficulties involved in microgravity experiments, it is impossible to examine a wide spectrum of polymeric materials. It is desirable to investigate a polymer whose combustion is less complicated, and yet will lead to a better understanding of the burning characteristics of other more complicated materials. Therefore, a typical non-charring polymer is selected for use in this experimental study. PMMA (polymethylmethacrylate) has been chosen because its thermo-physical properties are well characterized. Although the combustion of PMMA has been extensively studied in 1G experiments, only a limited amount of work has been conducted in low gravity. A spherical sample geometry is chosen in this study because it is the simplest configuration in terms of the microgravity hardware design requirements. Furthermore, a burning PMMA sphere in microgravity represents a one-dimensional flame with overall combustion characteristics expected to be analogous to the combustion of a liquid fuel droplet, a field with many well-developed theories and models. However, differences can also be expected such as the flame-front standoff ratios and the condensed phase processes occurring during combustion.

Yang, Jiann C.↗

NASA NTRS1989

Investigations on gel forming media use in low gravity bioseparations research

Research on gelling media and conditions suitable for the preservation of the spatial configuration of cell suspensions and macromolecular solutions after separation in free fluid during low gravity experiments is presented. The examples studied included free electrophoresis of cells in a cylindrical column and two-phase aqueous polymer separation. Microgravity electrophoresis experiments were simulated by separating model cell types (animal or human) in a vertical density gradient containing low-conductivity buffer, 1.7-6.5 percent Ficoll, 6.8-5.0 percent sucrose, and 1 percent SeaPrep low-melting temperature agarose. Upon cooling, a gel formed in the column and cells could be captured at the forming locations. Two-phase extraction experiments were simulated using two-polymer solutions in which phase separation occurs in normal saline at temperatures compatible with cell viability and in which one or both phases form a gel upon cooling. Suitable polymers included commercial agaroses (1-2 percent), maltodextrin (5-7 percent), and gelatin (5-20 percent).

Todd, Paul↗

NASA NTRS1970

Improved process for synthesizing anilinosilane compounds

New process gives good yields of anilinosilane compounds that can be readily isolated in a high state of purity. S-collidine is used as an HCl acceptor. Silane compounds can be melt-condensed with aromatic diols to provide high molecular weight polyaryloxysilane materials that are of importance in polymer technology.

Dunnavant, W. R.↗

NASA NTRS1984

Structures and Properties of Polymers Important to Their Wear Behavior

The wear and transfer of various semicrystalline polymers sliding against smooth steel or glass surfaces were examined. The effects of structures, and properties of polymers on their wear behavior are discussed. It is found that the high wear characteristics of PTFE is due to the easy destruction of the banded structure of PTFE. The size of spherulites and the molecular profile are closely related to the magnitude of wear rates of typical semicrystalline polymers. The effects of these factors on the wear rate on the basis of the destruction or melting of spherulites at the frictional surface are discussed. Although the fatigue theory of wear indicates that some mechanical properties are important to wear behavior, it is shown that the theory does not always explain the experimental result obtained on a smooth surface.

Tanaka, K.↗

NASA NTRS1993

New monomers for high performance polymers

This laboratory has been concerned with the development of new polymeric materials with high thermo-oxidative stability for use in the aerospace and electronics industries. Currently, there is special emphasis on developing matrix resins and composites for the high speed civil transport (HSCT) program. This application requires polymers that have service lifetimes of 60,000 hr at 350 F (177 C) and that are readily processible into void-free composites, preferably by melt-flow or powder techniques that avoid the use of high boiling solvents. Recent work has focused on copolymers which have thermally stable imide groups separated by flexible arylene ether linkages, some with trifluoromethyl groups attached to the aromatic rings. The presence of trifluoromethyl groups in monomers and polymers often improves their solubility and processibility. The goal of this research was to synthesize several new monomers containing pendant trifluoromethyl groups and to incorporate these monomers into new imide/arylene ether copolymers. Initially, work was begun on the synthesis of three target compounds. The first two, 3,5-dihydroxybenzo trifluoride and 3-amino 5-hydroxybenzo trifluoride, are intermediates in the synthesis of more complex monomers. The third, 3,5-bis (3-amino-phenoxy) benzotrifluoride, is an interesting diamine that could be incorporated into a polyimide directly.

Gratz, Roy F.↗

DOE OSTI2024

Efficient and Robust Dynamic Crosslinking for Compatibilizing Immiscible Mixed Plastics through In Situ Generated Singlet Nitrenes

Abstract Creating a sustainable economy for plastics demands the exploration of new strategies for efficient management of mixed plastic waste. The inherent incompatibility of different plastics poses a major challenge in plastic mechanical recycling, resulting in phase‐separated materials with inferior mechanical properties. Here, this study presents a robust and efficient dynamic crosslinking chemistry that effectively compatibilizes mixed plastics. Composed of aromatic sulfonyl azides, the dynamic crosslinker shows high thermal stability and generates singlet nitrene species in situ during solvent‐free melt‐extrusion, effectively promoting C─H insertion across diverse plastics. This new method demonstrates successful compatibilization of binary polymer blends and model mixed plastics, enhancing mechanical performance and improving phase morphology. It holds promise for managing mixed plastic waste, supporting a more sustainable lifecycle for plastics.

Chemistry↗

NASA NTRS1979

Crystalline polyimides

Aromatic crystalline polyimides are disclosed that are synthesized from polyamide-acid and when heated to 200 C to 300 C become cyclized to afford an opaque polymer. X-ray diffraction of the unoriented film exhibited 47 percent crystallinity. Differential scanning calorimetry reveals a melt at 425 C with no glass transition in these crystalline polyimides.

St.clair, T. L.↗

NASA NTRS1987

Thermoplastic matrix composites - LARC-TPI, polyimidesulfone and their blends

Composites were fabricated from unidirectional unsized AS-4 carbon fiber and two baseline polyimides: benzophenone dianhydride-3,3'-diaminodiphenylsulfone (PISO2) and benzophenone dianhydride-3,3'-diaminobenzophenone (LARC-TPI). In addition, each polymer solution prior to prepregging was doped with various amounts of crystalline LARC-TPI powder to enhance melt flow during press molding. The 2:1, 1:1, and 1:2 ratios of crystalline to amorphous resin, respectively, were studied in the LARC-TPI system and the 1:2 ratio in the PISO2 system. Matrix characterization, prepreg fabrication/characterization and composite fabrication and physical/mechanical properties are described. The latter include three point short beam shear and flexure, dry and wet, as well as fracture toughness properties in selected compositions.

Johnston, Norman J.↗

NASA NTRS1985

Concentrations and behavior of oxygen and oxide ion in melts of composition CaO.MgO.xSiO2

The behavior of oxygen and oxide ion in silicate melts was investigated through their electrochemical reactions at a platinum electrode. Values are given for the diffusion coefficient for molecular oxygen in diopside melt and the activation energy of diffusion. It is shown that molecular oxygen dissociates prior to undergoing reduction and that oxide ion reacts quickly with silicate polymers when it is produced. The concentration of oxide ion is kept low by a buffering effect of the silicate, the exact level being dependent on the silicate composition. Data on the kinetics of reaction of the dissociation of molecular oxygen and on the buffering reactions are provided. It is demonstrated that the data on oxygen in these silicate melts are consistent with those for solid buffers.

Semkow, K. W.↗

NASA NTRS2003

Characterizations of Enriched Metallic Single-Walled Carbon Nanotubes in Polymer Composite

Using different processing conditions, we disperse the single-walled carbon nanotube (SWNT) into the polymethyl methacrylate (PMMA) to form composites. In the melt-blended sample, the SWNTs originally semiconducting - became predominantly metallic after dispersion into the melt-blended composite. The interaction of the PMMA and SWNT is investigated by the polarized Raman studies. The structure changes in the PMMA and SWNT shows that the anisotropic interactions are responsible for SWNT electronic density of states (DOS) changes. The increased metallic SWNT percentage is confirmed by the conductivity and dielectric constant measurements .

Chen, Bin↗

NASA NTRS2006

Patches for Repairing Ceramics and Ceramic-Matrix Composites

Patches consisting mostly of ceramic fabrics impregnated with partially cured polymers and ceramic particles are being developed as means of repairing ceramics and ceramic-matrix composites (CMCs) that must withstand temperatures above the melting points of refractory metal alloys. These patches were conceived for use by space-suited, space-walking astronauts in repairing damaged space-shuttle leading edges: as such, these patches could be applied in the field, in relatively simple procedures, and with minimal requirements for specialized tools. These design characteristics also make the patches useful for repairing ceramics and CMCs in terrestrial settings. In a typical patch as supplied to an astronaut or repair technician, the polymer would be in a tacky condition, denoted as an A stage, produced by partial polymerization of a monomeric liquid. The patch would be pressed against the ceramic or CMC object to be repaired, relying on the tackiness for temporary adhesion. The patch would then be bonded to the workpiece and cured by using a portable device to heat the polymer to a curing temperature above ambient temperature but well below the maximum operating temperature to which the workpiece is expected to be exposed. The patch would subsequently become pyrolized to a ceramic/glass condition upon initial exposure to the high operating temperature. In the original space-shuttle application, this exposure would be Earth-atmosphere-reentry heating to about 3,000 F (about 1,600 C). Patch formulations for space-shuttle applications include SiC and ZrO2 fabrics, a commercial SiC-based pre-ceramic polymer, and suitable proportions of both SiC and ZrO2 particles having sizes of the order of 1 m. These formulations have been tailored for the space-shuttle leading-edge material, atmospheric composition, and reentry temperature profile so as to enable repairs to survive re-entry heating with expected margin. Other formulations could be tailored for specific terrestrial applications.

Hogenson, Peter A.↗