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At least 559 records · Page 31

The effects of atomic oxygen on polymeric materials

At the altitudes of low-earth orbit (LEO), atomic oxygen (AO) is the most abundant chemical species. This strong oxidizing agent reacts with virtually any organic material that is not already fully oxidized. Erosion by AO can be extensive and jeopardizes any protective coatings, thermal blankets, adhesives, and structural composites exposed on the exterior of satellites in LEO. Researchers prepared and tested organic materials for their susceptibility to AO using a commercial plasma asher which approximately simulates the oxygen effects in LEO. Experiments were performed on a polyimide, a polysulfone, and two epoxy adhesives into which low molecular-weight additives have been dissolved. Incorporated in the molecular structure of these additives are elements such as silicon whose nonvolatile oxides, which are formed on exposure to AO, remain as a coating on the surface to create a barrier between the remainder of the organic material and the AO. We find that the additives protect the materials, but the low solubility of some limit their utility. Concurrent studies are underway to measure the effect of the additives on the thermal expansion coefficients of the materials. Tows of aramid fibers, which are important components in the proposed tether satellite systems, have been eroded in the asher. The results which show that the square root of the mass remaining decreases linearly with the time of exposure (see the figure) are consistent with a constant rate of surface erosion. The tensile strength of these eroded tows decreases with time of exposure also; additional measurements are in progress.

Orwoll, Robert A.↗

Analyses of Aliphatic Aldehydes and Ketones in Carbonaceous Chondrites

Aliphatic aldehydes and ketones are essential building blocks for the synthesis of more complex organic compounds. Despite their potentially key role as precursors of astrobiologically important molecules, such as amino acids and carboxylic acids, this family of compounds has scarcely been evaluated in carbonaceous chondrites. The paucity of such analyses likely derives from the low concentration of aldehydes and ketones in the meteorites and from the currently used chromatographic methodologies that have not been optimized for meteorite analysis. In this work, we report the development of a novel analytical method to quantify the molecular distribution and compound-specific isotopic analysis of 29 aliphatic aldehydes and ketones. Using this method, we have investigated the molecular distribution and C-13-isotopic composition of aldehydes and ketones in 10 carbonaceous chondrites from the CI, CM, CR, and CV groups. The total concentration of carbonyl compounds ranged from 130 to 1000 nmol g(exp -1) of meteorite with formaldehyde, acetaldehyde, and acetone being the most abundant species in all investigated samples. The C-13-isotopic values ranged from -67 to +64‰ and we did not observe clear relationships between C-13-content and molecular weight. Accurately measuring the relative abundances, determining the molecular distribution and isotopic composition of chondritic organic compounds is central in assessing both their formation chemistry and synthetic relationships.

Organic carbon↗

Detailed Characterization of Vitrinite-Rich Subbituminous and Bituminous Coals for Utilization in Carbon Fiber Precursor Production

Chemical structures of candidate coals (one subbituminous coal from the Powder River Basin and three bituminous Eastern US coals) were examined for potential low-cost carbon fiber precursor production. Here, the structural evaluation examined the carbon skeleton ( 13 C nuclear magnetic resonance (NMR) and high-resolution transmission electron microscopy (HRTEM)), the heteroatom functionality (X-ray photoelectron spectroscopy (XPS) Fourier transform infrared spectroscopy (FTIR) and NMR), the structural ordering and distribution of PAH sizes (HRTEM), and an estimation of the molecular weight distribution (laser desorption ionization mass spectrometry, LDIMS). The molecular compositional distributions were also evaluated for a mixed solvent extract (atmospheric pressure photoionization, 21 T Fourier transform ion cyclotron resonance mass spectrometry, FT-ICR MS). Significant structural differences existed between the subbituminous and bituminous coals, as expected with coalification (with the bituminous coals having a higher carbon content, lower oxygen content, higher aromaticity values, larger cluster sizes, and so forth). While the bituminous coals were similar in structure (close in rank with Blue Gem being hvAb and the rest being hvBb), structural differences were still evident. Specifically, structural similarities were evident for the average properties of Herrin and Springfield coals: same rank, similar moisture, and volatile matter yields, along with similar aromaticity and carbon and hydrogen content. However, significant structural differences were observed at the molecular level by 21 T FT-ICR MS, which showed that the Springfield coal was structurally more complex. Specifically, 21740, 16931, 30190, and 12982 unique elemental compositions were identified for the Monarch, Herrin, Springfield, and Blue Gem coals, further illustrating the complexity of the coal.

01 COAL, LIGNITE, AND PEAT↗

Ion Mobilities, Transference Numbers, and Inverse Haven Ratios of Polymeric Ionic Liquids

We probe the ion mobilities, transference numbers, and inverse Haven ratio of ionic liquids and polymerized ionic liquids as a function of their molecular weight using a combination of atomistic equilibrium and nonequilibrium molecular dynamics simulations. In contrast to expectations, we demonstrate that the inverse Haven ratio increases with increasing degree of polymerization (N) and then decreases at larger N. For a fixed center of mass reference frame, we demonstrate that such results arise as a consequence of the strong cation–cation correlated motions, which exceed (in magnitude) the selfdiffusivity of cations. Together, our findings challenge the premise underlying the pursuit of pure polymeric ionic liquids as high transference number, single-ion conducting electrolytes.

36 MATERIALS SCIENCE↗

LDEF polymeric materials: 10 months versus 5.8 years of exposure

The chemical characterization of several polymeric materials which received 10 months of exposure and 5.8 years of exposure on a Row 9 Long Duration Exposure Facility (LDEF) experiment (A0134) is reported. Specimens include fluorinated ethylene propylene (FEP) teflon film, polysulfone film, and graphite fiber reinforced epoxy amd polysulfone matrix composites. The responses of these materials to the two LEO exposures are compared. The results of infrared, thermal, x-ray photoelectron, and scanning electron microscope analyses are reported. Solution property measurements of various molecular weight parameters are presented for the thermoplastic polysulfone materials. Molecular level effects attributable to exposure that were present in 10-month exposed specimens were not found in 5.8-year exposed specimens. This result suggests that increased atomic oxygen fluence toward the end of the LDEF mission may have eroded away selected environmentally induced changes in surface chemistry for 5.8-year exposure specimens.

Young, Philip R.↗

Development of a Linear Ion Trap Mass Spectrometer (LITMS) Investigation for Future Planetary Surface Missions

Future surface missions to Mars and other planetary bodies will benefit from continued advances in miniature sensor and sample handling technologies that enable high-performance chemical analyses of natural samples. Fine-scale (approx.1 mm and below) analyses of rock surfaces and interiors, such as exposed on a drill core, will permit (1) the detection of habitability markers including complex organics in association with their original depositional environment, and (2) the characterization of successive layers and gradients that can reveal the time-evolution of those environments. In particular, if broad-based and highly-sensitive mass spectrometry techniques could be brought to such scales, the resulting planetary science capability would be truly powerful. The Linear Ion Trap Mass Spectrometer (LITMS) investigation is designed to conduct fine-scale organic and inorganic analyses of short (approx.5-10 cm) rock cores such as could be acquired by a planetary lander or rover arm-based drill. LITMS combines both pyrolysis/gas chromatograph mass spectrometry (GCMS) of sub-sampled core fines, and laser desorption mass spectrometry (LDMS) of the intact core surface, using a common mass analyzer, enhanced from the design used in the Mars Organic Molecule Analyzer (MOMA) instrument on the 2018 ExoMars rover. LITMS additionally features developments based on the Sample Analysis at Mars (SAM) investigation on MSL and recent NASA-funded prototype efforts in laser mass spectrometry, pyrolysis, and precision subsampling. LITMS brings these combined capabilities to achieve its four measurement objectives: (1) Organics: Broad Survey Detect organic molecules over a wide range of molecular weight, volatility, electronegativity, concentration, and host mineralogy. (2) Organic: Molecular Structure Characterize internal molecular structure to identify individual compounds, and reveal functionalization and processing. (3) Inorganic Host Environment Assess the local chemical/mineralogical makeup of organic host phases to help determine deposition and preservation factors. (4) Chemical Stratigraphy Analyze the fine spatial distribution and variation of key species with depth.

Mars↗

Utilizing Additive Manufacturing for Biomimetic Designs

Chronic kidney disease effects 15% of adult Americans. Current technology utilizes polymer membranes for separation of toxins and waste from the blood. Yet there still is room for development of new materials to improve anti-biofouling characteristics and able to filter a range of molecular weights. This short review describes nano-porous membranes for molecular separation as well as limitations with current membrane designs.

36 MATERIALS SCIENCE↗

Nitrile crosslinked polyphenyl-quinoxaline/graphite fiber composites

Studies were performed to reduce the 600 F thermoplasticity of polyphenylquinoxaline (PPQ) matrix resins by introducing crosslinking by the reaction of terminal nitrile groups. Seven solvents and solvent mixtures were studied as the crosslinking catalysts and used to fabricate crosslinked PPQ/HMS graphite fiber composites. The room temperature and 600 F composite mechanical properties after short time and prolonged 600 F air exposure and the 600 F composite weight loss were determined and compared to those properties of high molecular weight, linear PPQ/HMS graphite fiber composites.

Alston, W. B.↗

Stimulation of body weight increase and epiphyseal cartilage growth by insulin like growth factor

The ability of insulin-like growth factor (IGF) to induce growth in hypophysectomized immature rats was tested by continuous infusion of the partially purified factor at daily doses of 6, 21, and 46 mU for an 8-day period. A dose-dependent growth of the proximal epiphyseal cartilage of the tibia and an associated stimulation of the primary spongiosa were produced by these amounts of IGF. The two highest doses of IGF also resulted in dose-dependent increases of body weight. Gel permeation of the sera at neutrality showed that the large-molecular-weight IGF binding protein was not induced by the infusion of IGF, whereas it ws generated in the sera of hypophysectomized rats that were infused with daily doses of 86 mU of human growth hormone.

Ellis, S.↗

Mass spectrometry without ions.

Molecular flow mass spectrometer analysis of porous metal membranes for gases of different molecular weights

POROUS MATERIAL↗

Natural organic matter composition and nanomaterial surface coating determine the nature of platinum nanomaterial-natural organic matter corona

Natural organic matter corona (NOM corona) is an interfacial area between nanomaterials (NMs) and the sur- rounding environment, which gives rise to NMs' unique surface identity. While the importance of the formation of natural organic matter (NOM) corona on engineered nanomaterials (NMs) to NM behavior, fate, and toxicity has been well-established, the understanding of how NOM molecular properties affect NOM corona composition remains elusive due to the complexity and heterogeneity of NOM. This is further complicated by the variation of NOMs from different origins. Here we use eight NOM isolates of different molecular composition and ultrahigh resolution Fourier-transform ion cyclotron resonance-mass spectrometry (ESI-FT-ICR-MS) to determine the mol- ecular composition of platinum NM-NOM corona as a function of NOM composition and NM surface coating. We observed that the composition of PtNM-NOM corona varied with the composition of the original NOM. The per- centage of NOM formulas that formed PVP-PtNM-NOM corona was higher than those formed citrate-PtNM-NOM corona, due to increased sorption of NOM formulas, in particular condensed hydrocarbons, to the PVP coating. The relative abundance of heteroatom formulas (CHON, CHOS, and CHOP) was higher in the PVP-PtNM-NOM corona than in citrate-PtNM-corona which was in turn higher than those in the original NOM isolate, indicating preferential partitioning of heteroatom-rich molecules to NM surfaces. The relative abundance of CHO, CHON, CHOS, CHOP and condensed hydrocarbons in PtNM-NOM corona increased with their increase in NOM isolates. Furthermore, PtNM-NOM corona is rich with compounds with high molecular weight. This study demonstrates that the composition and properties of PtNM-NOM corona depend on NOM molecular properties and PtNM sur- face coating. The results here provide evidence of molecular interactions between NOM and NMs, which are crit- ical to understanding NM colloidal properties (e.g., surface charge and stability), interaction forces (e.g., van der Waals and hydrphobic), environmental behaviors (e.g., aggregation, disso.

Baalousha, Mohammed↗

Unveiling the Role of Compositional Drifts on the Tack of Pressure‐Sensitive‐Adhesives

Abstract Pressure‐sensitive‐adhesives (PSAs) are pervasive in electronic, automobile, packaging, and biomedical applications due to their ability to stick to numerous surfaces without undergoing chemical reactions. These materials are typically synthesized by the free radical copolymerization of alkyl acrylates and acrylic acid, leading to an ensemble of polymer chains with varying composition and molecular weight. Here, reversible addition−fragmentation chain‐transfer (RAFT) copolymerizations in a semi‐batch reactor are used to tailor the molecular architecture and bulk mechanical properties of acrylic copolymers. In the absence of cross‐links, the localization of acrylic acid toward the chain ends leads to microphase separation, creep resistance, and enhanced tack. However, in the presence of Al(acac) 3 crosslinker, the creep resistance remains unchanged and mostly the large‐strain mechanical properties are affected. This behavior is attributed to microphase separation, but also to a change in the energy required to break physical associations, and untangle and elongate associative polymers to large deformations.

Polymer Science↗

Machine learning predictions of diffusion in bulk and confined ionic liquids using simple descriptors

Ionic liquids have many intriguing properties and widespread applications such as separations and energy storage. However, ionic liquids are complex fluids and predicting their behavior is difficult, particularly in confined environments. We introduce fast and computationally efficient machine learning (ML) models that can predict diffusion coefficients and ionic conductivity of bulk and nanoconfined ionic liquids over a wide temperature range (350–500 K). The ML models are trained on molecular dynamics simulation data for 29 unique ionic liquids as bulk fluids and confined in graphite slit pores. This model is based on simple physical descriptors of the cations and anions such as molecular weight and surface area. Here, we also demonstrate that accurate results can be obtained using only descriptors derived from SMILES (simplified molecular-input line-entry system) codes for the ions with minimal computational effort. This offers a fast and efficient method for estimating diffusion and conductivity of nanoconfined ionic liquids at various temperatures without the need for expensive molecular dynamics simulations.

74 ATOMIC AND MOLECULAR PHYSICS↗

Heat, Moisture and Chemical Resistant Polyimide Compositions and Methods for Making and Using Them

Polyimides having a desired combination of high thermo-oxidative stability, low moisture absorption and excellent chemical and corrosion resistance are prepared by reacting a mixture of compounds including (a) 3,3',4,4'- benzophenonetetracarboxylic dianhydride (BTDA), (b) 3,4'- oxydianiline (3,4'-ODA), and (c) 5-norbornene-2,3- dicarboxylic anhydride (NA) in a high boiling, aprotic solvent to give 5 to 35% by weight of polyamic acid solution. The ratio of (a), (b), and (c) is selected to afford a family of polyimides having different molecular weights and properties. The mixture first forms a polyamic acid precursor. Upon heating at or above 300 C, the polyamic acids form polyimides, which are particularly suitable for use as a high temperature coating, adhesive, thin film, or composite matrix resin.

Ruth H Pater↗

Radiation Shielding of Lunar Regolith/Polyethylene Composites and Lunar Regolith/Water Mixtures

Space radiation is a complex mixed field of ionizing radiation that can pose hazardous risks to sophisticated electronics and humans. Mission planning for lunar exploration and long duration habitat construction will face tremendous challenges of shielding against various types of space radiation in an attempt to minimize the detrimental effects it may have on materials, electronics, and humans. In late 2009, the Lunar Crater Observation and Sensing Satellite (LCROSS) discovered that water content in lunar regolith found in certain areas on the moon can be up to 5.6 +/-2.8 weight percent (wt%) [A. Colaprete, et. al., Science, Vol. 330, 463 (2010). ]. In this work, shielding studies were performed utilizing ultra high molecular weight polyethylene (UHMWPE) and aluminum, both being standard space shielding materials, simulated lunar regolith/ polyethylene composites, and simulated lunar regolith mixed with UHMWPE particles and water. Based on the LCROSS findings, radiation shielding experiments were conducted to test for shielding efficiency of regolith/UHMWPE/water mixtures with various percentages of water to compare relative shielding characteristics of these materials. One set of radiation studies were performed using the proton synchrotron at the Loma Linda Medical University where high energy protons similar to those found on the surface of the moon can be generated. A similar experimental protocol was also used at a high energy spalation neutron source at Los Alamos Neutron Science Center (LANSCE). These experiments studied the shielding efficiency against secondary neutrons, another major component of space radiation field. In both the proton and neutron studies, shielding efficiency was determined by utilizing a tissue equivalent proportional counter (TEPC) behind various thicknesses of shielding composite panels or mixture materials. Preliminary results from these studies indicated that adding 2 wt% water to regolith particles could increase shielding of the regolith materials by about 6%. The findings may be utilized to extend the possibilities of potential candidate materials for lunar habitat structures, will potentially impact the design criteria of future human bases on the moon, and provide some guidelines for future space mission planning with respect to radiation exposure and risks posed on astronauts.

Johnson, Quincy F.↗

Space simulation ultimate pressure lowered two decades by removal of diffusion pump oil contaminants during operation

The complex problem why large space simulation chambers do not realize the true ultimate vacuum was investigated. Some contaminating factors affecting diffusion pump performance have been identified and some advances in vacuum/distillation/fractionation technology have been achieved which resulted in a two decade or more lower ultimate pressure. Data are presented to show the overall or individual contaminating effect of commonly used phthalate ester plasticizers of 390 to 530 molecular weight on diffusion pump performance. Methods for removing contaminants from diffusion pump silicone oil during operation and reclaiming contaminated oil by high vacuum molecular distillation are described.

Buggele, A. E.↗