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All sourcesNASA NTRSDOE OSTI
NASA NTRS2012

High-Temperature Shape Memory Polymers

physical conformation changes when exposed to an external stimulus, such as a change in temperature. Such materials have a permanent shape, but can be reshaped above a critical temperature and fixed into a temporary shape when cooled under stress to below the critical temperature. When reheated above the critical temperature (Tc, also sometimes called the triggering or switching temperature), the materials revert to the permanent shape. The current innovation involves a chemically treated (sulfonated, carboxylated, phosphonated, or other polar function group), high-temperature, semicrystalline thermoplastic poly(ether ether ketone) (Tg .140 C, Tm = 340 C) mix containing organometallic complexes (Zn++, Li+, or other metal, ammonium, or phosphonium salts), or high-temperature ionic liquids (e.g. hexafluorosilicate salt with 1-propyl-3- methyl imidazolium, Tm = 210 C) to form a network where dipolar or ionic interactions between the polymer and the low-molecular-weight or inorganic compound forms a complex that provides a physical crosslink. Hereafter, these compounds will be referred to as "additives". The polymer is semicrystalline, and the high-melt-point crystals provide a temporary crosslink that acts as a permanent crosslink just so long as the melting temperature is not exceeded. In this example case, the melting point is .340 C, and the shape memory critical temperature is between 150 and 250 C. PEEK is an engineering thermoplastic with a high Young fs modulus, nominally 3.6 GPa. An important aspect of the invention is the control of the PEEK functionalization (in this example, the sulfonation degree), and the thermal properties (i.e. melting point) of the additive, which determines the switching temperature. Because the compound is thermoplastic, it can be formed into the "permanent" shape by conventional plastics processing operations. In addition, the compound may be covalently cross - linked after forming the permanent shape by S-PEEK by applying ionizing radiation ( radiation, neutrons), or by chemical crosslinking to form a covalent permanent network. With respect to other shape memory polymers, this invention is novel in that it describes the use of a thermoplastic composition that can be thermally molded or solution-cast into complex "permanent" shapes, and then reheated or redissolved and recast from solution to prepare another shape. It is also unique in that the shape memory behavior is provided by a non-polymer additive.

Yoonessi, Mitra↗
DOE OSTI2023

Subtle Molecular Changes Largely Modulate Chiral Helical Assemblies of Achiral Conjugated Polymers by Tuning Solution-State Aggregation

Understanding the solution-state aggregate structure and the consequent hierarchical assembly of conjugated polymers is crucial for controlling multiscale morphologies during solid thin-film deposition and the resultant electronic properties. However, it remains challenging to comprehend detailed solution aggregate structures of conjugated polymers, let alone their chiral assembly due to the complex aggregation behavior. Herein, we present solution-state aggregate structures and their impact on hierarchical chiral helical assembly using an achiral diketopyrrolopyrrole-quaterthiophene (DPP-T4) copolymer and its two close structural analogues wherein the bithiophene is functionalized with methyl groups (DPP-T2M2) or fluorine atoms (DPP-T2F2). Combining in-depth small-angle X-ray scattering analysis with various microscopic solution imaging techniques, we find distinct aggregate in each DPP solution: (i) semicrystalline 1D fiber aggregates of DPP-T2F2 with a strongly bound internal structure, (ii) semicrystalline 1D fiber aggregates of DPP-T2M2 with a weakly bound internal structure, and (iii) highly crystalline 2D sheet aggregates of DPP-T4. These nanoscopic aggregates develop into lyotropic chiral helical liquid crystal (LC) mesophases at high solution concentrations. Intriguingly, the dimensionality of solution aggregates largely modulates hierarchical chiral helical pitches across nanoscopic to micrometer scales, with the more rigid 2D sheet aggregate of DPP-T4 creating much larger pitch length than the more flexible 1D fiber aggregates. Combining relatively small helical pitch with long-range order, the striped twist-bent mesophase of DPP-T2F2 composed of highly ordered, more rigid 1D fiber aggregate exhibits an anisotropic dissymmetry factor (g-factor) as high as 0.09. This study can be a prominent addition to our knowledge on a solution-state hierarchical assembly of conjugated polymers and, in particular, chiral helical assembly of achiral organic semiconductors that can catalyze an emerging field of chiral (opto)electronics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2000

Microgravity Platforms

The world's space agencies have been conducting microgravity research since the beginning of space flight. Initially driven by the need to understand the impact of less than- earth gravity physics on manned space flight, microgravity research has evolved into a broad class of scientific experimentation that utilizes extreme low acceleration environments. The U.S. NASA microgravity research program supports both basic and applied research in five key areas: biotechnology - focusing on macro-molecular crystal growth as well as the use of the unique space environment to assemble and grow mammalian tissue; combustion science - focusing on the process of ignition, flame propagation, and extinction of gaseous, liquid, and solid fuels; fluid physics - including aspects of fluid dynamics and transport phenomena; fundamental physics - including the study of critical phenomena, low-temperature, atomic, and gravitational physics; and materials science - including electronic and photonic materials, glasses and ceramics, polymers, and metals and alloys. Similar activities prevail within the Chinese, European, Japanese, and Russian agencies with participation from additional international organizations as well. While scientific research remains the principal objective behind these program, all hope to drive toward commercialization to sustain a long range infrastructure which .benefits the national technology and economy. In the 1997 International Space Station Commercialization Study, conducted by the Potomac Institute for Policy Studies, some viable microgravity commercial ventures were identified, however, none appeared sufficiently robust to privately fund space access at that time. Thus, government funded micro gravity research continues on an evolutionary path with revolutionary potential.

Del Basso, Steve↗
DOE OSTI2022

Activated relaxation in supercooled monodisperse atomic and polymeric WCA fluids: Simulation and ECNLE theory

Here, we combine simulation and Elastically Collective Nonlinear Langevin Equation (ECNLE) theory to study the activated relaxation in monodisperse atomic and polymeric Weeks–Chandler–Andersen (WCA) liquids over a wide range of temperatures and densities in the supercooled regime under isochoric conditions. By employing novel crystal-avoiding simulations, metastable equilibrium dynamics is probed in the absence of complications associated with size polydispersity. Based on a highly accurate structural input from integral equation theory, ECNLE theory is found to describe well the simulated density and temperature dependences of the alpha relaxation time of atomic fluids using a single system-specific parameter, a c , that reflects the nonuniversal relative importance of local cage and collective elastic barriers. For polymer fluids, the explicit dynamical effect of local chain connectivity is modeled at the fundamental dynamic free energy trajectory level based on a different parameter, N c , that quantifies the degree of intramolecular correlation of bonded segment activated barrier hopping. For the flexible chain model studied, a physically intuitive value of N c ≈ 2 results in good agreement between simulation and theory. A direct comparison between atomic and polymeric systems reveals that chain connectivity can speed up activated segmental relaxation due to weakening of equilibrium packing correlations but can slow down relaxation due to local bonding constraints. The empirical thermodynamic scaling idea for the alpha time is found to work well at high densities or temperatures but fails when both density and temperature are low. The rich and subtle behaviors revealed from simulation for atomic and polymeric WCA fluids are all well captured by ECNLE theory.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1993

Defects in electro-optically active polymer solids

There is considerable current interest in the application of organic and polymeric materials for electronic and photonic devices. The rapid, non-linear optical (NLO) response of these materials makes them attractive candidates for waveguides, interferometers, and frequency doublers. In order to realize the full potential of these systems, it is necessary to develop processing schemes which can fabricate these molecules into ordered arrangements. There is enormous potential for introducing well-defined, local variations in microstructure to control the photonic properties of organic materials by rational 'defect engineering.' This effort may eventually become as technologically important as the manipulation of the electronic structure of solid-state silicon based devices is at present. The success of this endeavor will require complimentary efforts in the synthesis, processing, and characterization of new materials. Detailed information about local microstructure will be necessary to understand the influence of symmetry breaking of the solid phases near point, line, and planar defects. In metallic and inorganic polycrystalline materials, defects play an important role in modifying macroscopic properties. To understand the influence of particular defects on the properties of materials, it has proven useful to isolate the defect by creating bicrystals between two-component single crystals. In this way the geometry of a grain boundary defect and its effect on macroscopic properties can be determined unambiguously. In crystalline polymers it would be valuable to establish a similar depth of understanding about the relationship between defect structure and macroscopic properties. Conventionally processed crystalline polymers have small crystallites (10-20 nm), which implies a large defect density in the solid state. Although this means that defects may play an important or even dominant role in crystalline or liquid crystalline polymer systems, it also makes it difficult to isolate the effect of a particular boundary on a macroscopically observed property. However, the development of solid-state and thin-film polymerization mechanisms have facilitated the synthesis of highly organized and ordered polymers. These systems provide a unique opportunity to isolate and investigate in detail the structure of covalently bonded solids near defects and the effect of these defects on the properties of the material. The study of defects in solid polymers has been the subject of a recent review (Martin, 1993).

Martin, David C.↗
NASA NTRS1974

Study to define behavior of liquid lubricants in an elastohydrodynamic contact

The spectra of an ester and a saturated hydrocarbon polymer were obtained at pressures ranging from ambient to 2 GN/sq m (20 kilobar) and at temperatures between ambient and 180 C in absorption and between 150 C and 210 C in emission. To simulate contact conditions the fluids were contained in the tiny sample volume of a diamond cell, i.e., the hole in a metal spacer separating two diamonds pressed against each other in a nut crackerlike arrangement. Pressures could be deduced from bandshifts and states of aggregation from bandwidths in the fluorescence spectrum of a ruby crystal immersed in the fluids. An infrared Fourier transform spectrometer was used with attachments specially designed to analyze the radiation passed through the sample and both diamonds (absorption technique) or the radiation emanating from the heated sample and passing through only one diamond (emission technique). The latter technique is applicable to operating EHD contacts. Spectral changes pointing to possible glass transitions and composition changes were observed. Emission and absorption spectra were generally equivalent. Some emission bandshapes appear to be temperature sensitive enough to be useful as internal temperature probes.

Lauer, J. L.↗
NASA NTRS1998

Thin Film Mediated Phase Change Phenomena: Crystallization, Evaporation and Wetting

We focus on two distinct materials science problems that arise in two distinct microgravity environments: In space and within the space of a polymeric network. In the former environment, we consider a near eutectic alloy film in contact with its vapor which, when evaporating on earth, will experience compositionally induced buoyancy driven convection. The latter will significantly influence the morphology of the crystallized end member. In the absence of gravity, the morphology will be dominated by molecular diffusion and Marangoni driven viscous flow, and we study these phenomena theoretically and experimentally. The second microgravity environment exists in liquids, gels, and other soft materials where the small mass of individual molecules makes the effect of gravity negligible next to the relatively strong forces of intermolecular collisions. In such materials, an essential question concerns how to relate the molecular dynamics to the bulk rheological behavior. Here, we observe experimentally the diffusive motion of a single molecule in a single polymer filament, embedded within a polymer network and find anomalous diffusive behavior.

Wettlaufer, John S.↗
DOE OSTI2021

Anhydrous vs Hydrated f-Element Acetate Polymers Dictated by the Stoichiometry of Protic Acidic/Basic Azole Mixtures

Continuing our investigations of ionic liquid (IL) based routes to a library of f-element/soft donor complexes which could be studied crystallographically, we have explored the dissolution of f-element salts in protic imidazole-based ILs containing only soft donors at high temperatures to drive off volatiles, including water and carboxylic or mineral acids. Here we present our results, reacting acidic and basic azoles in 1:3 or 1:1 stoichiometric compositions at elevated temperature, followed by saturation with Nd(OAc) 3 ·xH 2 O or Ce(OAc) 3 ·xH 2 O, which led to 13 new metal–acetate polymeric complexes identified by single-crystal X-ray diffraction. We found that the diversity in coordination modes of the simple acetate ligand that interfere with substitution of the softer N donors led to several readily crystallizable complexes forming two distinct groups with respect to f-element interaction with the ionic liquid precursors. When the acidic/basic azole ratio was 1:3, acetate and a neutral basic azole were found to be coordinated to the metal centers but no water, although in one case (2) water was observed in the secondary coordination sphere: [Ce(μ 2 -OAc) 3 (C 1 im)] n (1, C 1 im = 1-methylimidazole), [Nd(μ 2 -(OAc) 3 (C 1 im)] n ·nH 2 O (2), [Ce(μ 2 -OAc) 3 (C 2 im)] n (3, C 2 im = 1-ethylimidazole), [Ln(μ 2 -OAc) 3 DMF] n (Ln = Nd (4), Ce (5); dimethylformamide (DMF) was substituted for the azole mixture), and [Nd(μ 2 -OAc) 3 (C 4 im)] n (6, C 4 im = 1-butylimidazole). However, when the stoichiometric ratio was 1:1, water was always observed coordinated to the metal ions with the acidic azole included in the structure as a solvate or cocrystal, despite a higher reaction temperature: [Nd(μ 2 -OAc) 3 (OH 2 )] n ·n(1,2,3-Taz) (7, 1,2,3-Taz = 1,2,3-triazole), [Ln(μ 2 -OAc) 3 (OH 2 )] n ·n(4,5-DCim) (Ln = Nd (8), Ce (9), 4,5-DCim = 4,5-dicyanoimidazole), [Ln(μ 2 -OAc) 3 (OH 2 )] n ·n(3,5-diNH 2 -1,2,4-Taz) (Ln = Nd (10), Ce (11), 3,5-diNH 2 -1,2,4-Taz = 3,5-diamino-1,2,4-triazole), [Ce(μ 2 -OAc) 3 (OH 2 )] n ·n(3-NH 2 -1,2,4-Taz) (12, 3-NH 2 -1,2,4-Taz = 3-amino-1,2,4-triazole), and [Nd(μ 2 -OAc) 3 (OH 2 )] n ·n(5-NH 2 -Tz) (13, 5-NH2-Tz = 5-aminotetrazole). All of the compounds retain the Ln:OAc– ratio of 1:3 and form 1D polymeric chains; however, they exhibit a variety of coordination modes affecting the degree of chain condensation. The isolation of both hydrated and anhydrous products revealed different abilities of the investigated soft N-donors to compete with O-donors finding their place in the coordination sphere of the lanthanide or in the crystal lattice.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Hierarchical assemblies of polypeptoids for rational design of advanced functional nanomaterials

Polypeptoids (poly-N-substituent glycines) are a class of highly tailorable peptidomimetic polymers. Polypeptoids have identical backbones as polypeptides (poly-C-substituent glycines), but sidechains of polypeptoids are appended to backbone nitrogen rather than α-carbon of polypeptides. As a result, peptoid backbone lacks of chirality and hydrogen bond donors. This unique structure gives polypeptoids a combined merit of both high stability as synthetic polymers and biocompatibility as biopolymers. In addition, peptoid sequences can be engineered precisely to assemble specific crystalline patterns such as spheres, fibers, ribbons, tubes, and sheets, which shows promising potentials of polypeptoids for different applications such as antimicrobials, catalysts, drug delivery, and templating inorganic materials. In this review, we summarize recent investigations into hierarchical self-assembly pathways and molecular structures of peptoid crystals that are of interest as templates for fabricating functional materials for potential biomedical, biochemical, and bioengineering applications. Furthermore, this review provides a summary of recent experimental and computational studies of polypeptoid assembly in solution and solid-liquid interfaces, current achievements in the field, and discusses future challenges and opportunities for the rational design of self-assembled polypeptoid nanomaterials.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Effect of Polymer Chain Length on the Superlattice Assembly of Functionalized Gold Nanoparticles

We report on the assembly of gold nanoparticle (AuNPs) superlattices at the liquid/vapor interface and in the bulk of their suspensions. Interparticle distances in the assemblies are achieved on multiple length scales by varying chain lengths of surface grafted AuNPs by polyethylene glycol (PEG) with molecular weights in the range 2000–40,000 Da. Crystal structures and lattice constants in both 2D and 3D assemblies are determined by synchrotron-based surface-sensitive and small-angle X-ray scattering. Here, assuming knowledge of grafting density, we show that experimentally determined interparticle distances are adequately modeled by spherical brushes close to the θ point (Flory–Huggins parameter, x ≈ 1/2) for 2D superlattices at a liquid interface and a nonsolvent (χ = ∞) for the 3D dry superlattices.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Strongly Correlated Ion Dynamics in Plastic Ionic Crystals and Polymerized Ionic Liquids

Understanding the mechanisms controlling ionic conductivity is critical for the development of the next generation of batteries and supercapacitors. This paper discusses the significant role played by ionic correlations in conductivity of concentrated ionic systems. Our studies of an organic ionic plastic crystal reveal that correlations in ions dynamics suppress conductivity by 25–100 times in comparison to the expected uncorrelated ionic conductivity estimated from the Nernst–Einstein relationship. Furthermore, additional analysis also demonstrates that ionic correlations suppress conductivity in polymerized ionic liquids and gel by ~10 times. Thus, ionic correlations, usually neglected in many studies, play a very important role in conductivity of concentrated ionic systems. These results cannot be explained by a diffusion of ion pairs because all these systems are essentially single ion conductors. In contrast, strongly correlated motions of mobile ions with the same charge (cation–cation or anion–anion correlations) are the major mechanism suppressing the ionic conductivity in these systems. Finally, on the basis of these results, we emphasize that charge transport rather than ion diffusion is critical for electrolyte performance and suggest the potential design of plastic crystals and polymer electrolytes with enhanced ionic conductivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

A twist grain boundary phase in aqueous solutions of the nucleic acid tetramer GTAC

At high concentration, long Watson/Crick (WC) double-helixed DNA forms columnar crystal or liquid crystal phases of linear, parallel duplex chains packed on periodic lattices. This can also be a structural motif of short NA oligomers such as the 5’-GTAC-3’ studied here, which makes four-base WC duplexes having hydrophobic blunt ends. End-to-end aggregation then assembles these duplexes into columns and columnar phases are stabilized, in spite of breaks in the double helix every four bases. But the new degrees of freedom introduced by such breaks also enable opportunities for a more diverse palette of self-assembly modes, producing striking self-assemblies of DNA that would not be achievable with contiguous polymers. These include recently reported three-dimensional (3D) periodic low-density nanoscale networks of GCCG, and the twist grain boundary (TGB) phase presented here. In the TGB, columns of GTAC pairs assemble into monolayer sheets in which the duplex columns are mutually parallel. However, unlike in the columnar crystals, these sheets stack in helical fashion into lamellar arrays in which the column axis of each layer is rotated through a 60° angle with respect to the columns in neighboring layers. This assembly of DNA is unique in that it the fills a 3D volume wherein the major grooves of columns in each layer mutually enter and interlock with the major grooves of columns in neighboring layers. This locking is optimized by small adjustments in structure enabled by the breaks in the duplex backbones.

DNA↗
DOE OSTI2023

Pertechnetate/perrhenate–capped Zr/Hf–Dihydroxide Dimers: Elucidating Zr–TcO 4 Co–Mobility in the Nuclear Fuel Cycle

Spent nuclear fuel contains heavy element fission products that must be separated for effective reprocessing for a safe and sustainable nuclear fuel cycle. 93 Zr and 99 Tc are high-yield fission products that co-transport in liquid-liquid extraction processes. Here we seek atomic-level information of this co-extraction process, as well as fundamental knowledge about Zr IV (and Hf IV ) aqueous speciation in the presence of topology-directing ligands such as pertechnetate (TcO 4 – ) and non-radioactive surrogate perrhenate (ReO 4 – ). In this context, we show that the flat tetrameric oxyhydroxyl-cluster [M IV 4 (OH) 8 (H 2 O) 16 ] 8+ (and related polymers) is dissociated by perrhenate/pertechnetate to yield isostructural dimers, M 2 (OH) 2 (XO 4 – ) 6 (H 2 O) 6 • 3H 2 O (M=Zr/Hf IV ; X=Re/Tc VII ), elucidated by single-crystal X-ray diffraction. We used these model compounds to understand the pervasive 93 Zr- 99 Tc coextraction with further speciation studies in water, nitric acid, and tetrabutylphosphate (TBP) -kerosene; where the latter two media are relevant to nuclear fuel reprocessing. SAXS (small angle X-ray scattering), compositional evaluation, and where experimentally feasible, ESI-MS (electrospray ionization mass spectrometry) showed that perrhenate/pertechnetate influence Zr/Hf IV -speciation in water. Here, in Zr-XO 4 solvent extraction studies to simulate fuel reprocessing, we provide evidence that TcO 4 – enhances extraction of Zr IV , and compositional analysis of the extracted metal-complexes (Zr-ReO 4 study) is consistent with the crystallized Zr IV 2 (OH) 2 (Re VII O 4 – ) 6 (H 2 O) 6 •dimer.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
NASA NTRS2013

Polymer-Reinforced, Non-Brittle, Lightweight Cryogenic Insulation

The primary application for cryogenic insulating foams will be fuel tank applications for fueling systems. It is crucial for this insulation to be incorporated into systems that survive vacuum and terrestrial environments. It is hypothesized that by forming an open-cell silica-reinforced polymer structure, the foam structures will exhibit the necessary strength to maintain shape. This will, in turn, maintain the insulating capabilities of the foam insulation. Besides mechanical stability in the form of crush resistance, it is important for these insulating materials to exhibit water penetration resistance. Hydrocarbon-terminated foam surfaces were implemented to impart hydrophobic functionality that apparently limits moisture penetration through the foam. During the freezing process, water accumulates on the surfaces of the foams. However, when hydrocarbon-terminated surfaces are present, water apparently beads and forms crystals, leading to less apparent accumulation. The object of this work is to develop inexpensive structural cryogenic insulation foam that has increased impact resistance for launch and ground-based cryogenic systems. Two parallel approaches will be pursued: a silica-polymer co-foaming technique and a post foam coating technique. Insulation characteristics, flexibility, and water uptake can be fine-tuned through the manipulation of the polyurethane foam scaffold. Silicate coatings for polyurethane foams and aerogel-impregnated polyurethane foams have been developed and tested. A highly porous aerogel-like material may be fabricated using a co-foam and coated foam techniques, and can insulate at liquid temperatures using the composite foam

Hess, David M.↗
DOE OSTI2023

Thermal Conductivity of a Novel Salt-Hydrogel Complex as a Phase Change Material for Building Thermal Management

Use of electricity for space heating, ventilation and air conditioning in buildings may be better managed through temporary energy storage. Compared with electrochemical storage, the levelized cost of thermal energy storage systems can be lower depending on geographical location and thermophysical properties [1]. In any phase change material (PCM), the rate of absorption and release of thermal energy increases with higher thermal conductivity [2]. However, leading PCMs like paraffin waxes have thermal conductivities on the order of 0.1 W/mK. Glauber’s salt, a salt hydrate, possesses a relatively high thermal conductivity but suffers from supercooling and phase segregation. Research has shown that polymer-based composites with salt hydrates can prevent phase segregation and limit supercooling over hundreds of cycles [3] though the thermal conductivity of the composite may be reduced leading to low energy storage rates. Here, we report thermal conductivity measurements on polymer hydrogels which are stable in solutions of Glauber’s salt. To measure thermal conductivity of soft gels, we use a 3-omega method [4] where heat flows bidirectionally through a substrate below and through a gel placed on top. This suits measurements of both gels and liquids unlike transient plane heat source or transient hot wire methods. We report measurements of thermal conductivity of salt-hydrogel complexes as a function of temperature, cross-linking and salt concentration. In addition, we present modeling of thermal conductivity of sodium sulfate solutions with available theories. We finally employ polarized optical microscopy to observe inside the transparent hydrogel networks, showing that precipitating crystals may influence thermal conductivity measurements for high salt concentrations. Our thermal conductivity results combined with enthalpy of phase change, mass density and specific heat are essential to accurately design thermal storage systems for energy-efficient buildings.

composite, thermal conductivity↗
NASA NTRS2006

Wholly Aromatic Ether-Imides as n-Type Semiconductors

Some wholly aromatic ether-imides consisting of rod-shaped, relatively-low-mass molecules that can form liquid crystals have been investigated for potential utility as electron-donor-type (ntype) organic semiconductors. It is envisioned that after further research to improve understanding of their physical and chemical properties, compounds of this type would be used to make thin film semiconductor devices (e.g., photovoltaic cells and field-effect transistors) on flexible electronic-circuit substrates. This investigation was inspired by several prior developments: Poly(ether-imides) [PEIs] are a class of engineering plastics that have been used extensively in the form of films in a variety of electronic applications, including insulating layers, circuit boards, and low-permittivity coatings. Wholly aromatic PEIs containing naphthalene and perylene moieties have been shown to be useful as electrochromic polymers. More recently, low-molecular-weight imides comprising naphthalene-based molecules with terminal fluorinated tails were shown to be useful as n-type organic semiconductors in such devices as field-effect transistors and Schottky diodes. Poly(etherimide)s as structural resins have been extensively investigated at NASA Langley Research Center for over 30 years. More recently, the need for multi-functional materials has become increasingly important. This n-type semiconductor illustrates the scope of current work towards new families of PEIs that not only can be used as structural resins for carbon-fiber reinforced composites, but also can function as sensors. Such a multi-functional material would permit so-called in-situ health monitoring of composite structures during service. The work presented here demonstrates that parts of the PEI backbone can be used as an n-type semiconductor with such materials being sensitive to damage, temperature, stress, and pressure. In the near future, multi-functional or "smart" composite structures are envisioned to be able to communicate such important parameters to the flight crew and provide vital information with respect to the operational status of their aircraft.

Weiser, Erik↗
NASA NTRS1992

The study of the thermal behavior of a new semicrystalline polyimide

Thermal properties of a new semicrystalline polyimide synthesized from 3,3',4,4' benzophenone tetracarboxylic dianhydride (BTDA) and 2,2 dimethyl 1,2-(4 aminophenoxy) propane (DMDA) were studied. Heat capacities in the solid and liquid states of BTDA-DMDA were measured. The heat capacity increase at the glass transition temperature (T sub g = 230 C) is 145 J/(C mol) for amorphous BTDA-DMDA. The equilibrium heat of fusion of the BTDA-DMDA crystals was obtained using wide angle X ray diffraction and differential scanning calorimetry measurements, and it is 75.8 kJ/mol. Based on the information of crystallinity and the heat capacity increase at T sub g, a rigid amorphous fraction is identified in semicrystalline BTDA-DMDA samples. The rigid amorphous fraction represents an interfacial region between the crystalline and amorphous states. In particular, this fraction increases with the crystallinity of the sample which should be associated with crystal sizes, and therefore, with crystal morphology. It was also found that this polymer has a high temperature crystal phase upon annealing above its original melting temperature. The thermal degradation activation energies are determined to be 154 and 150 kJ/mol in nitrogen and air, respectively.

Cheng, Stephen Z. D.↗
DOE OSTI2021

Moisture-induced autonomous surface potential oscillations for energy harvesting

A variety of autonomous oscillations in nature such as heartbeats and some biochemical reactions have been widely studied and utilized for applications in the fields of bioscience and engineering. Here, we report a unique phenomenon of moisture-induced electrical potential oscillations on polymers, poly([2-(methacryloyloxy)ethyl] dimethyl-(3-sulfopropyl) ammonium hydroxide-co-acrylic acid), during the diffusion of water molecules. Chemical reactions are modeled by kinetic simulations while system dynamic equations and the stability matrix are analyzed to show the chaotic nature of the system which oscillates with hidden attractors to induce the autonomous surface potential oscillation. Using moisture in the ambient environment as the activation source, this self-excited chemoelectrical reaction could have broad influences and usages in surface-reaction based devices and systems. As a proof-of-concept demonstration, an energy harvester is constructed and achieved the continuous energy production for more than 15,000 seconds with an energy density of 16.8 mJ/cm 2 . A 2-Volts output voltage has been produced to power a liquid crystal display toward practical applications with five energy harvesters connected in series.

42 ENGINEERING↗