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At least 595 records · Page 33

Investigation of chemical stabilities and contact angle of 3D printed polymers with CO 2 capture solvents to enhance absorber performance

Increasing absorption rate in aqueous amine CCS systems is one avenue to decrease capital cost by reducing the overall size of the absorber column. One potential route is by replacing conventional steel packing with custom designed packing made from 3D printed polymers. 3D printing offers endless flexibility in packing designs to better enhance liquid/gas contact, increase CO 2 mass transfer and create compact absorber columns. Additionally, before exploring novel packing designs, it is necessary to identify polymer materials that can be 3D printed while also showing long-term physical and surface property stability upon exposure to corrosive amine solutions. Four polymers that are commonly used for 3D printing were evaluated using CO 2 -loaded amine solution at temperatures typically observed in the absorber column. Three polymers, high-density polystyrene (HDPS), acrylonitrile butadiene styrene (ABS) and nylon were found to be physically stable after 5000 hr of amine exposure at temperatures up to 60 °C. The contact angle (wetting) of water and CO 2 -loaded aqueous amine solution on the polymer surfaces were also stable after exposure to the CO2-loaded amine solution.

36 MATERIALS SCIENCE↗

Solid and gas thermal conductivity models improvement and validation in various porous insulation materials

In the past few decades, significant efforts have been made to improve the theoretical understanding of thermal transport mechanisms in thermal insulation materials and push the thermal conductivity's lower limits. However, most works focused singularly on specific types of materials, and the models used for thermal conductivity predictions are diverse - a model that fits one material might not fit others. Here, we improve and unify the gas and solid thermal conductivity models for porous materials. Through experimental characterization of several different materials as well as literature data for other materials, these models are validated. Further, we have also found that the pressure-dependent gas thermal conductivity of most materials can be well fitted by using one or two pore sizes without using a complex pore size distribution. With the refined models, we decompose the effective thermal conductivity of several thermal insulation materials into gas, solid, and radiation contributions. For cellular (polystyrene and polyurethane) foams, the relative contributions from air, solid, and radiation are 58–75%, 3–11%, 16–38%, respectively. For granular porous materials (polyurethane and silica in this work), the contributions from air, solid, and radiation are 45–66%, 34–46%, and 0–8%, respectively. This work is expected to provide guidance on the design and optimization of the next generation of thermal insulation materials, for example, through the effort of reducing gas conduction and radiation in foams and suppressing gas and solid conduction in aerogels.

36 MATERIALS SCIENCE↗

Encapsulation of hygroscopic liquids via polymer precipitation in non-aqueous emulsions

Here, encapsulation of ionic liquids (ILs) and phase change materials (PCMs) can overcome limitations associated with bulk materials, e.g., slow mass transfer rates, high viscosities, or susceptibility to external environment. Single step soft-templated encapsulation methods commonly use interfacial polymerization for shell formation, with a multifunctional monomer in the continuous phase and another in the discontinuous phase, and thus do not give pristine core material. We posit that polymer precipitation onto emulsion droplets in non-aqueous emulsions could produce a robust shell without contamination of the core, ideal for the encapsulation of water-sensitive or water-miscible materials. Solutions of commodity polymers were added to the continuous phase of non-aqueous Pickering emulsions stabilized by alkylated graphene oxide (GO) nanosheets such that the change in solubility of the polymer led to formation of robust shells and the production of capsules that could be isolated. We demonstrate that a polymer precipitation approach can produce capsules with pristine core of the IL 1-ethyl-3-methylimidazolium hexafluorophosphate [Emim][PF 6 ] or the salt hydrate PCM magnesium nitrate hexahydrate (MNH) and shell of nanosheets and polystyrene, poly(methyl methacrylate), or polyethylene. The capsules are approximately 80 wt% [Emim][PF 6 ] or >90 wt% MNH, and the core can undergo multiple cycles of solidification and melting without leakage or destruction. This novel, single-step methodology provides a distinct advantage to access capsules with pristine core composition and is amenable to different core and shell, paving the way for tailoring capsule composition for desired applications.

36 MATERIALS SCIENCE↗

Facile polymerization in a bicellar template to produce polymer nano-rings

We report a well-defined discoidal bicelle composed of three lipids, specifically zwitterionic long-chain 1,2-dipalmitoyl phosphocholine (DPPC) and short-chain 1,2-dihexanoyl phosphocholine (DHPC) doped with anionic 1,2-dipalmitoyl phosphoglycerol (DPPG) provides a generalized template for the synthesis of hydrophobic polymer nano-rings. The lipid molar ratio of DPPC/DHPC/DPPG is 0.71/0.25/0.04. The detailed investigation and discussion were based on styrene but tested on three other vinyl monomers. The structure of nano-rings is identified through the detailed analysis of small angle X-ray/neutron scattering (SAXS and SANS) data and transmission electron micrographs (TEM), supported by the differential scanning calorimetric (DSC) data before and after polymerization. The investigation covers samples with a styrene-to-lipid ratio ranged varied from 1:50 to 1:10.The styrene monomers are initially located at both the discoidal planar (long-chain lipid rich) and rim (short-chain lipid rich) regions. During polymerization, they migrate to the more fluid rim region-section. The formation mechanism involves the interplay of hydrophobic interaction, mismatched miscibility of polystyrene between the ordered and disordered phases, and crystallinity of the long lipid acyl chains. This facile synthesis is proven applicable for several hydrophobic monomers. The well-defined nano-rings greatly enhance the interfacial area and have the potential to be the building blocks for functional materials, if monomers are incorporated with desirable functions, for future applications. Crosslinked polymer nano-rings are produced in well-defined discoidal bicelles. The enhanced immiscibility in the planar region drives the hydrophobic polymers to the fluidic rim. The platform can be generalized for synthesis of other hydrophobic polymer nano-rings.

36 MATERIALS SCIENCE↗

Characterization of supersonic radiation diffusion waves

Supersonic and diffusive radiation flow is an important test problem for the radiative transfer models used in radiation-hydrodynamics computer codes owing to solutions being accessible via analytic and numeric methods. We present experimental results with which we compare these solutions by studying supersonic and diffusive flow in the laboratory. Here, we present results of higher-accuracy experiments than previously possible studying radiation flow through up to 7 high-temperature mean free paths of low-density, chlorine-doped polystyrene foam and silicon dioxide aerogel contained by an Au tube. Measurements of the heat front position and absolute measurements of the x-ray emission arrival at the end of the tube are used to test numerical and analytical models. We find excellent absolute agreement with simulations provided that the opacity and the equation of state are adjusted within expected uncertainties; analytical models provide a good phenomenological match to measurements but are not in quantitative agreement due to their limited scope.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

The role of polymer films on the oxidation of magnetite nanoparticles

A detailed investigation about the role of polymer films on the oxidation process of magnetite nanoparticles (∼7 nm diameter), under laser irradiation is performed employing micro Raman spectroscopy. To support this investigation, Fe{sub 3}O{sub 4}-np are synthesized by the co-precipitation method and assembled layer-by-layer with sodium sulfonated polystyrene (PSS). Polymer films (Fe{sub 3}O{sub 4}-np/PSS){sub n} with n=2,3,5,7,10 and 25 bilayers are employed as a model system to study the oxidation process under laser irradiation. Raman data are further processed by principal component analysis. Our findings suggest that PSS protects Fe{sub 3}O{sub 4}-np from oxidation when compared to powder samples, even for the sample with the greater number of bilayers. Further, the oxidation of magnetite to maghemite occurs preferably for thinner films up to 7 bilayers, while the onset for the formation of the hematite phase depends on the laser intensity for thicker films. Water takes part on the oxidation processes of magnetite, the oxidation/phase transformation of Fe{sub 3}O{sub 4}-np is intensified in films with more bilayers, since more water is included in those films. Encapsulation of Fe{sub 3}O{sub 4}-np by PSS in layer-by-layer films showed to be very efficient to avoid the oxidation process in nanosized magnetite. - Graphical abstract: Encapsulation of Fe{sub 3}O{sub 4}-np by PSS in layer-by-layer films avoids the oxidation and phase transformation of nanosized magnetite. - Highlights: • (Fe{sub 3}O{sub 4}-np/PSS){sub n} nanofilms, with n=2 up to 25, where layer-by-layer assembled. • The influence of film architecture on the Fe{sub 3}O{sub 4}-np oxidation was investigated through Raman spectroscopy. • Encapsulation of Fe{sub 3}O{sub 4}-np by PSS showed to be very efficient to avoid the Fe{sub 3}O{sub 4}-np oxidation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Phenomenal improvement of external quantum efficiency, detectivity and responsivity of nitrogen doped graphene quantum dot decorated zinc oxide nanorod/polymer schottky junction UV detector

Highlights: • ZnO nanorods/conducting polymer Schottky junction UV detector was fabricated. • GQDs and NGQDs were attached with nanorods to improve the detector performance. • The photodetector demonstrated high EQE, detectivity and responsivity. • NGQDs sensitized nanorod based detectors showed superior performances. • NGQD sensitized device showed high photocurrent even at lower intensity of UV light. - Abstract: Photodetector properties of nitrogen doped graphene quantum dot (NGQD) sensitized ZnO nanorods/poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) Schottky junction has been investigated. The photodetector demonstrated superior external quantum efficiency (EQE) (∼57681% at −1 V bias) at wavelength ∼340 nm, which is 4 times higher than graphene quantum dot (GQD) modified ZnO NRs based detector and 35 times higher than pristine ZnO NRs detector. NGQD modified detectors also showed higher responsivity (∼158 A/W), detectivity (8.7 × 10{sup 12} Hz{sup 1/2}/W) at 340 nm wavelength. The response and recovery times of the detector is very fast compared to GQD modified and pristine ZnO nanorod based detectors. Our UV detector also demonstrated higher photocurrent even at lower intensity range of incident light.

36 MATERIALS SCIENCE↗

Benchmark CO 2 separation achieved by highly fluorinated nanoporous molecular sieve membranes from nonporous precursor via in situ cross-linking

Molecular sieve membranes with rigid micropores and CO 2 -philic functionalities within the architectures are promising candidates in CO 2 separation. However, the development of ctieve approaches for their fabrication still remains a significant challenge. In this study, an in situ cross-linking strategy is developed for the preparation of nanoporous fluorinated moleffecular sieve membranes using commercially available dense and non-porous polystyrene (M PS ) as a precursor template. Based on the dehydrative Friedel-Crafts reactions with highly fluorinated benzylic alcohols, M PS membranes are cross-linked in situ upon exposure to Brønsted acid (CF 3 SO 3 H), affording fluorinated microporous polymeric membranes with surface areas up to 523 m 2 g –1 and the presence of micropores centered at 1.1–1.3 nm as well as ultra-micropores (~0.6 nm). The obtained modified membranes exhibit good ideal CO 2 permeability of 797 barrer and CO 2 /N 2 selectivity of 28.5. In addition, high fluorine content (up to 28.5 wt%) and good thermal stability made the cross-linked membranes promising candidates to produce fluorinated carbon molecular sieve membranes with improved textural properties, exhibiting surface areas up to 1020 m 2 g –1 and ultra-micropores of ~0.4 nm. These membranes achieve superior CO 2 /N 2 separation performances exceeding the Robeson upper bound limit (2008).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Exfoliation of surfactant swollen layered MWW zeolites into two-dimensional zeolite nanosheets using telechelic liquid polybutadiene

We report two-dimensional (2D) zeolites have the potential to enhance mass transport by reducing diffusion lengths and thus find applications in catalysis and separation. High aspect ratio 2D zeolite nanosheets are required for fabrication of thin, high-flux zeolite membranes. Preparation of 2D zeolite nanosheets can be achieved by exfoliation of layered zeolite precursors, which usually requires multiple steps including swelling with cationic surfactants, exfoliation by applying a mechanical force such as shearing or sonication, purification and removal of the surfactants. The exfoliation of surfactant swollen layered zeolite precursors has been studied using molten polystyrene and telechelic liquid polybutadiene, but still requires extensive shearing force. Recently, a novel one-step exfoliation method has been developed for nonswollen MWW zeolite precursors using tetrabutylammonium hydroxide (TBAOH) solution. In this work, we study the exfoliation of surfactant swollen MWW layered precursors (with and without aluminum) in commercially available liquid hydroxyl-terminated polybutadiene (HTPB) with the aim to provide fundamental understanding of the interaction between the liquid polybutadiene and the surfactant swollen layered zeolite precursors. It was found that surfactant swollen ITQ-1, (ITQ-1(S)), a pure silica layered precursor with MWW framework after being swollen with a cationic surfactant, can be exfoliated in liquid HTPB at room temperature without applying any additional shearing force. The aluminum containing surfactant swollen MWW precursors can be also exfoliated in HTPB at room temperature, but require additional shearing forces. The exfoliation process was monitored using rheology experiments and studied by tuning the composition of the zeolite precursors. The interaction between the layered zeolite precursor and the hydroxyl group of the liquid polybutadiene allows the polymer to intercalate the precursor and exfoliate it into nanosheets. The presence of framework aluminum and the nature of the organic structure directing agents (OSDAs) are key parameters affecting the exfoliation process. Framework Al is unfavorable for the exfoliation possibly due to the surface charges introduced by the aluminum. Bulky OSDA, trimethyladamantammonium (TMAda + ), in the interlayer spacing may facilitate the exfoliation.

2D nanosheets↗

Orientation mapping of semicrystalline polymers using scanning electron nanobeam diffraction

Here, we demonstrate a scanning electron nanobeam diffraction technique that can be used for mapping the size and distribution of nanoscale crystalline regions in a polymer blend. In addition, it can map the relative orientation of crystallites and the degree of crystallinity of the material. The model polymer blend is a 50:50 w/w mixture of semicrystalline poly(3-hexylthiophene-2,5-diyl) (P3HT) and amorphous polystyrene (PS). The technique uses a scanning electron beam to raster across the sample and acquires a diffraction image at each probe position. Through image alignment and filtering, the diffraction image dataset enables mapping of the crystalline regions within the scanned area and construction of an orientation map.

36 MATERIALS SCIENCE↗

Liquid chromatography at critical conditions (LCCC): Capabilities and limitations for polymer analysis

This paper investigates liquid chromatography at critical condition (LCCC) for polymer analysis. Based on controversial claims on the separation of cyclic polymers from linear analogues in the literature, the efficiency of LCCC for separation and purity analysis is questioned. Polyisobutylene (PIB) and poly(3,6-dioxa-1,8-octanedithiols) (polyDODT) were used for the study. Here, the structure of low molecular weight cyclic and linear polyDODT was demonstrated by MALDI-ToF. NMR did not show the presence of thiol end groups in higher molecular weight PIB-disulfide and polyDODT samples, so they were considered cyclic polymers. When a low molecular weight polyDODT oligomer with only traces of cycles, as demonstrated by MALDI-ToF, was mixed with an M n = 27K g/mol cyclic sample, LCCC did not detect the presence of linear oligomers at 6 wt%. Based on the data presented here, it can be concluded that the LCCC method is not capable of measuring < 6 wt% linear contamination so earlier claims for cyclic polystyrene (PS) samples purified by LCCC having < 3 % linear contaminants are questioned.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Properties of vapor-deposited and solution-processed targets for laser-driven inertial confinement fusion experiments

Targets for low-adiabat direct-drive-implosion experiments on OMEGA must meet rigorous specifications and tight tolerances on the diameter, wall thickness, wall-thickness uniformity, and presence of surface features. Of these, restrictions on the size and number of defects (bumps and depressions) on the surface are the most challenging. The properties of targets that are made using vapor-deposition and solution-based microencapsulation techniques are reviewed. Targets were characterized using confocal microscopy, bright- and dark-field microscopy, atomic force microscopy, electron microscopy, and interferometry. Each technique has merits and limitations, and a combination of these techniques is necessary to adequately characterize a target. The main limitation with the glow-discharge polymerization (GDP) method for making targets is that it produces hundreds of domes with a lateral dimension of 0.7–2 μm. Polishing these targets reduces the size of some but not all domes, but it adds scratches and grooves to the surface. Solution-made polystyrene shells lack the dome features of GDP targets but have hundreds of submicrometer-size voids throughout the wall of the target; a few of these voids can be as large as ∼12 μm at the surface.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Low-cost, multi-mode detector solutions

Low-cost radiation detectors capable of providing efficient gamma-ray and neutron detection are essential in passive nuclear monitoring systems such as radiation portal monitors (RPMs) and detection of Special Nuclear Materials (SNM) through Active Interrogation (AI). Here, three low-cost detector solutions are discussed—(1) Large-area polystyrene-based plastic scintillators for AI (2) Pulse Shape Discrimination (PSD) capable plastic scintillators doped with heavy-metals for imparting gamma-ray spectroscopy (3) Composite detector technology based on inorganic scintillator submerged into the plastic scintillator, for detection of thermal and fast neutrons in addition to gamma-ray spectroscopy. Composite detectors using inorganic component such as Cs 2 LiYCl 6 (CLYC), Cs 2 LiLaBr x Cl 6-x (CLLBC), or CsI:Tl have been developed up to 4” sizes. Neutron and gamma efficiencies are compared for samples with different inorganic loading.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Tensile, flexural, and light output measurements of selected organic scintillators for evaluation of their potential as structural materials

In order to design structures, such as unmanned vehicle structures, out of plastic scintillator, e.g., for radionuclide searches, suitable materials must either be identified or developed. In searches utilizing unmanned vehicles, the absence of an additional detector attached to the vehicle body as a payload could enable the vehicle to travel faster, carry a longer lived battery, or carry other auxiliary equipment which may be useful for search and/or response. To this end, four mechanical characteristics of selected organic scintillators manufactured by Eljen technologies, Sandia Livermore, and Lawrence Livermore National Lab have been measured. Specifically, tensile and flexural tests have been performed to ASTM specifications on organic scintillators with polyvinyl toluene (PVT), polystyrene (PS), or crosslinked versions of these bases. In addition to these mechanical tests, light output testing was performed in order to quantify whether crosslinking or adding organometallic complexes affects light output in the particular scintillator compositions we measured. We found that the tested plastic scintillators have strengths that are comparable to common structural plastics. We also show that chemically modifying the polymer base can show improvements in the mechanical properties without being overly detrimental to the scintillator light output.

42 ENGINEERING↗

Plastic scintillators stable for operating in wide ranges of humidity and temperature variations

To provide efficient and reproducible response to nuclear radiation, scintillating plastics should be prepared as materials of high optical transparency and homogeneity that should remain intact during the lifetime of their operation. A problem with traditionally used polyvinyltoluene (PVT) or polystyrene (PS) plastic scintillators arises from their exposure to repeated large temperature swings that cause surface and volume defects, resulting in decreased sensitivity of the detection properties. We find that the problem can be avoided by composition modifications that enable preparation of plastics with properties that are resistant to the continuous variations in environmental conditions. This paper describes improvements in physical properties that can be achieved by the addition of crosslinkers (such as divinylbenzene, DVB) and oxygen-containing compounds or copolymers (e.g. polymethylamethacrylate, PMMA) to the traditional PVT or PS polymer matrices. Results of characterization show that the new materials can be prepared with the scintillation performance equal to that of commercial plastic scintillators, such as EJ-200.

36 MATERIALS SCIENCE↗

Investigations of degradation and encapsulation of plastic scintillator

Studies have revealed that plastic scintillators such as polyvinyl toluene and polystyrene can undergo environmentally related material damage (“fogging”) that adversely affects detection performance under certain conditions and histories. A significant decrease in sensitivity has been seen in some gamma-ray detectors as they age as a result of this damage. Performance degradation due to such damage is characterized by a signal change from the detector, which shifts to lower energy, and ultimately a reduction in the ability to detect gamma radiation. This degradation is due to the permeation of water into the plastic, which can then cause temporary fogging and permanent damage to the material. As an example, a 1-mm thick barrier of high-density polyethylene with an area of 1 m 2 would allow 5 g per year of water transmission at 100% relative humidity. Thus, significant amounts of water can penetrate plastics over time and provide the potential for damage to the plastic. Such damage to plastic scintillator can cause problems for radiation detection applications in uncontrolled environments. Mitigation approaches that have been proposed to prevent damage to plastic scintillator include encapsulation of the plastic scintillator to prevent water intrusion that leads to damage during cold cycles. It is concluded that an encapsulation material with a moisture vapor transmission rate on the order of 10 -4 g∙m -2 ∙d -1 or better is needed for protecting large pieces of plastic scintillator from fogging over years of use. This article presents information on testing of bare and encapsulated plastic scintillator samples and on diagnostic approaches to measure the nature and progression of the fogging condition. It is shown that several encapsulation approaches fail to prevent water intrusion, while a couple methods can successfully encapsulate plastic and prevent water from penetrating the plastic and producing fogging.

36 MATERIALS SCIENCE↗

Characterization of 6 Li-loaded pulse-shape-discriminating plastic scintillators

Lithium-loaded organic plastic scintillators combine sensitivity to γ rays with the ability to detect both fast and slow neutrons, making them valuable for applications in nuclear security and in basic nuclear and particle physics. The goal of this work is to characterize the neutron response of two custom lithium-loaded organic plastic scintillators developed at Lawrence Livermore National Laboratory. Both are ternary polystyrene-based formulations containing 1.5 wt.% 6 Li salts of isobutyric acid, but they differ in their primary and secondary dye compositions: one uses m-terphenyl as the primary fluor and with Exalite 404 as the wavelength shifter, whereas the other uses 2,5-diphenyloxazole (PPO) and 9,10-diphenyl-anthracene, respectively. The temporal response of the scintillators was measured via time-correlated single photon counting for γ-ray and neutron events. The proton light yield was measured using the double time-of-flight technique from 1.3 to 15 MeV at the 88-Inch Cyclotron at Lawrence Berkeley National Laboratory. For the slow neutron response, an AmBe source moderated with polyethylene was used, and the light output from the 6 Li(n,α)t reaction was characterized. Differences in ionization quenching and temporal response were observed between the two materials with the PPO-containing scintillator exhibiting higher ionization quenching. These results provide performance benchmarks that can guide the design and optimization of future lithium-loaded plastic scintillators for use in basic science and applications.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗