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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 253 records · Page 14
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Structural, Thermal, and Mechanical Characterization of a Thermally Conductive Polymer Composite for Heat Exchanger Applications

Polymer composites are being considered for numerous thermal applications because of their inherent benefits, such as light weight, corrosion resistance, and reduced cost. In this work, the microstructural, thermal, and mechanical properties of a 3D printed polymer composite with high thermal conductivity are examined using multiple characterization techniques. Infrared spectroscopy and X-ray diffraction reveal that the composite contains a polyphenylene sulfide matrix with graphitic fillers, which is responsible for the high thermal conductivity. Furthermore, differential scanning calorimetry determines that the glass transition and melting point of the composite are 87.6 °C and 285.6 °C, respectively. Thermogravimetric analysis reveals that the composite is thermally stable up to ~400 °C. Creep tests are performed at different isotherms to evaluate the long-term performance of the composite. The creep result indicates that the composite can maintain mechanical integrity when used below its glass transition temperature. Nanoindentation tests reveal that modulus and hardness of the composite is not significantly influenced by heating or creep conditions. These findings indicate that the composite is potentially suitable for heat exchanger applications.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Mechanical and Thermal Characterization of Phase-Change Material and High-Density Polyethylene Functional Composites for Thermal Energy Storage

Abstract Phase-change materials (PCMs) can be used to develop thermal energy storage systems as they absorb large amount of latent heat nearly at a constant temperature when changing phase from a solid to a liquid. To prevent leakage when in a liquid state, PCM is shape stabilized in a polymer matrix of high-density polyethylene (HDPE). The present research explores the injection-molded mechanical and thermal properties of different PCM/HDPE composite ratios. The tensile strength and modulus of elasticity at room temperature and with the PCM fully melted within the composite are measured. Additionally, the hardness, latent heat of fusion, phase-change temperature, and thermal conductivity are investigated. An analysis of microstructures of the composite is used to support the findings. The PCM within the PCM/HDPE composite gives it the benefit of thermal storage but causes a decrease in mechanical properties.

Energy & Fuels↗
DOE OSTI2021

Sub-nanometer confinement enables facile condensation of gas electrolyte for low-temperature batteries

Abstract Confining molecules in the nanoscale environment can lead to dramatic changes of their physical and chemical properties, which opens possibilities for new applications. There is a growing interest in liquefied gas electrolytes for electrochemical devices operating at low temperatures due to their low melting point. However, their high vapor pressure still poses potential safety concerns for practical usages. Herein, we report facile capillary condensation of gas electrolyte by strong confinement in sub-nanometer pores of metal-organic framework (MOF). By designing MOF-polymer membranes (MPMs) that present dense and continuous micropore (~0.8 nm) networks, we show significant uptake of hydrofluorocarbon molecules in MOF pores at pressure lower than the bulk counterpart. This unique property enables lithium/fluorinated graphite batteries with MPM-based electrolytes to deliver a significantly higher capacity than those with commercial separator membranes (~500 mAh g −1 vs. <0.03 mAh g −1 ) at −40 °C under reduced pressure of the electrolyte.

25 ENERGY STORAGE↗
DOE OSTI2021

Developing a New Polyolefin Precursor for Low-Cost, High-Strength Carbon Fiber

Current high-strength carbon fibers (CFs) are mostly derived from PAN polymer precursor, which are very expensive with limited usage in the high-end products. On the other hand, it has also stimulated research interest to develop new low-cost precursors and manufacturing process. Despite numerous studies, researchers have yet to develop a new polymeric precursor that is less expensive, melt-spinnable, and offers a high C-yield. In this three-year R&D project, we proposed three consecutive research phases, including (i) the development of new polyolefin-based precursors that can be thermally transformed to C material in one heating step under inert atmosphere and achieved a C-yield >80%, which is more than 60% higher than that of current PAN precursor, (ii) With the suitable new polyolefin-based precursor, we can focus on CF manufacturing process, including fiber spinning, stabilization, and carbonization, to form high quality carbon fibers with the desirable polymorphous morphology, and (iii) the investigation of thermal conversion process under tension for converting polyolefin-based precursor fibers to high tensile strength carbon fibers with specific graphite crystallite size, orientation of basal line, order-disorder ratio, fiber diameter, and reduced structural defect (voids). composites.

08 HYDROGEN↗
DOE OSTI2024

Coherence in Polycrystalline Thin Films of Twisted Molecular Crystals

Helicoidal crystallites in rhythmically banded spherulites manifest spectacular optical patterns in small molecules and polymers. It is shown that concentric optical bands indicating crystallographic orientations typically lose coherence (in-phase twisting) with growth from the center of nucleation. Here, coherence is shown to increase as the twist period decreases for seven molecular crystals grown from the melt. This dependence was correlated to crystallite fiber thickness and length, as well as crystallite branching frequency, a parameter that was extracted from scanning electron micrographs, and supported by numerical simulations. Hole mobilities for 2,5-didodecyl-3,6-di(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (DPP-C12) measured by using organic field-effect transistors demonstrated that more incoherent boundaries between optical bands in spherulites lead to higher charge transport for films with the same twist period. This was rationalized by combining our growth model with electrodynamic simulations. This work illustrates the emergence of complexity in crystallization processes (spherulite formation) that arises in the extra variable of helicoidal radial twisting. The details of the patterns analyzed here link the added complexity in crystal growth to the electronic and optical properties of the thin films.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Mechanically and thermally robust microporous copolymer separators for lithium ion batteries

Next generation, multifunctional separators can enhance energy storage, power, and safety performance of lithium ion batteries but must be simple to fabricate and incorporate with existing roll-to-roll manufacturing. Here, this study presents a strategy to facilely prepare these separators using UV-initiated polymerization-induced phase separation (PIPS), wherein microporous polymer separators are fabricated directly from constituent monomers and ethylene carbonate (EC) porogen. This enables a wide compositional design space as co-monomers with specific chemical functionality can be readily incorporated into the PIPS precursor mixture. Herein, 1,4-butanediol diacrylate (BDDA) was copolymerized with poly(ethylene glycol) diacrylate (PEGDA) to increase the acrylate conversion in the photopolymerization and improve mechanical properties. By tuning the ratio of PEGDA and EC, separators with high porosity (41.3%) and effective ionic conductivity (2.09 mS cm –1 ) were prepared. Inclusion of PEGDA was essential to increasing the elastic modulus to > 345 MPa, which is required for cell assembly by roll-to-roll manufacturing. All separators prepared were shown to enable reversible cycling of lithium metal/LiNi 0.5 Mn 0.3 Co 0.2 O 2 half-cells for 100 cycles. Unlike conventional polyolefin separators, which were shown to melt at 160 °C and shrink by up to 29.8% at elevated temperatures, the PIPS separators possess exceptional, safety-enhancing thermomechanical properties, undergoing no phase transitions or thermal shrinkage.

25 ENERGY STORAGE↗
DOE OSTI2023

Impact of hydrogen bonding pendant groups in polymer grafted nanoparticles on interlayer adhesion and mechanical properties in material extrusion printing

The addition of nanoparticles or copolymer grafted nanoparticles (CPGNPs) to polymeric matrices greatly improves thermomechanical properties of the resulting nanocomposite, but corresponding studies of nanocomposite systems created by 3D printing are few, especially in the realm of functional polymeric materials. Here we describe how silica nanoparticle-grafted, random copolymers of poly(methyl methacrylate-random-2-uriedo-[1H]-pyrimidinone methacrylate) (P(MMA-r-UPyMA) dramatically increases the mechanical properties of poly(methyl methacrylate) (PMMA) based nanocomposite specimens created by melt extrusion printing. Most notably, when these novel CPGNPs are combined with PMMA matrix chains via a solution-based process, printed specimens containing only 0.5 wt% additive show significant increases in Young’s modulus (90%), storage modulus (93%), tensile modulus (148%) and ultimate tensile strength (110%). These improvements are ascribed to strengthening of adhesion across interfaces due to multi-point hydrogen bonding between UPyMA groups, the reinforcement effect of the P(MMA-r-UPyMA)-grafted silica nanoparticles, as well as hydrogen bonding interactions and entanglements between graft and matrix chains. Imaging of fracture surfaces after tensile testing reveals that in comparison to nanocomposites created by simple mechanical mixing of solids, the solution-casting process improves the dispersion of nanoparticles and reduces the void spaces between printed roads. These studies demonstrate that introducing functionality into polymer grafts, such as hydrogen bonding interactions, and intimate mixing of polymer-modified nanomaterials can greatly improve interlayer adhesion and mechanical properties, thereby advancing this method of polymer additive manufacturing

36 MATERIALS SCIENCE↗
DOE OSTI2021

Using Nanofiller Assemblies to Control the Crystallization Kinetics of High-Density Polyethylene

Polyethylene-grafted nanoparticles (NPs) are organized into a variety of assemblies in a polydisperse polyethylene melt by tailoring the graft density and molecular weights of the graft chains. Under these conditions we systematically vary NP assemble state and study is consequences on crystal nucleation and growth rates. We find that the nucleation rate is suppressed below that of the unfilled polymer for good NP spatial dispersion. However, poorer dispersion, which leads to the formation of NP assemblies, can accelerate nucleation likely by providing multiple heterogenous sites due to topographical features. We find that a key parameter, the chain overcrowding in the brush, can predict these nucleation trends – in this language, the most enhanced nucleation rate is found when the grafts are the most overcrowded, and hence the least interpenetrated with the matrix chains. This result is consistent with one other literature result which utilized short crystallizable polyethylene glycol grafts in short PEO matrices. The growth kinetics were retarded for all nanocomposites, their temperature dependences were essentially equal to that for the pure polymer (in the absence of NPs) – the NPs thus do not affect secondary nucleation, indicating that the transport of the matrix to the growth front is the rate determining step. Thus, evidently the increase in matrix viscosity, or reduction in growth rates, is directly determined by the agglomeration state of the NPs. These results are consistent with past works with bare silica NPs in PEO, and with silica NPs grafted with amorphous chains in a PEO matrix, suggesting that growth kinetics in these systems apparently follow “universal” behavior. Additionally, there are initial hints that the ratio of the effective surface area of the NP clusters per unit matrix volume provides a unified description of the NP induced confinement that slows growth kinetics. Furthermore, our work thus shows that there is an evolving understanding of the role of NPs on crystallization kinetics, in particular crystal growth where trends appear to be independent of the grafts ability to crystallize.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Distributed Magnetic Field and Temperature Monitoring for Superconducting Radio Frequency Cavities

The overall objective of the proposed Phase I program was to design, construct and demonstrate a fiber optic sensing system capable of providing temperature and magnetic field measurements with an enhanced spatial resolution that can be implemented over a large surface area (cryomodules) to survey superconducting radio frequency cavities and magnets. A magnetic field sensor capable of detecting fluxes on the order of 1 μT is required to detect the distribution of trapped flux on the cavity surface. A unique distributed magnetic field sensor was successfully designed and constructed to demonstrate the detection of magnetic fluxes less than 500 nT. The sensor leveraged the ultra-high sensitivity of Sentek’s picoDAS to measure the magnetostriction induced vibrations in a commercially available Metglas 2605 SC ribbon that was in physical contact with sensing fiber. Static magnetic fields were detected by applying an alternating current a copper wire proximate to the Metglas 2605SC ribbon to create an AC bias magnetic field. In an alternative approach, an AC bias magnetic field was applied to a special magnetic field sensing fiber with Metglas 2605SC cladding successfully detect a magnetic field flux of a 3 μT. Exhaustive testing was performed to characterize the dependency of sensor response on the direction of the applied magnetic field. Although the special sensing fiber based magnetic field sensor did not exhibit an observable dependence on the direction of the magnetic field, the Metglas 2605SC ribbon sensor exhibited a clear directional dependence. A wide variety of polymer materials were evaluated to enhance the temperature response of an FBG based sensor at cryogenic temperatures. The processing and performance challenges provided the motivation to develop a new simple cryogenic temperature sensor that uses a commercially available fiber optic splice protector. The EVA hot melt tube that becomes adhered to the optical fiber and the polyolefin outer tube that shrinks upon heating in the fusion splicer heater provide the high thermal expansion coefficient necessary to impart a significant strain on the FBG when exposed to cryogenic temperatures. The temperature sensitivity (Δ𝜆𝐵𝑟𝑎𝑔𝑔~ 62 𝑝𝑝𝑚/℃) of the FBG-based sensor was on par with the best reported to date. The simple design, use of readily available cost-effective materials, and well-established processing techniques lends this approach to the creation of hundreds to thousands of temperature sensors on one single optical fiber length. The inherently small form factor also allows for co-location with the distributed magnetic field sensor. In preparation for field testing of the prototype sensing system at the Jefferson Labs in potential Phase II program, several different cable designs were evaluated to package the sensors. The preliminary successful demonstration of fully functional sensing cables provides the foundation for subsequent development efforts to advance the Technology Readiness Level of the technology. The technical feasibility of the proposed approach was successfully demonstrated in this Phase I effort.

43 PARTICLE ACCELERATORS↗
DOE OSTI2021

Effects of a Layered Morphology on Drip Suppression in Burning Polymers

Fire safety in polymers is critically important with products such as textiles and consumer goods, as well as materials used in construction, aerospace, transportation, and furniture. Additives used as anti-dripping and flame-retardant agents impose acute human health issues and have negative environmental impacts. With a focus on developing additive-free solutions, here we used multilayer coextrusion to fabricate layered polyethylene/polypropylene (PE/PP) films and investigated the effect of a layered morphology on dripping and burning rates. The experimental results for multilayered PE/PP samples were compared to control groups of melt blended PE/PP samples. The multilayer configuration provides two significant advantages: 154% delay in the time to the first drip and up to 87% reduction in the number of drips compared to the value for the melt blended samples with no additives. PE/PP blends with up to 2 wt % polytetrafluoroethylene, a commonly used anti-dripping agent in the industry, showed only 85% delay in the time to the first drip and about 60% reduction in the number of drips. We discovered a linear relationship between film thickness and burning rate, which allows for the use of the volumetric burning rate to normalize the effect of film thickness. No benefit in the burning rate was observed when comparing multilayered structures and conventional melt blended architectures or blends with PTFE. Annealing studies and transmission electron microscopy at areas close to the combustion zones confirmed that higher extensional viscosities induced by the layered structures and morphological changes due to the layer breakup play an important role in reducing dripping. By combining the first drip time and overall drip numbers, a parameter, “dripping index”, was defined to establish a fire safety map to simplify material comparisons. This study demonstrates that a multilayer film geometry can provide an additive-free solution to yield control over fire safety parameters in polymers.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Ionic Conductivity Enhancement of Polymer Electrolytes by Directed Crystallization

Here, we report that hot stretching of poly(ethylene oxide) (PEO)-based solid polymer electrolytes (SPEs) can lead to a preferred orientation of PEO crystalline lamellae, thereby reducing the tortuosity of the ion-conduction pathway along the thickness direction of the SPE film, causing improved ionic conductivity. The hot stretching method is implemented by stretching SPE films above the melting point of PEO in an inert environment followed by crystallization at room temperature while maintaining the applied strain. The effect of hot stretching on the crystalline orientation, crystallinity, morphology, and ion transport in PEO with two types of salts, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and lithium triflate (LiCF3SO3), is investigated in detail. Wide-angle X-ray scattering (WAXS) and small-angle X-ray scattering (SAXS) show that the orientation of PEO crystalline lamellae induces the formation of a short ion-conduction pathway along the through-plane direction of the SPE films, leading to 1.4- to 3.5-fold enhancement in the through-plane ionic conductivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Effects of tacticity and chiral center-to-dipole distance on mesogen-free liquid crystalline self-assembly of sulfonyl-containing comb-like polymers

In this report, new approaches were implemented to achieve novel ferroelectric liquid crystalline self-assembly in mesogen-free comb-like isotactic polyoxypropylenes (iPOPs) bearing mono- or di-sulfonyl groups, which have potential to exhibit high spontaneous polarization for applications in advanced electronic devices. iPOPs with n-alkylsulfonylpentylthioether side chains (iPOP-SC 5 SO 2 C n , where C n is the alkyl tail with n being either 12 or 8) were prepared via a post-polymerization substitution reaction from isotactic poly[(R)-(–)-epichlorohydrin]. Here, the effects of main-chain tacticity, chiral center-to-dipole distance, number of sulfonyl dipoles per side chain, and n-alkyl tail length on the liquid crystalline self-assembly behavior were investigated by comparing iPOPs with their atactic counterparts. First, when the sulfonyl dipole was placed far away from the chiral center in iPOP-SC 5 SO 2 C n compared with our previously reported isotactic polyethers with n-alkylsulfonyl side chains (iPOP-SO 2 C n ), the dipole–dipole interactions among the side chains decreased, which led to more liquid crystalline phases. Smectic E (SmE) and A (SmA) phases were observed after crystal melting; however, the main-chain chiral center was found to have an insignificant effect on the liquid crystalline assembly when compared to the atactic samples. Second, the longer C n tails increased the transition temperatures as a result of stronger van der Waals interactions. Third, after the thioether linkage in the side chain was oxidized into the sulfonyl group, the chiral center–dipole and dipole–dipole interactions in the resultant polymers (i.e., iPOP-SO 2 C 5 SO 2 C n ) enhanced. As a result, the liquid crystalline phase transitions (i.e., crystal → SmE → SmA → I) were pushed to higher temperatures. The knowledge gained in this study will help us further design and achieve the ferroelectric smectic C* phase in mesogen-free comb-like sulfonylated liquid crystalline polymers.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Reprocessable polyhydroxyurethane networks reinforced with reactive polyhedral oligomeric silsesquioxanes (POSS) and exhibiting excellent elevated temperature creep resistance

The rapid development of covalent adaptable networks or vitrimers shows promise for addressing the long-standing recycling issues associated with conventional, permanently cross-linked thermosets. At the same time, it is important to demonstrate that properties of reprocessable polymer networks can be optimized to meet the ongoing demand for high-performance materials. We have fabricated reprocessable polyhydroxyurethane (PHU) network composites reinforced with reactive polyhedral oligomeric silsesquioxanes (POSS). With functionalized POSS serving as a fraction of the cross-linkers, the PHU–POSS network nanocomposites exhibit significantly enhanced storage modulus at the rubbery plateau region relative to the neat PHU network. With up to 10 wt% POSS loading, these network composites can undergo melt-state reprocessing at 140 °C with 100% property recovery associated with cross-link density. We also show that hydroxyurethane dynamic chemistry leads to excellent creep resistance at elevated temperature up to 90 °C and is unaffected by reactive incorporation of POSS. In conclusion, this study demonstrates the effectiveness of POSS as nanofillers for designing high-performance, organic-inorganic dynamic PHU networks with excellent reprocessability.

42 ENGINEERING↗
DOE OSTI2025

Understanding Viscoelasticity of an Entangled Silicone Copolymer via Coarse-Grained Molecular Dynamics Simulations

Entangled dynamics is important for understanding rheological properties of long-chain polymers. For entangled homopolymers, the classic tube-reptation model and its refinements have been successfully applied to quantify properties like diffusion coefficient and zero-rate viscosity. However, the application of such models to copolymers has been limited despite scientific and industrial importance. Here, we study the entangled melt dynamics of poly(dimethyl-co-diphenyl)siloxane random copolymer for a range of mean-composition-ratio ϕ of the diphenyl component via long-term molecular dynamics simulation with a recently developed coarse-grained model. We found that the segmental relaxation is heterogeneous at the monomeric level because of compositional fluctuations. However, at the chain-entanglement level and higher length scales, the viscoelastic response is homogeneous with compositional dependence only through the overall diphenyl fraction ϕ. The relaxation modulus of the entangled copolymer melt conforms to the Likhtman–McLeish model, and the viscosity predicted using our current coarse-grained parameters is in good quantitative agreement with experimental data.

Copolymers↗
DOE OSTI2026

In‐Process Melt Separation of PE/PET Blends for Upcycling via Twin‐Screw Extrusion. Impact of Catalyst Reagents on PET Depolymerization

Part 1 of this work focused on depolymerizing polyethylene terephthalate (PET) in twin-screw extrusion, as part of a broader project to continuously separate PET from polyolefins in the melt. This study focused on linear low-density polyethylene (LLDPE) and PET films and the use of ethylene glycol (EG), diethylene glycol (DEG), triethylene glycol (TEG), and bis(2-hydroxyethyl) terephthalate (BHET) to depolymerize the PET in the extruder to levels above 90% Mw. In part 2, the focus will shift to achieving separation of the two polymers in the twin-screw extruder, which is made possible due to a 90% reduction in the Mw of the PET, which caused a decrease of its viscosity by several orders of magnitude. Owing to the viscosity difference and pressure buildup in the die, the low-viscosity PET preferentially exited a degassing vent instead of going through the die. This is because the flow of the PET would travel through a non-pressure vent rather than through a high-pressure die. However, owing to the higher viscosity of the LLDPE, the pressure was too high to pass through such a small diameter vent hole. Supercritical CO₂ (SCCO₂) was used to assist in this extraction, but SCCO₂ negatively impacted the overall degree of separation. Through analysis of the separated materials, it was concluded that a very high separation of the two materials was achieved. TGA and FTIR confirmed that the material separated from the vent was 100% PET. The material removed from the die was composed of 90% LLDPE and 10% PET.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Biodegradation Studies of Polyhydroxybutyrate and Polyhydroxybutyrate- co -Polyhydroxyvalerate Films in Soil

Due to increased environmental pressures, significant research has focused on finding suitable biodegradable plastics to replace ubiquitous petrochemical-derived polymers. Polyhydroxyalkanoates (PHAs) are a class of polymers that can be synthesized by microorganisms and are biodegradable, making them suitable candidates. The present study looks at the degradation properties of two PHA polymers: polyhydroxybutyrate (PHB) and polyhydroxybutyrate-co-polyhydroxyvalerate (PHBV; 8 wt.% valerate), in two different soil conditions: soil fully saturated with water (100% relative humidity, RH) and soil with 40% RH. The degradation was evaluated by observing the changes in appearance, chemical signatures, mechanical properties, and molecular weight of samples. Both PHB and PHBV were degraded completely after two weeks in 100% RH soil conditions and showed significant reductions in mechanical properties after just three days. The samples in 40% RH soil, however, showed minimal changes in mechanical properties, melting temperatures/crystallinity, and molecular weight over six weeks. By observing the degradation behavior for different soil conditions, these results can pave the way for identifying situations where the current use of plastics can be replaced with biodegradable alternatives.

36 MATERIALS SCIENCE↗