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At least 955 records · Page 53

Space Durable Polyimide/Carbon Nanotube Composite Films for Electrostatic Charge Mitigation

Low color, space environmentally durable polymeric films with sufficient electrical conductivity to mitigate electrostatic charge (ESC) build-up have been under investigation as part of a materials development activity. These materials have potential applications on advanced spacecraft, particularly on large, deployable, ultra-light weight Gossamer spacecraft. The approach taken to impart sufficient electrical conductivity into the polymer film is based on the use of single walled carbon nanotubes (SWNT) as conductive additives. Earlier approaches investigated in our lab involved both an in-situ polymerization approach and addition of SWNT to an oligomer containing reactive end-groups as methods to improve SWNT dispersion. The work described herein is based on the spray coating of a SWNT/solvent dispersion onto the film surface. Two types of polyimides were investigated, one with reactive end groups that can lead to bond formation between the oligomer chain and the SWNT surface and those without reactive end-groups. Surface conductivities (measured as surface resistance) in the range sufficient for ESC mitigation were achieved with minimal effects on the mechanical, optical, thermo-optical properties of the film as compared to the other methods. The chemistry and physical properties of these nanocomposites will be discussed.

Watson, Kent A.↗

Miniature High-Force, Long-Stroke SMA Linear Actuators

Improved long-stroke shape-memory-alloy (SMA) linear actuators are being developed to exert significantly higher forces and operate at higher activation temperatures than do prior SMA actuators. In these actuators, long linear strokes are achieved through the principle of displacement multiplication, according to which there are multiple stages, each intermediate stage being connected by straight SMA wire segments to the next stage so that relative motions of stages are additive toward the final stage, which is the output stage. Prior SMA actuators typically include polymer housings or shells, steel or aluminum stages, and polymer pads between successive stages of displacement-multiplication assemblies. Typical output forces of prior SMA actuators range from 10 to 20 N, and typical strokes range from 0.5 to 1.5 cm. An important disadvantage of prior SMA wire actuators is relatively low cycle speed, which is related to actuation temperature as follows: The SMA wires in prior SMA actuators are typically made of a durable nickel/titanium alloy that has a shape-memory activation temperature of 80 C. An SMA wire can be heated quickly from below to above its activation temperature to obtain a stroke in one direction, but must then be allowed to cool to somewhat below its activation temperature (typically, less than or equal to 60 C in the case of an activation temperature of 80 C) to obtain a stroke in the opposite direction (return stroke). At typical ambient temperatures, cooling times are of the order of several seconds. Cooling times thus limit cycle speeds. Wires made of SMA alloys having significantly higher activation temperatures [denoted ultra-high-temperature (UHT) SMA alloys] cool to the required lower return-stroke temperatures more rapidly, making it possible to increase cycle speeds. The present development is motivated by a need, in some applications (especially aeronautical and space-flight applications) for SMA actuators that exert higher forces, operate at greater cycle speeds, and have stronger housings that can withstand greater externally applied forces and impacts. The main novel features of the improved SMA actuators are the following: 1) The ends of the wires are anchored in compact crimps made from short steel tubes. Each wire end is inserted in a tube, the tube is flattened between planar jaws to make the tube grip the wire, the tube is compressed to a slight U-cross-section deformation to strengthen the grip, then the crimp is welded onto one of the actuator stages. The pull strength of a typical crimp is about 125 N -- comparable to the strength of the SMA wire and greater than the typical pull strengths of wire-end anchors in prior SMA actuators. Greater pull strength is one of the keys to achievement of higher actuation force; 2) For greater strength and resistance to impacts, housings are milled from aluminum instead of being made from polymers. Each housing is made from two pieces in a clamshell configuration. The pieces are anodized to reduce sliding friction; 3) Stages are made stronger (to bear greater compression loads without excessive flexing) by making them from steel sheets thicker than those used in prior SMA actuators. The stages contain recessed pockets to accommodate the crimps. Recessing the pockets helps to keep overall dimensions as small as possible; and, 4) UHT SMA wires are used to satisfy the higher-speed/higher-temperature requirement.

Cummin, Mark A.↗

A Review of Direct Ink Writing of Polymer Derived Ceramics

With the growing demand for materials capable of withstanding extreme temperatures and pressures, ceramic components with exceptional corrosion resistance and reliable mechanical properties have experienced a significant surge in demand. However, traditional ceramic forming methods involve high-temperatures and energy-intensive processes that often struggle to produce complex parts or composites efficiently. Polymer-Derived Ceramics (PDCs) offer a transformative solution by using polymeric precursors that can be converted into a wide variety of silicon-based and non-silicon-based ceramics through heat treatment. The polymeric nature of PDC precursors enables the fabrication of geometrically intricate components using conventional polymer-forming techniques at significantly lower processing temperatures. Furthermore, PDCs are well-suited for additive manufacturing (AM), allowing the production of complex structural and functional components through cost-effective, low-temperature processes. By leveraging the diverse properties of PDC materials – each with unique advantages and limitations – manufacturers can optimise performance for specific applications. This review provides an overview of the types of PDCs developed to date and their broad range of applications. Specifically, it delves into the Direct Ink Writing (DIW) process, exploring its rheological requirements and the critical role of fillers in tailoring the rheological properties of polymeric precursors to meet the specific demands of DIW.

Victoria Bishop↗

Increased Static Charge–Induced Threshold Voltage Shifts and Memristor Activity in Pentacene OFETs Comprising Polystyrene–Based Gate Dielectrics Containing Electroactive Small Molecule Crystallites

Top-contact bottom-gate pentacene OFETs are fabricated with single layer dielectrics comprised of either polystyrene (PS), poly(4-methylstyrene) (P4MS), or poly(4-tert-butylstyrene) (P4TBS). The polystyrenes are blended with varying concentrations of two different small molecules, dibenzotetrathiafulvalene (DBTTF) and 2,8-difluoro-5,11-bis(triethylsilylethynyl)anthradithiophene (diF-TES-ADT), to form small, separated crystallites contained throughout the polymer dielectric layer. The OFET characteristics of these devices are investigated and their threshold voltage shifts are measured after –70 V static charging for 5 min. Two-terminal measurements are conducted using multiple different gate biases in the range of –50 to +50 V to investigate memristor behavior in the devices. OFETs containing DBTTF exhibited ΔVth increases as large as 330% relative to control OFETs containing no DBTTF, while OFETs containing at least 7.5 wt.% DBTTF exhibited memristor activity, with currents ranging from 20 nA to 44 µA depending on the applied bias. Furthermore, this work demonstrates that including small, separated crystallites in polymer dielectrics enhances their charge storage ability and can be promising for creating nonbinary memory devices for data processing. Additionally, the observed memristor activity indicates the OFETs in this work can be used in development of neuromorphic systems that aim to mimic the synaptic behavior of the human nervous system.

25 ENERGY STORAGE↗

Ab initio Quantum Chemical Studies of Reactions in Astrophysical Ices. Reactions Involving CH3OH, CO2, CO, HNCO in H2CO/NH3/H2O Ices

While reactions between closed shell molecules generally involve prohibitive barriers in the gas phase, prior experimental and theoretical studies have demonstrated that some of these reactions are significantly enhanced when confined within an icy grain mantle and can occur efficiently at temperatures below 100 K with no additional energy processing. The archetypal case is the reaction of formaldehyde (H2CO) and ammonia (NH3) to yield hydroxymethylamine (NH2CH2OH). In the present work we have characterized reactions involving methanol (CH3OH), carbon dioxide (CO2), carbon monoxide (CO), and isocyanic acid (HNCO) in search of other favorable cases. Most of the emphasis is on CH3OH, which was investigated in the two-body reaction with one H2CO and the three-body reaction with two H2CO molecules. The addition of a second H2CO to the product of the reaction between CH3OH and H2CO was also considered as an alternative route to longer polyoxymethylene polymers of the -CH2O- form. The reaction between HNCO and NH3 was studied to determine if it can compete against the barrierless charge transfer process that yields OCN(-) and NH4(+). Finally, the H2CO + NH3 reaction was revisited with additional benchmark calculations that confirm that little or no barrier is present when it occurs in ice.

Woon, David E.↗

The effect of Low Earth Orbit exposure on some experimental fluorine and silicon-containing polymers

Several experimental fluorine and silicon-containing polymers in film form were exposed to low Earth orbit (LEO) on a Space Shuttle flight experiment (STS-46, Evaluation of Oxygen Interaction with Materials, EOIM-3). The environmental parameters of primary concern were atomic oxygen (AO) and ultraviolet (UV) radiation. The materials were exposed to 2.3 plus or minus 0.1 x 10(exp 20) oxygen atoms/sq cm and 30.6 UV sun hours during the flight. In some cases, the samples were exposed at ambient, 120 C and 200 C. The effects of exposure on these materials were assessed utilizing a variety of characterization techniques including optical, scanning electron (SEM) and scanning tunneling (STM) microscopy, UV-visible (UV-VIS) transmission, diffuse reflectance infrared (DR-FTIR), x-ray photoelectron (XPS) spectroscopy, and in a few cases, gel permeation chromatography (GPC). In addition, weight losses of the films, presumably due to AO erosion, were measured. The fluorine-containing polymers exhibited significant AO erosion and exposed films were diffuse or 'frosted' in appearance and consequently displayed dramatic reductions in optical transmission. The silicon-containing films exhibited minimum AO erosion and the optical transmission of exposed films was essentially unchanged. The silicon near the exposed surface in the films was converted to silicate/silicon oxide upon AO exposure which subsequently provided protection for the underlying material. The silicon-containing epoxies are potentially useful as AO resistant coatings and matrix resins as they are readily processed into carbon fiber reinforced composites and cured via electron radiation.

Connell, John W.↗

An in situ generated polymer electrolyte via anionic ring-opening polymerization for lithium–sulfur batteries

The use of solid polymer electrolytes has previously proven to be an effective approach to address the lithium polysulfide dissolution and high electrode interfacial impedance of Li–S batteries via an in situ polymerization process. However, the conventional in situ synthesis employs a cationic ring-opening polymerization (CROP) of 1,3-dioxolane (DOL) catalyzed by a strong Lewis acid. New polymerization chemistry that is more compatible with Li–S chemistry needs to be developed to mitigate the disadvantages associated with the CROP process. Herein we report a new approach to in situ polymerize a set of new episulfide monomers in solution with LiTFSI salt via an anionic ring-opening polymerization (AROP). This new polymer system takes advantage of the inherent cell chemistry present in the Li–S cell through the nucleophilic lithium sulfides which are generated during the initial discharge cycle and act as the initiator for the polymerization. Additionally, their presence was shown to initiate the monomer solvents through AROP with no need for additional catalysts, rather than the more commonly utilized cationic systems which require an external Lewis acid catalyst. This work offers an important pathway toward in situ polymer electrolytes for Li–S batteries and offers a new avenue of exploration for polymer electrolyte synthesis.

25 ENERGY STORAGE↗

Anisotropic Dynamics and Mechanics of Macromolecular Crystals Containing Lattice-Patterned Polymer Networks

The mechanical and functional properties of many crystalline materials depend on cooperative changes in lattice arrangements in response to external perturbations. However, the flexibility and adaptiveness of crystalline materials are limited. Additionally, the bottom-up, molecular-level design of crystals with desired dynamic and mechanical properties at the macroscopic level remains a considerable challenge. To address these challenges, we had previously integrated mesoporous, cubic ferritin crystals with hydrogel networks, resulting in hybrid materials (polymer integrated crystals or PIX) which could undergo dramatic structural changes while maintaining crystalline periodicity and display efficient self-healing. Here, the dynamics and mechanics of these ferritin-PIX were devoid of directionality, which is an important attribute of many molecular and macroscopic materials/devices. In this study, we report that such directionality can be achieved through the use of ferritin crystals with anisotropic symmetries (rhombohedral or trigonal), which enable the templated formation of patterned hydrogel networks in crystallo. The resulting PIX expand and contract anisotropically without losing crystallinity, undergo prompt bending motions in response to stimuli, and self-heal efficiently, capturing some of the essential features of sophisticated biological devices like skeletal muscles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Rheology guiding the design and printability of aqueous colloidal composites for additive manufacturing

Vat photopolymerization (VP) and direct ink write (DIW) additive manufacturing (AM) provide complex geometries with precise spatial control employing a vast array of photo-reactive polymeric systems. Although VP is recognized for superior resolution and surface finish, DIW provides versatility for higher viscosity systems. However, each AM platform presents specific rheological requirements that are essential for successful 3D printing. First, viscosity requirements constrain VP polymeric materials to viscosities below 10 Pa s. Thus, this requirement presents a challenging paradox that must be overcome to attain the physical performance of high molecular weight polymers while maintaining suitable viscosities for VP polymeric materials. Second, the necessary rheological complexity that is required for DIW pastes requires additional rheological measurements to ensure desirable thixotropic behavior. Further, this manuscript describes the importance of rheological measurements when designing polymeric latexes for AM. Latexes effectively decouple the dependency of viscosity on molecular weight, thus enabling high molecular weight polymers with low viscosities. Photo-crosslinking of water-soluble monomers and telechelic oligomeric diacrylates in the presence of the latex enables the fabrication of a scaffold, which is restricted to the continuous aqueous phase and effectively surrounds the latex nanoparticles enabling the printing of otherwise inaccessible high molecular weight polymers. Rheological testing, including both steady and oscillatory shear experiments, provides insights into system properties and provides predictability for successful printing. This perspective article aims to provide an understanding of both chemical functionality (photo- and thermal-reactivity) and rheological response and their importance for the successful design and evaluation of VP and DIW processable latex formulations.

36 MATERIALS SCIENCE↗

Lewis Acid‐Activated Charge Trapping in Dielectric Polymers for Superior High‐Temperature Electrostatic Energy Storage

Dielectric polymer capacitors are essential for electrostatic energy storage but suffer from charge transport-induced energy losses, particularly at elevated temperatures where thermally activated charge carriers exacerbate conduction. Conventional mitigation strategies rely on introducing heterogeneous interfaces to create charge traps, complicating scalable film fabrication. A homogeneous molecular trapping mechanism would circumvent these complexities, yet remains underexplored. Herein, a charge trapping strategy is devised by modifying the lowest occupied molecular orbitals of dielectric polymers through Lewis acid-base adduct formation. The use of tris(pentafluorophenyl)boron (BCF) as a Lewis acidic molecular additive introduces deeper charge traps in commercial polyetherimide (PEI) while retaining homogeneity. With only 0.5 wt.% loading, the PEI-BCF film exhibits greatly improved breakdown strength, achieving an ultrahigh discharged energy density of 7.3 J cm-3 with excellent cycle stability at 200 °C. This work establishes a facile molecular approach to decoupling charge trapping from heterogeneous interfaces, enabling high-energy-density polymer capacitors operable under extreme thermal conditions.

Fan, Lu↗

Multifunctional Polymers and Composites for Aerospace Applications

System needs and challenges for commercial aviation and space exploration are constantly changing. Multifunctional materials are ideal for aerospace applications because their integration into structural components has the potential to not only improve efficiency, but it can increase payload and mission capabilities without the burden of significant additions to mass and volume. Multiconstituent materials will play an important role in enabling structures with the potential to demonstrate true multifunctionality; however, modifications to traditional polymer processing methods may be necessary. This presentation will cover multifunctional materials development efforts underway at the NASA Glenn Research Center pertaining to fabricating novel electrical insulation to advance electric aircraft propulsion, impact resistant and electrically conductive textiles for space, and hybrid reinforcement for toughened polymer matrix composites.

Textiles↗

3D Additive Construction with Regolith for Surface Systems

Planetary surface exploration on Asteroids, the Moon, Mars and Martian Moons will require the stabilization of loose, fine, dusty regolith to avoid the effects of vertical lander rocket plume impingement, to keep abrasive and harmful dust from getting lofted and for dust free operations. In addition, the same regolith stabilization process can be used for 3 Dimensional ( 3D) printing, additive construction techniques by repeating the 2D stabilization in many vertical layers. This will allow in-situ construction with regolith so that materials will not have to be transported from Earth. Recent work in the NASA Kennedy Space Center (KSC) Surface Systems Office (NE-S) Swamp Works and at the University of Southern California (USC) under two NASA Innovative Advanced Concept (NIAC) awards have shown promising results with regolith (crushed basalt rock) materials for in-situ heat shields, bricks, landing/launch pads, berms, roads, and other structures that could be fabricated using regolith that is sintered or mixed with a polymer binder. The technical goals and objectives of this project are to prove the feasibility of 3D printing additive construction using planetary regolith simulants and to show that they have structural integrity and practical applications in space exploration.

Technology Portfolio System↗

Hydrocarboxylation of C=C Bonds in Polycyclooctene: Progress Toward Valorization of Waste Polyolefins

Upcycling of waste polyolefins into higher-value functional polymers through chemical functionalization is a promising strategy to recover value and minimize their environmental impact. We report the hydrocarboxylation of polycyclooctene as a model for accessing ethylene acrylic acid copolymers (EAA) from waste polyethylene. The effects of various process parameters on the hydrocarboxylation were investigated. The relationship between carboxylic acid concentration and material properties, including crystallinity, melting temperature, glass transition temperature, adhesive properties, and wettability, was studied in comparison to an unfunctionalized polyethylene. Among the catalysts evaluated, Co 2 (CO) 8 exhibited relatively slow kinetics toward the hydrocarboxylation and was not compatible with 2,6-di-tert-butyl hydroxytoluene, a common additive present in commercial polyolefins. PdCl 2 (PPh 3 ) 2 exhibited a higher reactivity toward the hydrocarboxylation, though polymer gelation was observed with extended reaction times or high catalyst loadings. Carboxylic acid incorporation into the polymer was readily controlled by varying the reaction time. Altogether, the resultant COOH-functionalized polyolefins possessed properties analogous to commercial EAA.

36 MATERIALS SCIENCE↗

Vibronic exciton model for low bandgap donor–acceptor polymers

In this study, a vibronic exciton model is introduced to describe the excited state band structure and associated absorption spectra of low bandgap donor–acceptor conjugated polymers. The Hamiltonian is represented in a diabatic basis consisting of Frenkel-like donor and acceptor fragment excitations as well as charge-transfer (CT) excitations between neighboring fragments. States are coupled to each other through electron and hole transfer as well as Coulombically, through interacting fragment transition dipole moments. Local vibronic coupling involving the prominent aromatic-quinoidal vibrational mode, which is responsible for pronounced vibronic progressions in most conjugated oligomers and polymers, is also included. The DAD repeat unit is shown to behave like a J-aggregate trimer, driven by both the sizable in-phase electron and hole transfer integrals between donor and acceptor fragments as well as negative Coulomb coupling between donor and acceptor fragment excitations. The J-aggregate behavior is enhanced in the polymer limit through inter-repeat unit coupling, with the 0–0 vibronic peak significantly enhanced in the lowest-energy near-IR band. In addition, the radiative rate is enhanced by the number of coherently connected repeat units. The near-IR band is shown to possess roughly equal admixtures of CT and Frenkel-like excitations. Applications are made to the polymer PffBT4T-2DT, with the simulated absorption spectrum quantitatively capturing the salient features of the measured spectrum.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Enhancing Heavy-Oil-Recovery Efficiency by Combining Low-Salinity-Water and Polymer Flooding

Summary Combining low-salinity-water (LSW) and polymer flooding was proposed to unlock the tremendous heavy-oil resources on the Alaska North Slope (ANS). The synergy of LSW and polymer flooding was demonstrated through coreflooding experiments at various conditions. The results indicate that the high-salinity polymer (HSP) (salinity = 27,500 ppm) requires nearly two-thirds more polymer than the low-salinity polymer (LSP) (salinity = 2,500 ppm) to achieve the target viscosity at the condition of this study. Additional oil was recovered from LSW flooding after extensive high-salinity-water (HSW) flooding [3 to 9% of original oil in place (OOIP)]. LSW flooding performed in secondary mode achieved higher recovery than that in tertiary mode. Also, the occurrence of water breakthrough can be delayed in the LSW flooding compared with the HSW flooding. Strikingly, after extensive LSW flooding and HSP flooding, incremental oil recovery (approximately 8% of OOIP) was still achieved by LSP flooding with the same viscosity as the HSP. The pH increase of the effluent during LSW/LSP flooding was significantly greater than that during HSW/HSP flooding, indicating the presence of the low-salinity effect (LSE). The residual-oil-saturation (Sor) reduction induced by the LSE in the area unswept during the LSW flooding (mainly smaller pores) would contribute to the increased oil recovery. LSP flooding performed directly after waterflooding recovered more incremental oil (approximately 10% of OOIP) compared with HSP flooding performed in the same scheme. Apart from the improved sweep efficiency by polymer, the low-salinity-induced Sor reduction also would contribute to the increased oil recovery by the LSP. A nearly 2-year pilot test in the Milne Point Field on the ANS has shown impressive success of the proposed hybrid enhanced-oil-recovery (EOR) process: water-cut reduction (70 to less than 15%), increasing oil rate, and no polymer breakthrough so far. This work has demonstrated the remarkable economical and technical benefits of combining LSW and polymer flooding in enhancing heavy-oil recovery.

Engineering↗

Constitutive Modeling of Piezoelectric Polymer Composites

A new modeling approach is proposed for predicting the bulk electromechanical properties of piezoelectric composites. The proposed model offers the same level of convenience as the well-known Mori-Tanaka method. In addition, it is shown to yield predicted properties that are, in most cases, more accurate or equally as accurate as the Mori-Tanaka scheme. In particular, the proposed method is used to determine the electromechanical properties of four piezoelectric polymer composite materials as a function of inclusion volume fraction. The predicted properties are compared to those calculated using the Mori-Tanaka and finite element methods.

Odegard, Gregory M.↗

Space environmental effects on materials

Research efforts at NASA-Langley to characterize the durability of composite materials which are candidates for use as components on various space hardware systems are reviewed. The material applications include large space structures, antennas, cables, thermal control coatings, solar reflectors, and satellite power systems. Simulation facilities have been built to study radiation effects on polymer matrix composites, and the dimensional stability of the matrix composites and tension stabilized cables. Numerical models are being developed for radiation effects on the mechanical, physical, and optical properties. Additionally, chemical and microstructural analyses are performed to identify damage mechanisms and the limits of effectiveness of accelerating life tests. It is noted that no residual strength reduction has been detected in polymer films after dosages of 5 billion rads of electron radiation.

Tenney, D. R.↗

Depolymerization of Hydroxylated Polymers via Light-Driven C–C Bond Cleavage

The accumulation of persistent plastic waste in the environment is widely recognized as an ecological crisis. New chemical technologies are necessary both to recycle existing plastic waste streams into high-value chemical feedstocks and to develop next-generation materials that are degradable by design. Here, we report a catalytic methodology for the depolymerization of a commercial phenoxy resin and high molecular weight hydroxylated polyolefin derivatives upon visible light irradiation near ambient temperature. Proton-coupled electron transfer (PCET) activation of hydroxyl groups periodically spaced along the polymer backbone furnishes reactive alkoxy radicals that promote chain fragmentation through C–C bond β-scission. The depolymerization produces well-defined and isolable product mixtures that are readily diversified to polycondensation monomers. In addition to controlling depolymerization, the hydroxyl group modulates the thermomechanical properties of these polyolefin derivatives, yielding materials with diverse properties. Furthermore, these results demonstrate a new approach to polymer recycling based on light-driven C–C bond cleavage that has the potential to establish new links within a circular polymer economy and influence the development of new degradable-by-design polyolefin materials.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗