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At least 757 records · Page 42

Study on the Thermal Stabilizing Process of Layered Double Hydroxides in PVC Resin

Poly(vinyl chloride) (PVC) is widely used in various fields and requires the use of thermal stabilizers to enhance its thermal stability during processing because of its poor thermal stability. Layered double hydroxides (LDHs) are widely considered to be one kind of highly efficient and environmentally friendly PVC thermal stabilizer. To investigate the thermal stabilizing process of layered double hydroxides (LDHs) in PVC resin, PVC and MgAl-LDHs powders with different interlayer anions (CO 3 2- , Cl - , and NO 3 - ) were physically mixed and aged at 180 °C. The structure of LDHs at different aging times was studied using XRD, SEM, and FT-IR. The results show that the thermal stabilizing process of LDHs on PVC mainly has three stages. In the first stage, the layers of LDHs undergo a reaction with HCl, which is released during the thermal decomposition of PVC. Subsequently, the ion exchange process occurs between Cl - and interlayer CO 3 2- , resulting in the formation of MgAl-Cl-LDHs. Finally, the layers of MgAl-Cl-LDHs react with HCl slowly. During the thermal stabilizing process of MgAl-Cl-LDHs, the peak intensity of XRD reduces slightly, and no new XRD peak emerges. It indicates that only the first step happens for MgAl-Cl-LDHs. The TG-DTA analysis of LDHs indicates that the interaction of LDHs with different interlayer anions has the following order: NO 3 - < CO 3 2- < Cl - , according to the early coloring in the thermal aging test of PVC composites. The results of the thermal aging tests suggest that LDHs with a weak interaction between interlayer anions and layers can enhance the early stability of PVC significantly. Furthermore, the thermal aging test demonstrates that LDHs with high HCl absorption capacities exhibit superior long-term stabilizing effects on PVC resin. This finding provides a valuable hint for designing an LDHs/PVC resin with a novel structure and excellent thermal stability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Design and Gas Separation Performance of Imidazolium Poly(ILs) Containing Multivalent Imidazolium Fillers and Crosslinking Agents

This work introduces a series of vinyl-imidazolium-based polyelectrolyte composites, which were structurally modified via impregnation with multivalent imidazolium-benzene ionic liquids (ILs) or crosslinked with novel cationic crosslinkers which possess internal imidazolium cations and vinylimidazolium cations at the periphery. A set of eight [C4vim][Tf2N]-based membranes were prepared via UV-initiated free radical polymerization, including four composites containing di-, tri-, tetra-, and hexa-imidazolium benzene ILs and four crosslinked derivatives which utilized tri- and tetra- vinylimidazolium benzene crosslinking agents. Structural and functional characterizations were performed, and pure gas permeation data were collected to better understand the effects of “free” ILs dispersed in the polymeric matrix versus integrated ionic crosslinks on the transport behaviors of these thin films. These imidazolium PIL:IL composites exhibited moderately high CO2 permeabilities (~20–40 Barrer), a 4–7× increase relative to corresponding neat PIL, with excellent selectivities against N2 or CH4. The addition of imidazolium-benzene fillers with increased imidazolium content were shown to correspondingly enhance CO2 solubility (di- < tri- < tetra- < hexa-), with the [C4vim][Tf2N]: [Hexa(Im+)Benz ][Tf2N] composite showing the highest CO2 permeability (PCO2 = 38.4 Barrer), while maintaining modest selectivities (αCO2/CH4 = 20.2, αCO2/N2 = 23.6). Additionally, these metrics were similarly improved with the integration of more ionic content bonded to the polymeric matrix; increased PCO2 with increased wt% of the tri- and tetra-vinylimidazolium benzene crosslinking agent was observed. This study demonstrates the intriguing interactions and effects of ionic additives or crosslinkers within a PIL matrix, revealing the potential for the tuning of the properties and transport behaviors of ionic polymers using ionic liquid-inspired small molecules.

36 MATERIALS SCIENCE↗

Accessibility and Mechanical Stability of Nanoporous Zinc Oxide and Aluminum Oxide Coatings Synthesized via Infiltration of Polymer Templates

The conformal nanoporous inorganic coatings with accessible pores that are stable under applied thermal and mechanical stresses represent an important class of materials used in the design of sensors, optical coatings, and biomedical systems. Here, we synthesize porous AlO x and ZnO coatings by the sequential infiltration synthesis (SIS) of two types of polymers that enable the design of porous conformal coatings—polymers of intrinsic microporosity (PIM) and block co-polymer (BCP) templates. Using quartz crystal microbalance (QCM), we show that alumina precursors infiltrate both polymer templates four times more efficiently than zinc oxide precursors. Using the quartz crystal microbalance (QCM) technique, we provide a comprehensive study on the room temperature accessibility to water and ethanol of pores in block copolymers (BCPs) and porous polymer templates using polystyrene-block-poly-4-vinyl pyridine (PS75-b-P4VP25) and polymers of intrinsic microporosity (PIM-1), polymer templates modified by swelling, and porous inorganic coatings such as AlO x and ZnO synthesized by SIS using such templates. Importantly, we demonstrate that no structural damage occurs in inorganic nanoporous AlO x and ZnO coatings synthesized via infiltration of the polymer templates during the water freezing/melting cycling tests, suggesting excellent mechanical stability of the coatings, even though the hardness of the inorganic nanoporous coating is affected by the polymer and precursor selections. We show that the hardness of the coatings is further improved by their annealing at 900 °C for 1 h, though for all the cases except ZnO obtained using the BCP template, this annealing has a negligible effect on the porosity of the material, as is confirmed by the consistency in the optical characteristics. These findings unravel new potential for the materials being used across various environment and temperature conditions.

36 MATERIALS SCIENCE↗

Fabricating Reactive Surfaces with Brush-like and Crosslinked Films of Azlactone-Functionalized Block Co-Polymers

Here in this work, fabrication methods that generate novel surfaces using the azlactone-based block co-polymer, poly (glycidyl methacrylate)-block-poly (vinyl dimethyl azlactone) (PGMA-b-PVDMA), are presented. Due to the high reactivity of azlactone groups towards amine, thiol, and hydroxyl groups, PGMA-b-PVDMA surfaces can be modified with secondary molecules to create chemically or biologically functionalized interfaces for a variety of applications. Previous reports of patterned PGMA-b-PVDMA interfaces have used traditional top-down patterning techniques that generate non-uniform films and poorly controlled background chemistries. Here, we describe customized patterning techniques that enable precise deposition of highly uniform PGMA-b-PVDMA films in backgrounds that are chemically inert or that have biomolecule-repellent properties. Importantly, these methods are designed to deposit PGMA-b-PVDMA films in a manner that completely preserves azlactone functionality through each processing step. Patterned films show well-controlled thicknesses that correspond to polymer brushes (~90 nm) or to highly crosslinked structures (~1-10 μm). Brush patterns are generated using either the parylene lift-off or interface directed assembly methods described and are useful for precise modulation of overall chemical surface reactivity by adjusting either the PGMA-b-PVDMA pattern density or the length of the VDMA block. In contrast, the thick, crosslinked PGMA-b-PVDMA patterns are obtained using a customized micro-contact printing technique and offer the benefit of higher loading or capture of secondary material due to higher surface area to volume ratios. Lastly, detailed experimental steps, critical film characterizations, and trouble-shooting guides for each fabrication method are discussed.

36 MATERIALS SCIENCE↗

Laboratory Investigations into the Spectra and Origin of Propylene Oxide: A Chiral Interstellar Molecule

Propylene oxide was recently identified in the interstellar medium, but few laboratory results are available for this molecule to guide current and future investigations. To address this situation, here we report infrared spectra, absorption coefficients, and band strengths of solid propylene oxide along with the first measurement of its refractive index and a calculation of its density, all for the amorphous solid form of the compound. We present the first experimental results showing a low-temperature formation pathway for propylene oxide near 10 K in interstellar ice analogs. Connections are drawn between our new results and the interstellar molecules propanal and acetone, and predictions are made about several as yet unobserved vinyl alcohols and methylketene. Comparisons are given to earlier laboratory work and a few applications to interstellar and solar system astrochemistry are described.

79 ASTRONOMY AND ASTROPHYSICS↗

On the Formation of the C{sub 2}H{sub 6}O Isomers Ethanol (C{sub 2}H{sub 5}OH) and Dimethyl Ether (CH{sub 3}OCH{sub 3}) in Star-forming Regions

The structural isomers ethanol (CH{sub 3}CH{sub 2}OH) and dimethyl ether (CH{sub 3}OCH{sub 3}) were detected in several low-, intermediate-, and high-mass star-forming regions, including Sgr B2, Orion, and W33A, with the relative abundance ratios of ethanol/dimethyl ether varying from about 0.03 to 3.4. Until now, no experimental data regarding the formation mechanisms and branching ratios of these two species in laboratory simulation experiments could be provided. Here, we exploit tunable photoionization reflectron time-of-flight mass spectrometry (PI-ReTOF-MS) to detect and analyze the production of complex organic molecules (COMs) resulting from the exposure of water/methane (H{sub 2}O/CH{sub 4}) ices to energetic electrons. The main goal is to understand the formation mechanisms in star-forming regions of two C{sub 2}H{sub 6}O isomers: ethanol (CH{sub 3}CH{sub 2}OH) and dimethyl ether (CH{sub 3}OCH{sub 3}). The results show that the experimental branching ratios favor the synthesis of ethanol versus dimethyl ether (31 ± 11:1). This finding diverges from the abundances observed toward most star-forming regions, suggesting that production routes on interstellar grains to form dimethyl ether might be missing; alternatively, ethanol can be overproduced in the present simulation experiments, such as via radical–radical recombination pathways involving ethyl and hydroxyl radicals. Finally, the PI-ReTOF-MS data suggest the formation of methylacetylene (C{sub 3}H{sub 4}), ketene (CH{sub 2}CO), propene (C{sub 3}H{sub 6}), vinyl alcohol (CH{sub 2}CHOH), acetaldehyde (CH{sub 3}CHO), and methyl hydroperoxide (CH{sub 3}OOH), in addition to ethane (C{sub 2}H{sub 6}), methanol (CH{sub 3}OH), and CO{sub 2} detected from infrared spectroscopy. The yield of all the confirmed species is also determined.

79 ASTRONOMY AND ASTROPHYSICS↗

What do correlations tell us about anthropogenic–biogenic interactions and SOA formation in the Sacramento plume during CARES?

Abstract. During the Carbonaceous Aerosols and Radiative Effects Study (CARES) the US Department of Energy (DOE) G-1 aircraft was used to sample aerosol and gas phase compounds in the Sacramento, CA, plume and surrounding region. We present data from 66 plume transects obtained during 13 flights in which southwesterly winds transported the plume towards the foothills of the Sierra Nevada. Plume transport occurred partly over land with high isoprene emission rates. Our objective is to empirically determine whether organic aerosol (OA) can be attributed to anthropogenic or biogenic sources, and to determine whether there is a synergistic effect whereby OA concentrations are enhanced by the simultaneous presence of high concentrations of carbon monoxide (CO) and either isoprene, MVK + MACR (sum of methyl vinyl ketone and methacrolein), or methanol, which are taken as tracers of anthropogenic and biogenic emissions, respectively. Linear and bilinear correlations between OA, CO, and each of three biogenic tracers, “Bio”, for individual plume transects indicate that most of the variance in OA over short timescales and distance scales can be explained by CO. For each transect and species a plume perturbation, (i.e., ΔOA, defined as the difference between 90th and 10th percentiles) was defined and regressions done amongst Δ values in order to probe day-to-day and location-dependent variability. Species that predicted the largest fraction of the variance in ΔOA were ΔO 3 and ΔCO. Background OA was highly correlated with background methanol and poorly correlated with other tracers. Because background OA was ~60 % of peak OA in the urban plume, peak OA should be primarily biogenic and therefore non-fossil, even though the day-to-day and spatial variability of plume OA is best described by an anthropogenic tracer, CO. Transects were split into subsets according to the percentile rankings of ΔCO and ΔBio, similar to an approach used by Setyan et al. (2012) and Shilling et al. (2013) to determine if anthropogenic–biogenic (A–B) interactions enhance OA production. As found earlier, ΔOA in the data subset having high ΔCO and high ΔBio was several-fold greater than in other subsets. Part of this difference is consistent with a synergistic interaction between anthropogenic and biogenic precursors and part to an independent linear dependence of ΔOA on precursors. The highest values of ΔO 3 , along with high temperatures, clear skies, and poor ventilation, also occurred in the high ΔCO–high ΔBio data set. A complicated mix of A–B interactions can result. After taking into account linear effects as predicted from low concentration data, an A–B enhancement of OA by a factor of 1.2 to 1.5 is estimated.

54 ENVIRONMENTAL SCIENCES↗

A novel Whole Air Sample Profiler (WASP) for the quantification of volatile organic compounds in the boundary layer

The emission and fate of reactive VOCs is of inherent interest to those studying chemical biosphere-atmosphere interactions. In-canopy VOC observations are obtainable using tower-based samplers, but the lack of suitable sampling systems for the full boundary 5 layer has limited the data characterizing the vertical structure of such gases above the canopy height and still in the boundary layer. This is the important region where many reactive VOCs are oxidized or otherwise removed. Here we describe an airborne sampling system designed to collect a vertical profile of air into a 3/800 OD tube 150m in length. The inlet ram air pressure is used to flow sampled air through the 10 tube, which results in a varying flow rate based on aircraft speed and altitude. Since aircraft velocity decreases during ascent, it is necessary to account for the variable flow rate into the tube. This is accomplished using a reference gas that is pulsed into the air stream so that the precise altitude of the collected air can be reconstructed post-collection. The pulsed injections are also used to determine any significant effect 15 from diffusion/mixing within the sampling tube, either during collection or subsequent extraction for gas analysis. This system has been successfully deployed, and we show some measured vertical profiles of isoprene and its oxidation products methacrolein and methyl vinyl ketone from a mixed canopy near Columbia, Missouri.

Mak, J. E.↗

EPCAPE-PT-LANL Measurements: Proton Transfer Reaction Mass Spectrometer

Coastal cities offer a unique environment for studying aerosol-cloud interactions and the effects of urban emissions on cloud properties. As part of the Eastern Pacific Cloud Aerosol Precipitation Experiment (EPCAPE), the Partitioning Thrust by Los Alamos National Laboratory (EPCAPE-PT-LANL) was conducted. Our campaign focused on measuring the optical and chemical properties of aerosols and their interactions within marine stratocumulus clouds in La Jolla, California. EPCAPE-PT-LANL enhances the primary goals of EPCAPE through innovative observations of vapor-phase transitions between aerosols and cloud droplets, the impact of black carbon on aerosol-cloud dynamics, and the effects of cloud processing on aerosol optical properties. Instrument: IONICON High-Resolution PTR-TOF-MS - Trace VOC Analyzer. Concentrations were calculated based on theoretical reaction rates of each species with H3O+. Details of the calculation are found in the PTR-MS Ionicon Manual. Data Notes: It is a high-resolution PTR-TOF-MS we have sub-selected relevant species. Contact us if you want additional data products from this instrument. Header: - CalculatedAcetonitrile[ppbv]: The concentration of acetonitrile expressed in parts per billion by volume (ppbv). - CalculatedAcetaldehyde[ppbv]: The concentration of acetaldehyde expressed in parts per billion by volume (ppbv). - CalculatedAcetone[ppbv]: The concentration of acetone expressed in parts per billion by volume (ppbv). - CalculatedAceticAcid[ppbv]: The concentration of acetic acid expressed in parts per billion by volume (ppbv). - CalculatedIsoprene[ppbv]: The concentration of isoprene expressed in parts per billion by volume (ppbv). - CalculatedMVK[ppbv]: The concentration of methyl vinyl ketone (MVK) and methacrolein (MACR) expressed in parts per billion by volume (ppbv). - CalculatedMEK[ppbv]: The concentration of methyl ethyl ketone (MEK) expressed in parts per billion by volume (ppbv). - CalculatedBenzene[ppbv]: The concentration of benzene expressed in parts per billion by volume (ppbv). - CalculatedToluene[ppbv]: The concentration of toluene expressed in parts per billion by volume (ppbv).

54 ENVIRONMENTAL SCIENCES↗

High Contrast Pattern Projection To Enable Background Oriented Schlieren Based Air Leak Detection Through Any Interior Or Exterior Building Surface

Air leakage in buildings wastes an estimated 4 quads of energy per year in the United States. Finding and sealing leakage sites is critical in existing buildings. Previous work has shown that background oriented Schlieren (BOS) imaging can be used to visualize air leakage but requires the leak to exit through a high contrast surface like a brick wall. To remedy this, different techniques of projecting various high contrast patterns on low contrast building surfaces like interior gypsum walls or vinyl siding were investigated. For each technique, the background quality was measured and compared to an ideal printed random dot background. The background quality metrics were correlated with the measured visualization metrics to understand which metrics are most important for maximizing air leak visualization performance. In this work, leakage visualization performance is presented for these various projected backgrounds with an aim to expand the building surfaces suitable for the BOS leak detector.

Jatana, Gurneesh [ORNL] (ORCID:0000000288903225)↗

Thermoplastic rubberlike material produced at low cost

Thermoplastic rubberlike material is prepared by blending a copolymer of ethylene and vinyl acetate with asphalt and a petroleum distillate. This low cost material is easily molded or extruded and is compatible with a variety of fillers.

Hendel, F. J.↗

Quick don-doff electrode pastes

Evaluation of electrode pastes for use in electrocardiographs and electroencephalographs found that the one having the desired don-doff properties had to be water soluble or a water dispersible base. Poly /methyl vinyl ether/maleic anhydride/ or starch gels of the gum drop variety are two such bases.

Mosier, B.↗

Use of nonwettable membranes for water transfer

Transfer of water through nonwettable vinyl fluoride membranes has two unique features - /1/ very low water transfer rates can be held constant by holding temperature and solute concentrations constant, /2/ the pressure gradient against which water is transported is limited only by solution breakthrough or membrane strength.

Hausch, H. G.↗