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At least 55 records · Page 3

Compatibility of mesophase pitch and linear low-density polyethylene for low-cost carbon fiber

Mesophase pitch and linear low-density polyethylene (LLDPE) were blended by shear mixing and extruded producing precursor fibers which were then converted to carbon fibers (CFs). LLDPE additives agglomerate within the isotropic spheres rather than uniformly dispersing throughout the entire matrix. The blends possess different thermal properties and precursor tensile properties evident by two-phase tensile stress nature not present in precursor fibers produced from pure pitch. The resultant CFs were oxidized at 280 °C for 4 h and carbonized at 1000 °C for 15 min. This process created pitch CFs with a tensile strength of 1.23 GPa and a Young’s modulus of 99 GPa. All CFs produced from blends of pitch and LLDPE possessed a tensile strength of 0.63 GPa and less. These CFs showed a microstructure slightly different from the pure pitch CFs with fractured CF cross sections revealing voids present in all blended CFs due to burnt off LLDPE stemming from carbonization. Further study into compatibilizers and new conversion processes is required to successfully blend LLDPE with mesophase pitch for the purpose of producing a new low-cost CF.

36 MATERIALS SCIENCE↗

Effect of tension during sulfonation stabilization for UHMWPE-derived carbon fibers

Polyethylene is a promising low-cost alternative precursor material for carbon fiber production, but it has yet to show mechanical properties near or surpassing polyacrylonitrile-derived carbon fibers. The high molecular weight and order of ultra-high molecular weight polyethylene (UHMWPE) may offer a pathway to realizing this promise by enabling long-range graphitic structure formation and superior mechanical properties. The tension applied during the precursor stabilization process is crucial to maintaining the shape of the fibers during the conversion process, but no published study has yet probed the relationship between sulfonation tension and carbon fiber microstructure and mechanical properties. In this work, a logarithmic sweep of tensile stress was applied to UHMWPE fibers during the stabilization process followed by carbonization. Increasing tension significantly reduced fiber shrinkage, resulted in straighter fibers with less severe kink bands, and greatly improved the mechanical properties of the fibers. Raman spectroscopy and X-ray diffraction revealed that in all cases the carbon fibers were largely amorphous, but increasing tension resulted in increased size and alignment of the turbostratic crystallites with the fiber axis. Large voids were present in the sample fibers, so the Griffith-Irwin relation was employed to predict the potential ultimate tensile strength of the fibers with voids reduced to sizes comparable to commercially produced fibers. Furthermore, this work demonstrates the importance of tension applied during the stabilization of polyethylene fibers for carbon fiber production and establishes a framework for achieving high mechanical properties from these precursors.

36 MATERIALS SCIENCE↗

Elucidating biodegradation of dimethyl terephthalate by two Rhodococcus strains for its valorization applications

Dimethyl terephthalate (DMT) serves as the precursor in the production of polyethylene terephthalate, polytrimethylene terephthalate, and polybutylene terephthalate. The widespread use of DMT in the polymer industry and its ubiquitous existence in end products raise alarms about its potential harm to humans and animals. DMT can enter the environment through the degradation of polymers and their end products, and cause endocrine disruption, oxidative stress, and an elevated risk of cancer. In recent years, DMT has also gained renewed interest in its potential for plastic recycling and upcycling. In this study, we identified two strains of Rhodococcus that possess DMT-degrading capabilities and utilized transcriptomic analysis and gene knockout to elucidate the mechanisms of DMT degradation. R. opacus PD630 and R. jostii RPET were found to convert up to 1 g/L DMT into mono-methyl terephthalate (MMT). A putative DMTase (RS34275) was identified for this conversion. R. jostii RPET also demonstrates the ability to convert DMT into MMT and to utilize MMT for its cellular growth via the terephthalate pathway. A putative MMTase (RS21885) as the sole enzyme was identified for the conversion of MMT into terephthalate in the RPET strain. In addition, we successfully produced lycopene and lipids from an engineered RPET strain using DMT as a substrate. Our findings will facilitate future DMT bioremediation and bio-upcycling of DMT-associated plastics, enabling the production of value-added products.

Biodegradation↗

A Constitutive Equation for Stratospheric Balloon Materials

The selection of a suitable material for use as a reliable stratospheric balloon gas barrier and structural component is based on a variety of properties. Due to a more desirable combination of properties, the low density polyethylene that has been used for the last half century has been replaced during the last decade by linear low density polyethylene (LLDPE). This paper describes the effort to characterize the time dependent properties of a 38 micron coextrusion of LLDPE. The nonlinear viscoelastic constitutive equation presented may be used to accurately describe the creep and/or relaxation of this film when subjected to a biaxial state of stress, such as might be required for an extended balloon flight. Recent laboratory data have been used to mod@ an existing model of LLDPE to account for differences caused by the coextrusion process. The new model will facilitate structural design optimization and reliability assessment, and may be further utilized as a predictive tool to benefit in-flight operations. Current structural analysis tech&ques based on linear elastic properties have predicted stresses in excess of those which would actually exist.

Rand, J. L.↗

One-pot synthesis of mechanically robust hierarchical graphene-polyethylene aerogels

Fabricating mechanically robust graphene aerogels (GAs) without compromising their notable features including superelasticity, large surface area, high porosity, and low density is challenging. Here, this work presents a new one-pot strategy based on ambient drying to fabricate a three-dimensional (3D) graphene-polyethylene aerogel (G-PEA) with a unique hierarchical porous structure, in which the highly porous polyethylene is encapsulated by graphene frameworks. The hierarchical G-PEA exhibited substantially enhanced compressive strength while maintaining low density and superelasticity comparable to those of bare GAs. The G-PEAs with 5 wt% PE (G-PEA5) showed a significant improvement (up to 2083 %) in compressive stress compared to bare GAs, which can be attributed to the porous PE support within the GA framework. The G-PEA5 retained 94% of its compressive stress after 100 compression cycles, which is still higher than that (∼80%) of bare GAs, and maintained good elastic recovery. The designed hierarchical G-PEAs show great promise in the applications that require outstanding mechanical properties.

Composite↗

The yield and post-yield behavior of high-density polyethylene

An experimental and analytical evaluation was made of the yield and post-yield behavior of high-density polyethylene, a semi-crystalline thermoplastic. Polyethylene was selected for study because it is very inexpensive and readily available in the form of thin-walled tubes. Thin-walled tubular specimens were subjected to axial loads and internal pressures, such that the specimens were subjected to a known biaxial loading. A constant octahederal shear stress rate was imposed during all tests. The measured yield and post-yield behavior was compared with predictions based on both isotropic and anisotropic models. Of particular interest was whether inelastic behavior was sensitive to the hydrostatic stress level. The major achievements and conclusions reached are discussed.

Semeliss, M. A.↗

Measurement of the intrinsic bond strength of brittle thin films on flexible substrates

The brittle cracking and subsequent debonding of nickel films deposited on polymer substrates subjected to uniaxial strain is investigated. Stress analyses for a film/substrate system are performed. Based on the analysis, the interfacial bond strength between brittle thin films and flexible substrates can be evaluated in terms of the tensile strength of the coating and the length of the largest segment that first debonds. Experiments were performed on Ni films with different thicknesses evaporated on polyethylene terephthalate substrates and the intrinsic bond strength was evaluated. The interfacial bond strengths were shown to be relatively independent of the film thickness for the range studied.

Guo, Q.↗

Testing of ACC-6 Carbon-Carbon at High Strain Rates and High Temperatures

Some materials, such as steel, titanium, and tungsten, have a yield stress that depends on the strain rate, and actually are stronger at high rates of load or deformation. The increase in strength is relevant; and if not taken into account, the computer models will not match the experimental behavior observed in typical shock loading, ordnance, or ballistic tests. For higher velocity (hypervelocity impacts), an equation of state that accounts for non-linearities and temperature in the pressure-volume relation, may also be needed. This rate-dependent behavior of the strength has also been observed in some composite materials. Southwest Research Institute® (SwRI®) has started an internal research effort to measure and better model the behavior of materials, in particular carbon/carbon composites like ACC-6, at ultra-high temperatures for both static and high rates of deformation. The ultimate objective is to obtain reliable computer models of carbon/carbon material under hypersonic flight conditions, hypervelocity impacts, shock-loading situations such as booster-vehicle separation, and munition operation events. SwRI® has successfully modeled in the past ballistic impact on other composites, namely S-2 glass/epoxy, Kevlar/resin, polyethylene fibers/resin, and carbon fiber composites. This presentation will show test results relevant to the strength properties of the ACC-6 C/C material which were measured at quasistatic, medium, and the moderately high strain rates (~103 s—1) achievable in a conventional Split Hopkinson bar apparatus. Some of the tests were performed at both high-rates and high temperatures typical of hypersonic flight, something that, to the authors’ knowledge, has never been published in the past for this particular material. The test method will be presented, as well as the comparison of the stress-strain curves for the different temperatures and strain-rates of interest. A discussion of how the results can be used in the typical hydrocodes of interest will be included.

carbon/carbon↗

Multi-Layer Laminated Thin Films for Inflatable Structures

Special-purpose balloons and other inflatable structures would be constructed as flexible laminates of multiple thin polymeric films interspersed with layers of adhesive, according to a proposal. In the original intended application, the laminate would serve as the envelope of the Titan Aerobot a proposed robotic airship for exploring Titan (one of the moons of Saturn). Potential terrestrial applications for such flexible laminates could include blimps and sails. In the original application, the multi-layered laminate would contain six layers of 0.14-mil (0.0036-mm)-thick Mylar (or equivalent) polyethylene terephthalate film with a layer of adhesive between each layer of Mylar . The overall thickness and areal density of this laminate would be nearly the same as those of 1-mil (0.0254-mm)-thick monolayer polyethylene terephthalate sheet. However, the laminate would offer several advantages over the monolayer sheet, especially with respect to interrelated considerations of flexing properties, formation of pinholes, and difficulty or ease of handling, as discussed next. Most of the damage during flexing of the laminate would be localized in the outermost layers, where the radii of bending in a given bend would be the largest and, hence, the bending stress would be the greatest. The adverse effects of formation of pinholes would be nearly completely mitigated in the laminate because a pinhole in a given layer would not propagate to adjacent layers. Hence, the laminate would tend to remain effective as a barrier to retain gas. Similar arguments can be made regarding cracks: While a crack could form as a result of stress or a defect in the film material, a crack would not propagate into adjacent layers, and the adjacent layer(s) would even arrest propagation of the crack. In the case of the monolayer sheet, surface damage (scratches, dents, permanent folds, pinholes, and the like) caused by handling would constitute or give rise to defects that could propagate through the thickness as cracks or pinholes that would render the sheet less effective or ineffective as a barrier. In contrast, because damage incurred during handling of the laminate would ordinarily be limited to the outermost layers, the barrier properties of the laminate would be less likely to be adversely affected. Therefore, handling of the laminate would be easier because there would be less of a need to exercise care to ensure against surface damage.

Yavrouian, Andre↗

Material characterization of seven photovoltaic backsheets using seven accelerated test conditions

A variety of polymeric backsheet materials can be found in fielded photovoltaic (PV) modules, mostly based on fluoropolymer and polyethylene terephthalate (PET) materials. Cost reduction and sustainability considerations drive the recent development of alternative backsheet materials and designs [1]. In some fielded PV installations, polymeric materials are susceptible to environmental degradation in the form of backsheet cracking. To prevent backsheet degradation that can result in a module failure, thorough laboratory reliability testing is needed. In this report we studied the durability of seven commercial and experimental PV backsheets through accelerated stress testing using seven photolytic, hygrometric, and custom tests with the goal to understand if novel fluoropolymer-free backsheets are sufficiently environmentally durable to be commercialized. We divided the mechanisms observed during aging into two categories: core degradation and surface degradation. Although core degradation due to hydrolysis was observed in all commercial PET-, and polyamide (PA)-based backsheets aged with 85 degrees C/85% relative humidity, this test is unlikely to be field relevant. Photo-oxidative reactions on the exposed surface during UV weathering affected all seven backsheets regardless of the outer layer polymer material and additives. This degradation was limited to the outermost micrometers of the surface, except for backsheets containing PA-12, which resulted in surface cracking. A custom test combining UV with water spray caused the most severe backsheet degradation, including surface erosion and loss of insulating properties in polyolefin (PO)- and PA-based backsheets. This highlights the importance of combined accelerated stress testing to screen for complex backsheet degradation mechanisms. We also showed that, with material and design optimization, coextruded experimental PO-based backsheets have the potential to be a durable alternative to commercial PET- and fluoropolymer-based PV backsheets.

14 SOLAR ENERGY↗

Acceleration Factors for Combined‐Accelerated Stress Testing of Photovoltaic Modules

Combined‐accelerated stress testing (C‐AST) is developed to establish the durability of photovoltaic (PV) products, including for degradation modes that are not a priori known or examined in standardized tests. C‐AST aims to comprehensively represent the sample, stress factors, and their combinations using levels at the statistical tails of the natural environment. Acceleration factors for relevant climate sequences within the C‐AST cycle with respect to the Florida USA climate are estimated for selected degradation mechanisms. It is found that for degradation of the outer backsheet polymer layer, the acceleration factor of the tropical climate sequence (the longest of the climate sequences) is f ( T , G ) = 17.3 with ultraviolet photodegradation; for polyethylene terephthalate hydrolysis (backsheets), f ( T , RH ) = 426; for electrochemical corrosion (PV cell), f ( I ) = 14.1; and for PbSn solder fatigue f (Δ T , r ( T )) = 17.3. Here, T is the module temperature, G is the broadband spectrum irradiance on the plane of array of the module, RH is the relative humidity on the module surface, I is the leakage current through the module packaging, and r ( T ), the number of temperature reversals. The methods discussed herein are generally applicable for evaluating acceleration factors in other accelerated test methods.

14 SOLAR ENERGY↗

Enhanced Interfacial Bonding of Graft Copolymers

To understand how thermoplastic welding strength can be tuned through chemical modifications and macromolecular topology, we combined coarse-grained molecular dynamics (MD) simulations with experimental validation. Our simulations examined the diffusion dynamics of both linear and graft polymers across representative interfaces, revealing that diffusion-controlled interdigitation follows a power law, with the exponent decreasing from 0.34 to 0.11 as grafting density increases from 7.5 to 196% (with side chains grafted to both sides of a monomer unit). The addition of side chains enhances welding efficiency, as dense bottlebrush polymers with high grafting density reach maximum rupture strength faster than linear polymers. However, their saturated rupture strength is lower. This observation is subsequently corroborated by experimental lap-shear tests comparing linear polyethylene with octene grafted polyethylene elastomers. Our MD simulations show that unlike linear polymers, where backbone entanglements dominate, the grafted side chains introduce mechanisms in addition to entanglement dilution. The rapid interdigitation of side chains creates a dense mesh of entropic van der Waals contacts, which can also enhance the film welding. Furthermore, our MD simulations reveal a brittle rupture behavior in linear and comb-like (mildly grafted) polymers, while bottlebrush (densely grafted) polymers display elastomeric behavior with a pronounced stress plateau prior to fracture. Our simulations deconvolute the influence of polymer topology on deformation behavior. The rate of polymer deformation becomes lower than the applied strain rate prior to rupture, and the onset of this deviation is progressively delayed from linear to bottlebrush polymers. This trend highlights the critical role of molecular architecture in governing the mechanical response. In conclusion, these results provide deeper insight into the underlying welding mechanisms of topological polymers and present a potential approach for mitigating the interface anisotropy that is inherent in advanced manufacturing techniques such as fused filament fabrication.

graft copolymers↗

Influence of plasticizers on thermal and mechanical properties of biocomposite filaments made from lignin and polylactic acid for 3D printing

Polylactic acid (PLA) and organosolv lignin were mixed at different ratios and extruded to obtain PLA-lignin composite filaments. PLA was replaced with lignin up to 20 wt%. Two plasticizers (polyethylene glycol (PEG) 2000 and struktol TR451) were added in varying concentrations to enhance the properties of PLA_L20 (20% lignin in PLA) composite filaments. Furthermore, the effect of lignin in PLA, and PEG, and struktol in PLA_L20 composites was investigated via tensile test, differential scanning calorimetry, thermogravimetric analysis, scanning electron microscopy, Fourier transform infrared spectroscopy of the filaments, and dynamic mechanical analysis of 3D printed samples. A 2 wt% PEG was able to enhance both tensile stress and elongation at maximum load of PLA_L20 composite by 19% and 35%, respectively, whereas struktol TR451 was able to improve elongation at maximum load by 24%.

3D printing↗

Oscillatory shear stress stimulates endothelial production of O2- from p47phox-dependent NAD(P)H oxidases, leading to monocyte adhesion

Arterial regions exposed to oscillatory shear (OS) in branched arteries are lesion-prone sites of atherosclerosis, whereas those of laminar shear (LS) are relatively well protected. Here, we examined the hypothesis that OS and LS differentially regulate production of O2- from the endothelial NAD(P)H oxidase, which, in turn, is responsible for their opposite effects on a critical atherogenic event, monocyte adhesion. We used aortic endothelial cells obtained from C57BL/6 (MAE-C57) and p47phox-/- (MAE-p47-/-) mice, which lack a component of NAD(P)H oxidase. O2- production was determined by dihydroethidium staining and an electron spin resonance using an electron spin trap methoxycarbonyl-2,2,5,5-tetramethyl-pyrrolidine. Chronic exposure (18 h) to an arterial level of OS (+/- 5 dynes/cm2) increased O2- (2-fold) and monocyte adhesion (3-fold) in MAE-C57 cells, whereas chronic LS (15 dynes/cm2, 18 h) significantly decreased both monocyte adhesion and O2- compared with static conditions. In contrast, neither LS nor OS were able to induce O2- production and monocyte adhesion to MAE-p47-/-. Treating MAE-C57 with a cell-permeable superoxide dismutase compound, polyethylene glycol-superoxide dismutase, also inhibited OS-induced monocyte adhesion. In addition, over-expressing p47phox in MAE-p47-/- restored OS-induced O2- production and monocyte adhesion. These results suggest that chronic exposure of endothelial cells to OS stimulates O2- and/or its derivatives produced from p47phox-dependent NAD(P)H oxidase, which, in turn, leads to monocyte adhesion, an early and critical atherogenic event.

NASA Program Fundamental Space Biology↗

Methodology for Producing a Uniform Distribution of UO2 in a Tungsten Matrix

Current work at NASA's Marshall Space Flight Center (MSFC) is focused on the development CERMET fuel materials for Nuclear Thermal Propulsion (NTP). The CERMETs consist of uranium dioxide (UO2) fuel particles embedded in a tungsten (W) metal matrix. Initial testing of W-UO2 samples fabricated from fine angular powders performed reasonably well, but suffered from significant fuel loss during repeated thermal cycling due to agglomeration of the UO2 (1). The blended powder mixtures resulted in a non-uniform dispersion of the UO2 particles in the tungsten matrix, which allows rapid vaporization of the interconnected UO2 from the sample edges into the bulk material. Also, the angular powders create areas of stress concentrations due to thermal expansion mismatch, which eventually cracks the tungsten matrix. Evenly coating spherical UO2 particles with chemical vapor deposited (CVD) tungsten prior to consolidation was previously demonstrated to provide improved performance. However, the CVD processing technology is expensive and not currently available. In order to reduce cost and enhance performance, a powder coating process has been developed at MSFC to produce a uniform distribution of the spherical UO2 particles in a tungsten matrix. The method involves utilization of a polyethylene binder during mixing which leads to fine tungsten powders clinging to the larger UO2 spherical particles. This process was developed using HfO2 as a surrogate for UO2. Enough powder was mixed to make 8 discs (2cm diameter x 8mm thickness) using spark plasma sintering. A uniaxial pressure of 50 MPa was used at four different temperatures (2 samples at each temperature). The first two samples were heated to 1400C and 1500C respectively for 5 minutes. Densities for these samples were less than 85% of theoretical, so the time at temperature was increased to 20 minutes for the remaining samples. The highest densities were achieved for the two samples sintered at 1700C (approx. 92% of theoretical). Scanning electron microscopy (SEM) of the mixed powders and the sintered samples along with energy dispersive x-ray analysis was obtained. The SEM of the powders clearly show the fine W powder adhered to the larger HfO2 particles and a uniform distribution of HfO2 particles in a tungsten matrix upon densification. Vicker's Microhardness testing was also performed on all samples using 0.5, 1.0 and 2.0 kg loads. Five indents were made at each load level. All indents were placed in the tungsten matrix to assist as a proxy in measuring densification. The highest hardness value was obtained for the 1700C specimens. The hardness average for these samples was 312.14 MPa. This powder processing method has been applied to W/UO2 powders with the SEM of the powders appearing similar to the W/HfO2 powder images.

Tucker, Dennis S.↗

Friction and wear of TPS fibers: A study of the adhesion and friction of high modulus fibers

The adhesional and frictional forces between filaments in a woven fabric or felt, strongly influenced the processability of the fiber and the mechanical durability of the final product. Even though the contact loads between fibers are low, the area of contact is extremely small giving rise to very high stresses; principally shear stresses. One consequence of these strong adhesional and frictional forces is the resistance of fibers to slide past each other during weaving or when processed into nonwoven mats or felts. Furthermore, the interfiber frictional forces may cause surface damage and thereby reduce the fiber strength. Once formed into fabrics, flexural handling and manipulation of the material again causes individual filaments to rub against each other resulting in modulus, brittle fibers such as those used in thermal protection systems (TPS). The adhesion and friction of organic fibers, notably polyethylene terephthalate (PET) fibers, have been extensively studied, but there has been very little work reported on high modulus inorganic fibers. An extensive study was made of the adhesion and friction of flame drawn silica fibers in order to develop experimental techniques and a scientific basis for data interpretation. Subsequently, these methods were applied to fibers of interest in TPS materials.

Bascom, Willard D.↗

Role of Amorphous Chains in Nanoplastic Formation from Semicrystalline Polymers

Semicrystalline polymers, e.g., polyethylene terephthalate (PET), release micro- (100 nm to 1 mm) and nanoplastics (up to 100 nm) [MNPL] when they are degraded under quiescent conditions. However, the exact molecular mechanisms leading to material fragmentation into MNPL are unknown. Here, we monitor the evolution of chain molecular weight and the MNPL production kinetics during hydrolysis of PET pellets. We find that only ~0.6% of the amorphous phase ester bonds are hydrolyzed at the onset of MNPL release. Then, by combining a random scission model with measured amorphous spacings, we estimate that only ~15% of the stress transmitters in the amorphous phase, namely, bridges and entangled loops, have failed by this point. Thus, spontaneous fragmentation of the semicrystalline nanostructure occurs despite significant intercrystalline connectivity. We resolve this apparent contradiction by proposing that fragmentation can only occur when progressive tie-chain scission causes the material to undergo the ductile/brittle transition. Mechanistically, we speculate that the internal stresses responsible for material fragmentation are caused by processing (i.e., residual stresses) and/or sample densification induced by chemi-crystallization. We discuss additional factors that may affect our analysis and thus require further investigation, such as skin-core effects, preferential degradation of stress transmitters and/or recrystallization processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗