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At least 1,747 records · Page 97

Lightweight, Low-CTE Tubes Made From Biaxially Oriented LCPs

Tubes made from biaxially oriented liquid-crystal polymers (LCPs) have been developed for use as penetrations on cryogenic tanks. ( Penetrations in this context denotes feed lines, vent lines, and sensor tubes, all of which contribute to the undesired conduction of heat into the tanks.) In comparison with corresponding prior cryogenic-tank penetrations made from stainless steels and nickel alloys, the LCP penetrations offer advantages of less weight and less thermal conduction. An additional major advantage of LCP components is that one can tailor their coefficients of thermal expansion (CTEs). The estimated cost of continuous production of LCP tubes of typical sizes is about $1.27/ft ($4.17/m) [based on 1998 prices]. LCP tubes that are compatible with liquid oxygen and that feature tailored biaxial molecular orientation and quasi-isotropic properties (including quasi-isotropic CTE) have been fabricated by a combination of proprietary and patented techniques that involve the use of counterrotating dies (CRDs). Tailoring of the angle of molecular orientation is what makes it possible to tailor the CTE over a wide range to match the CTEs of adjacent penetrations of other tank components; this, in turn, makes it possible to minimize differential-thermal expansion stresses that arise during thermal cycling. The fabrication of biaxially oriented LCP tubes by use of CRDs is not new in itself. The novelty of the present development lies in tailoring the orientations and thus the CTEs and other mechanical properties of the LCPs for the intended cryogenic applications and in modifications of the CRDs for this purpose. The LCP tubes and the 304-stainless-steel tubes that the LCP tubes were intended to supplant were tested with respect to burst strength, permeability, thermal conductivity, and CTE.

Rubin, Leslie↗

Cell separation by immunoaffinity partitioning with polyethylene glycol-modified Protein A in aqueous polymer two-phase systems

Previous work has shown that polyethylene glycol (PEG)-bound antibodies can be used as affinity ligands in PEG-dextran two-phase systems to provide selective partitioning of cells to the PEG-rich phase. In the present work it is shown that immunoaffinity partitioning can be simplified by use of PEG-modified Protein A which complexes with unmodified antibody and cells and shifts their partitioning into the PEG-rich phase, thus eliminating the need to prepare a PEG-modified antibody for each cell type. In addition, the paper provides a more rigorous test of the original technique with PEG-bound antibodies by showing that it is effective at shifting the partitioning of either cell type of a mixture of two cell populations.

Karr, Laurel J.↗

Bypassing Energy Barriers in Fiber-Polymer Torrefaction

The amount of waste generation has been increasing with a significant amount being landfilled. These non-recyclable wastes contain large number of fiber and plastic wastes which can be treated with thermal processes to turn them into energy sources since they have high calorific values, are abundant and usually tipping fees are paid to handle them. This paper studied the torrefaction of non-recyclable paper (fiber) wastes, mixed plastic wastes (MPW) and their blends at different ratios in the temperature range of 250–400°C through thermogravimetric analysis (TGA). The solid residues after the experiments were analyzed by nuclear magnetic resonance (NMR) spectroscopy. Significant synergy between fiber and MPW were observed at the range 250–300°C, showing both increase in the reaction rate as well as the overall mass loss. At 250°C, the maximum mass loss rate was more than two times higher and the mass loss at the end of the experiments were also much higher compared to the expected results. In addition, synergy was weakened with an increase of temperature, disappearing at 400°C. The existence of such interactions between fiber and plastic wastes indicates that the natural energy barriers during the individual torrefaction in paper waste or plastic waste could be bypassed, and the torrefaction of fiber and plastic blend can be achieved at lower temperatures and/or shorter residence times. The MPW and fiber wastes were also compounded by extrusion (to produce pellets) at 220°C with different blend ratios. The fiber-MPW pellets from extrusion were characterized by IR spectroscopy, rheology, thermal analysis and flexural properties and showed significant chemical changes from the non-extruded blends at the same ratios. From IR characterization, it was found that there was significant increase in hydroxyl (OH) group on account of the carbonyl (C = O) and etheric (C-O-C) groups. The interaction between paper and MPW can be attributed to the plastic polymers acting as a hydrogen donor during the reactive extrusion process. Synergistic effects were also found from mechanical and rheological properties.

09 BIOMASS FUELS↗

X-ray Phase Contrast Imaging of the Impact of Multiple HMX Particles in a Polymeric Matrix

The initiation of high explosives (HEs) under shock loading lacks a comprehensive understanding: particularly at the particle scale. One common explanation is the hot spot theory, which suggests that energy in the material resulting from the impact event is localized in a small area causing an increase in temperature that can lead to ignition. This study focuses on the response of HMX particles (a common HE) within a polymer matrix (Sylgard-184 (R)), a simplified example of a polymer-bound explosive (PBX). These PBXs consist of multiple HMX particles in a single polymer-bound sample. A light gas gun was used to load the samples at impact velocities above 400 m/s. The impact events were visualized using X-ray phase-contrast imaging (PCI) allowing real-time observation of the impact event. The experiment used two different types of samples (multi-particle and two crystals) and found evidence of cracking and debonding in both sample types. Additionally, it was found that the multiple particle samples showed similar evidence of damage at lower velocities than that of single particle samples. This is an expected result as the multiple particles add additional interfaces for stress concentration and frictional heating.

42 ENGINEERING↗

On the mechanism of marine fouling-prevention performance of oil-containing silicone elastomers

For many decades, silicone elastomers with oil incorporated have served as fouling-release coating for marine applications. In a comprehensive study involving a series of laboratory-based marine fouling assays and extensive global field studies of up to 2-year duration, we compare polydimethylsiloxane (PDMS) coatings of the same composition loaded with oil via two different methods. One method used a traditional, one-pot pre-cure oil addition approach (o-PDMS) and another method used a newer post-cure infusion approach (i-PDMS). The latter displays a substantial improvement in biofouling prevention performance that exceeds established commercial silicone-based fouling-release coating standards. We interpret the differences in performance between one-pot and infused PDMS by developing a mechanistic model based on the Flory–Rehner theory of swollen polymer networks. Using this model, we propose that the chemical potential of the incorporated oil is a key consideration for the design of future fouling-release coatings, as the improved performance is driven by the formation and stabilization of an anti-adhesion oil overlayer on the polymer surface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High-pressure elasticity and equation of state of the fluoroelastomer Viton® A-500

Viton® A is a semi-crystalline copolymer of polyvinylidene fluoride and hexafluoropropylene used in various engineering applications due to its mechanical properties and chemical inertness. In situ ultrasonic spectroscopy and x-ray radiography measurements were performed in a Paris–Edinburgh press to measure the pressure dependence of the transverse and longitudinal acoustic velocity of the fluoroelastomer A-500 from 2.7 to 5.7 GPa at 296 K. In addition, we performed high-pressure Brillouin scattering measurements to obtain acoustic velocities from ambient pressure to 5.7 GPa to supplement the ultrasonic measurements, especially at low pressures. The acoustic velocities were then used to calculate a pressure–volume (P–V) equation of state, the bulk and shear moduli, and the Poisson's ratio. These quantities are compared with the reported pressure-dependent properties of related polymers over this range of pressures.

Acoustical properties↗

Accessing pluripotent materials through tempering of dynamic covalent polymer networks

Pluripotency, which is defined as a system not fixed as to its developmental potentialities, is typically associated with biology and stem cells. Here, inspired by this concept, we report synthetic polymers that act as a single “pluripotent” feedstock and can be differentiated into a range of materials that exhibit different mechanical properties, from hard and brittle to soft and extensible. To achieve this, we have exploited dynamic covalent networks that contain labile, dynamic thia-Michael bonds, whose extent of bonding can be thermally modulated and retained through tempering, akin to the process used in metallurgy. In addition, we show that the shape memory behavior of these materials can be tailored through tempering and that these materials can be patterned to spatially control mechanical properties.

36 MATERIALS SCIENCE↗

PDRD Project 19039 - All metal vacuum scroll pump development for tritium

Currently the United States relies on a single source, foreign company, Eumeca (formerly Normetex) for the supply of an all metal vacuum scroll pump to process tritium. This “one of a kind”, all metal, vacuum scroll pump utilizes no “wetted”, polymeric materials that degrade prematurely when exposed to tritium. U.S. based vacuum scroll pump suppliers typically utilize a polymer, Teflon®, as a tip seal material at the edge of the scroll impellers for proper pump function. Teflon® is known to degrade within a relatively short time frame (approximately 1 year) when continually exposed to tritium gas. This degradation results in “flaking” of the Teflon® material which results in particulate contamination of the process gas stream. While filtration of the particulate is possible, doing so requires additional maintenance which is costly in a glovebox environment. In addition, filtration can degrade pumping system performance as particulate collects in the filter media over time. To date, all of the well established U.S and European based vacuum scroll pump manufacturers have been uninterested in developing an all metal vacuum scroll pump that does not use a polymeric scroll tip seal. This position is taken as the vacuum scroll pump manufacturers do not see a large enough market to make it profitable for them to develop and market an all metal vacuum scroll pump. In the mid 2000s, one company, Air Squared, Inc., a small Original Equipment Manufacturer (OEM) specializing in design and fabrication of custom scroll vacuum pumps and compressors, was willing to pursue the effort. The first design effort incorporated Vespel® as a polymeric tip seal material. Results of this effort led to realizing the affect that the Met-Bel MB-601 metal bellows pump has on performance when used as a backing pump for an all metal vacuum scroll pump without a scroll tip seal. As a result, Air Squared subsequently designed an all metal vacuum scroll pump without a tip seal material for evaluation. Although the initial, all metal version of the Air Squared pump was found deficient in regard to scroll impeller stiffness, which resulted in scroll contact, general design and pump performance was verified to be adequate. SRS PDRD Project 19039 was launched in 2019 as a 3rd attempt with Air Squared, Inc. in regard to development of an all metal vacuum scroll pump for consideration as an equivalent to the Eumeca/ Normetex pump. The effort specified 300 series stainless steel for the scroll impellers, all metal sealing, and design to meet tritium throughput and ultimate vacuum requirements. In addition, a 60 psig design pressure rating requirement was specified for the pump containment boundary. The 3rd generation Air Squared pump has been designed, fabricated, and has received preliminary testing. Preliminary testing has indicated proper leak tightness and pump performance. However, work continues regarding development of a pumping chamber containment bellows that can be subjected to 66 psig without damage to the bellows. Work will continue in 2020 and 2021 to pursue a pumping chamber containment bellows that meets the pressure rating requirement.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Current collection from the space plasma through defects in high voltage solar array insulation

For spacecraft operation in the near Earth environment, solar cell arrays constitute the major source of reliable long term power. Optimization of mass and power efficiency results in a general requirement for high voltage solar arrays. The space plasma environment, though, can result in large currents being collected by exposed solar cells. The solution of a protective covering of transparent insulation is not a complete solution, inasmuch as defects in the insulation result in anomalously large currents being collected through the defects. Tests simulating the electron collection from small defects in an insulation have shown that there are two major collection modes. The first mode involves current enhancement by means of a surface phenomenon involving the surrounding insulator. In the second mode the current collection is enhanced by vaporization and ionization of the insulators materials, in addition to the surface enhancement of the first mode. A model for the electron collection is the surface enhanced collection mode was developed. The model relates the secondary electron emission yield to the electron collection. It correctly predicts the qualitative effects of hole size, sample temperature and roughening of sample surface. The theory was also shown to predict electron collection within a factor of two for the polymers teflon and polyimide.

Stillwell, R. P.↗

Topics in electrochemical degradation of photovoltaic modules

Electrochemical degradation of photovoltaic modules was examined. It is found that the extent of electrochemical damage is dependent on the integrated leakage current. The PV electrochemical degradation mechanisms in the two polarities are different: (1) degradation rates in the two polarities are of the same order of magnitude; (2) center tapped grounded arrays are a preferred system configuration to minimize electrochemical degradation. The use of thicker pottant layers and polymer substrate films to reduce equilibrium leakage current values is suggested. A metallized substrate layer, if used, should be isolated from the pottant and the frame by polyester layers, and EVA modules appear to be consistent with 30 year life allocation levels for electrochemical damage. Temperature acceleration factors are well behaved and moderately well understood; humidity acceleration factors vary radically with module construction and materials and require additional research.

Mon, G. R.↗

ICAN sensitivity analysis

A computer program called Integrated Composite Analyzer (ICAN) was used to predict the properties of high-temperature polymer matrix composites. ICAN is a collection of NASA Lewis Research Center-developed computer codes designed to carry out analysis of multilayered fiber composites. The material properties used as input to the program were those of the thermoset polyimide resin PMR-15 and the carbon fiber Celion 6000. The sensitivity of the predicted composite properties to variations in the resin and fiber properties was examined. In addition, the predicted results were compared with experimental data. In most cases, the effect of changes in resin and fiber properties on composite properties was reasonable. However, the variations in the composite strengths with the moisture content of the PMR-15 resin were inconsistent. The ICAN-predicted composite moduli agreed fairly well with experimental values, but the predicted composite strengths were generally lower than experimental values.

Frimpong, Stephen↗

Origin of Chlorobenzene Detected by the Curiosity Rover in Yellowknife Bay: Evidence for Martian Organics in the Sheepbed Mudstone?

The Sample Analysis at Mars (SAM) instrument on the Curiosity rover is designed to determine the inventory of organic and inorganic volatiles thermally evolved from solid samples using a combination of evolved gas analysis (EGA), gas chromatography mass spectrometry (GCMS), and tunable laser spectroscopy. The first solid samples analyzed by SAM, a scoop of windblown dust and sand at Rocknest (RN), revealed chlorinated hydrocarbons derived primarily from reactions between a martian oxychlorine phase (e.g. perchlorate) and terrestrial carbon from N-methyl-N-(tert-butyldimethylsilyl)-trifluoroacetamide (MTBSTFA) vapor present in the SAM instrument background. Chlorobenzene (CBZ) was also identified by SAM GCMS at RN at trace levels (approx.0.007 nmol) and was attributed to the reaction of chlorine with the Tenax polymers used in the hydrocarbon traps. After the RN analyses, Curiosity traveled to Yellowknife Bay and drilled two separate holes designated John Klein (JK) and Cumberland (CB). Analyses of JK and CB by both SAM and the CheMin x-ray diffraction instrument revealed a mudstone consisting of approx.20 wt% smectite clays, which on Earth are known to aid the concentration and preservation of organic matter. In addition, higher abundances and a more diverse suite of chlorinated hydrocarbons in CB compared to RN suggests that martian or meteoritic organic sources may be preserved in the mudstone. Here we discuss the SAM EGA and GCMS measurements of volatiles released from the Sheepbed mudstone. We focus primarily on the elevated CBZ detections at CB and laboratory analog experiments conducted to help determine if CBZ is derived from primarily terrestrial, martian, or a combination of sources.

origin of↗

Experimental study on rheological and settling properties of shape memory polymer for fracture sealing in geothermal formations

This article studies the rheology and annular flow of a smart lost circulation material (LCM) at 160 °C, using a high-temperature flow loop. The smart LCM is a shape memory polymer (SMP) that activates at high temperatures, and its particle size increases to seal fractures in geothermal formations. SMP was mixed with the base fluid in two different concentrations, 1.0 and 3.0 wt%, to study rheology, wellbore hydraulics, activation process, and settling behavior under different testing conditions. The results of this study showed that the SMP could be activated at high temperatures. An increase of 80–100% in the particle size was observed at 160 °C. The mud samples showed a high shear-thinning behavior at the two concentrations with a Power-law flow index (n) ranging between 0.025 and 0.101. No additional frictional pressure losses were observed when SMP was added to the base fluid. SMP particles showed an excellent suspension at 1.0 wt% while, at 3.0 wt%, a bed was formed at a low flow rate and without pipe rotation. Increasing the drill pipe rotational speed or flow rate effectively removed the bed and homogeneously dispersed the SMP particles, ensuring a better sealing efficiency. SMP particle dispersion in inclined wells was better than in horizontal wells. Moreover, the findings of this study help optimize the lost circulation treatment by considering a wide range of operating parameters that can further be extended to different systems and geometries.

02 PETROLEUM↗

Thermodynamic stability versus kinetic accessibility: Pareto fronts for programmable self-assembly

A challenge in designing self-assembling building blocks is to ensure the target state is both thermodynamically stable and kinetically accessible. These two objectives are known to be typically in competition, but it is not known how to simultaneously optimize them. We consider this problem through the lens of multi-objective optimization theory: we develop a genetic algorithm to compute the Pareto fronts characterizing the tradeoff between equilibrium probability and folding rate, for a model system of small polymers of colloids with tunable short-ranged interaction energies. We use a coarse-grained model for the particles' dynamics that allows us to efficiently search over parameters, for systems small enough to be enumerated. For most target states there is a tradeoff when the number of types of particles is small, with medium-weak bonds favouring fast folding, and strong bonds favouring high equilibrium probability. Additionally, the tradeoff disappears when the number of particle types reaches a value m *, that is usually much less than the total number of particles. This general approach of computing Pareto fronts allows one to identify the minimum number of design parameters to avoid a thermodynamic–kinetic tradeoff. However, we argue, by contrasting our coarse-grained model's predictions with those of Brownian dynamics simulations, that particles with short-ranged isotropic interactions should generically have a tradeoff, and avoiding it in larger systems will require orientation-dependent interactions.

36 MATERIALS SCIENCE↗

Two-dimensional ring polymer molecular dynamics determination of the MnO + + H 2 /D 2 reaction rates on a Δ-machine learned potential energy surface

In this work, we investigate the impact of nuclear quantum effects in the kinetics of the MnO + + H 2 reaction, a prototypical system for gas-phase H 2 activation by transition metal oxide ions. The DFT based potential energy surfaces (PESs) for the lowest-lying quintet and septet spin states reported in our previous work are improved by 2953 newly calculated CCSD(T)/AVDZ points using a delta-machine learning (Δ-ML) method. To examine nuclear quantum effects, the rate coefficients are computed using ring-polymer molecular dynamics (RPMD). Due to the mechanistic complexity of the reaction, two reaction coordinates are necessary to map out the free-energy surface and an extended RPMD rate theory is developed. The calculated RPMD rate coefficients on the new PES are in better agreement with experimental data. The calculated kinetic isotope effects (KIEs) range from 1.6 to 1.8, also in good agreement with the experimental values. Additionally, the converged RPMD rate coefficients are 2.3 to 3.1 times higher than their classical counterparts across the studied temperature range, suggesting the presence of moderate nuclear quantum effects in this reaction.

Liu, Yang [University of New Mexico, Albuquerque, ↗

Intermediate-Temperature Proton Exchange Membranes Based on Cerium Ultraphosphate Composited with Polybenzimidazole

This paper reports the rational fabrication and structural, thermal, mechanical and electrochemical characterization of a new type of intermediate-temperature (IT) polymer-inorganic composite (PIC) proton exchange membranes (PEMs) that are made of cerium ultraphosphate (CeP 5 O 14 —CUP) as the solid-state proton conductor composited with a high-temperature (HT) polybenzimidazole (PBI) as the polymeric binder. Here, flexible PBI-CUP PIC membranes with the thickness of ~135 μ m and CUP mass fraction of up to 75% were prepared by solution-casting without additional acid-doping (e.g., phosphoric acid). The proton conductivity of the fabricated IT-PIC-PEMs was up to 5.80 × 10 –2 S cm –1 as measured from a prototype IT PEM fuel cell (PEMFC) operated at 200 °C in the humidified hydrogen and air environment. This type of IT-PIC-PEMs also demonstrated sufficient mechanical strength and flexibility, excellent thermal stability (up to 350 °C), and very good durability of the proton conductivity (within the test duration of 500 h). The present experimental study shows the promising future of the IT-PIC-PEMs for applications in various IT electrochemical processes including IT-PEMFCs, IT-electrolyzers, etc.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Recycling of PET by Dissolution-Purification-Recovery (DPR) Process Using Bioderived Solvent

Polyethylene terephthalate (PET) waste continues to accumulate at staggering rates, with the majority still routed to landfills due to limitations in current recycling methods. While mechanical recycling is widely implemented, it struggles to effectively remove colorants, additives, and harmful contaminants - resulting in discolored, degraded materials with limited reuse potential. In this presentation, we demonstrate a scalable dissolution-purification-recovery (DPR) process designed to selectively reclaim high-purity PET from post-consumer bottle flake. The method utilizes a food grade bio-based solvent for targeted PET dissolution, followed by activated carbon treatment for impurity removal and antisolvent-induced precipitation for polymer recovery. The resulting recycled PET exhibits complete decolorization, significantly reduced metal contamination, and minimal loss in molecular weight. These performance metrics indicate strong suitability for remanufacturing into new bottles, offering a circular alternative to traditional mechanical recycling pathways.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗