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At least 73 records · Page 4

An assessment of potential degradation products in the gas-phase reactions of alternative fluorocarbons in the troposphere

Tropospheric chemical transformations of alternative hydrofluorocarbons (HCF's) and hydrochlorofluorocarbons (HCFC's) are governed by hydroxyl radical initiated oxidation processes, which are likely to be analogous to those known for alkanes and chloroalkanes. A schematic diagram is used to illustrate plausible reaction mechanisms for their atmospheric degradation, where R, R', and R'' denote the F- and/or Cl-substituted alkyl groups derived from HCF's and HCFC's subsequent th the initial H atom abstraction by HO radicals. At present, virtually no kinetic data exist for the majority of these reactions, particularly for those involving RO. Potential degradation intermediates and final products include a large variety of fluorine- and/or chlorine-containing carbonyls, acids, peroxy acids, alcohols, hydrogen peroxides, nitrates and peroxy nitrates, as summarized in the attached table. Probably atmospheric lifetimes of these compounds were also estimated. For some carbonyl and nitrate products shown in this table, there seem to be no significant gas-phase removal mechanisms. Further chemical kinetics and photochemical data are needed to quantitatively assess the atmospheric fate of HCF's and HCFC's, and of the degradation products postulated in this report.

Niki, Hiromi↗

An assessment of potential impact of alternative fluorocarbons on tropospheric ozone

While the chlorofuorocarbons (CFCs) such as CFC-11 (CFCl3) and CFC-12 (CF2Cl2) are chemically inert in the troposphere, the hydrogen-containing halocarbons being considered as their replacements can, to a large extent, be removed in the troposphere by the HO radical. These alternative halocarbons include the hydrochlorofluorocarbons (HCFCs) 123 (CF3CHCl2), 141b (CFCl2CH3), 142b (CF2ClCH3), 22 (CHF2Cl), and 124 (CF3CHFCl) and the hydrofluorocarbons (HCFs) 134a (CF3CH2F), 152a (CHF2CH3) and 125 (CF3CHF2). Listed are the rate constants (k) for the HO radical reaction of these compounds and their estimated chemical lifetimes in the troposphere. In this table, values of the lifetimes of these selected HCFCs and HCFs are seen to vary by more than a factor of more than ten ranging from 1.6 years for HFC 152a and HCFC 125 to as long as 28 years for HFC 125. Clearly, from the standpoint of avoiding or minimizing impact on stratospheric O3, those halocarbons with short tropospheric lifetimes are the desirable alternates. However, potential environmental consequences of their degradation in the troposphere should be assessed and taken into account in the selection process.

Niki, Hiromi↗

Feature Profile Evolution of SiO2 Trenches In Fluorocarbon Plasmas

Etching of silicon microstructures for semiconductor manufacturing in chlorine plasmas has been well characterized. The etching proceeds in a two-part process, where the chlorine neutrals passivate the Si surface and then the ions etch away SiClx. However, etching in more complicated gas mixtures and materials, such as etching of SiO2 in Ar/C4F8, requires knowledge of the ion and neutral distribution functions as a function of angle and velocity, in addition to modeling the gas surface reactions. In order to address these needs, we have developed and integrated a suite of models to simulate the etching process from the plasma reactor level to the feature profile evolution level. This arrangement allows for a better understanding, control, and prediction of the influence of equipment level process parameters on feature profile evolution. We are currently using the HPEM (Hybrid Plasma Equipment Model) and PCMCM (Plasma Chemistry Monte Carlo Model) to generate plasma properties and ion and neutral distribution functions for argon/fluorocarbon discharges in a GEC Reference Cell. These quantities are then input to the feature scale model, Simulation of Profile Evolution by Level Sets (SPELS). A surface chemistry model is used to determine the interaction of the incoming species with the substrate material and simulate the evolution of the trench profile. The impact of change of gas pressure and inductive power on the relative flux of CFx and F to the wafer, the etch and polymerization rates, and feature profiles will be examined. Comparisons to experimental profiles will also be presented.

Hwang, Helen↗

Post-Flight Analysis of Selected Fluorocarbon and Other Thin Film Polymer Specimens Flown on MISSE-5

Twenty thin film specimens were flown on M1SSE-5 as a cooperative effort between several organizations. This presentation will report results of initial inspections and post-flight measurements of the optical properties and recession of these materials due to the approx.13 month exposure period on the exterior of the International Space Station. These specimens were located on the "anti-solar" side of the MISSE-5 container and received a low number of Equivalent Sun Hours of solar UV exposure. Profilometry and/or ATF measurements will be conducted to determine thickness changes and atomic oxygen-induced recession rates Six of the specimens were covered with thin Kapton films, 0.1 and 0.3 mil in thickness. The 0.1 mil Kapton was almost completely eroded, suggesting that the atomic oxygen fluence is <8 x 10(exp 19) atoms/sq cm, similar to levels experienced during Space Shuttle materials experiments in the 1980's and 1990's. A comparison of results from MISSE-5 and Space Shuttle experiments will be included for those materials common to both the short and long-term exposures.

DeGroh, Kim↗

Anisotropic Copoly(Imide Oxetane) Coatings and Articles of Manufacture, Copoly(Imide Oxetane)s Containing Pendant Fluorocarbon Moieties, Oligomers and Processes Therefor

Copoly(imide oxetane) materials are disclosed that can exhibit a low surface energy while possessing the mechanical, thermal, chemical and optical properties associated with polyimides. The copoly(imide oxetane)s are prepared using a minor amount of fluorinated oxetane-derived oligomer with sufficient fluorine-containing segments of the copoly(imide oxetane)s that migrate to the exterior surface of the polymeric material to yield low surface energies. Thus the coatings and articles of manufacture made with the copoly(imide oxetane)s of this invention are characterized as having an anisotropic fluorine composition. The low surface energies can be achieved with very low content of fluorinated oxetane-derived oligomer. The copolymers of this invention can enhance the viability of polyimides for many applications and may be acceptable where homopolyimide materials have been unacceptable.

Wohl, Christopher J.↗

Low-temperature oxidation pathways are critical to thermal incineration of PFAS-laden materials

With growing desire to destroy per- and poly-fluoroalkyl substances (PFAS) now known to be detrimental to human health, a sound understanding of fluorocarbon combustion chemistry is important to efficient thermal destruction within incinerators. While most fluorocarbon combustion models and the sets of reactions contained within them were originally developed for the high temperatures encountered in flame suppression applications, they have often been used to assess PFAS destruction in incinerators, which emphasize a lower range of temperatures. We present results that demonstrate that low-temperature fluorocarbon oxidation pathways—not yet known to play a role in fluorocarbon combustion—impact key incinerator performance metrics, including: PFAS surrogate mole fractions, products of incomplete destruction, and waste destruction efficiencies. The results further point to the utility of NO as a potential additive. The present results show the influence of these pathways for CF 3 O 2 , for which some data are available, but analogous pathways would also occur for other fluoroalkylperoxy radicals, for which little is known. Furthermore, the results demonstrate the need for future work to identify and characterize low-temperature pathways more generally, consider such pathways in kinetic model development, and experimentally probe intermediate temperature conditions to better understand, design, and control thermal destruction technologies for improved PFAS management.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Conclusions and Federal actions

Findings regarding fluorocarbon production, the roles of ozone and fluorocarbons in atmospheric chemistry, the depletion of stratospheric ozone by fluorocarbons, and various effects of this depletion are outlined. Research into these areas is described and recommendations are given for governmental action to reduce the release of fluorocarbons to the environment.

Source record↗

Compatibility of Fuel System Elastomers and Plastics with a Fast-Pyrolysis Oil (Bio-oil) at Room Temperature

Herein the compatibility of a fast-pyrolysis bio-oil with 17 elastomer and 21 plastic materials common to fuel storage, dispensing, and delivery systems was assessed by measuring volume and hardness. Diesel was used as the baseline for comparison. The elastomer and plastic specimens were exposed to the test fuels at 23 °C. The exposure times were 4 and 16 weeks for the elastomers and plastics, respectively. The elastomers (except for silicone and styrene butadiene) exhibited pronounced swelling in the bio-oil. This was especially true for the fluorocarbons and acrylonitrile rubbers. For the elastomers, a strong correlation between polarity and volume swell was observed. Compositional and structural analysis on one of the fluorocarbon materials showed that the bio-oil was less effective at extracting phthalate additives than the diesel. However, the crystallinity of a fluorocarbon was altered by the bio-oil. Unlike the elastomers, the plastic materials were less impacted by exposure to the bio-oil. This finding is attributed to their denser and more rigid molecular structures (compared to the elastomers). Notable swelling did occur in the nylons, but this swelling was attributed to water absorption rather than polarity. Comparison with previous studies showed that the observed swelling was lower for both the elastomers and the plastics. Solubility (and hence swell) increases with temperature, and because this study was conducted at 23 °C rather than 50 °C, the reduced temperature is responsible for the lower swell levels.

09 BIOMASS FUELS↗

Surface Acoustic Wave Sensors for Refrigerant Leak Detection: Compact, Inexpensive, Selective and Sensitive Sensors

Pacific Northwest National Laboratory (PNNL), in collaboration with Parker and Hannifin, is developing a compact, inexpensive, and highly sensitive and selective surface acoustic wave sensor coated with fluorophillic sorbent for detecting fluorocarbon leaks from HVAC systems. Having a highly effective sorbent sensitive to fluorocarbon refrigerant vapors provides a means to develop a sensing device for leak detection. Surface acoustic wave (SAW) sensors with a gas sensing film deposited between the delay lines or on the interdigital transducer have been used to detect gas and vapor molecules in harsh environments with high sensitivity. As part of this project, PNNL screened several sorbent materials that are shown to be selective towards fluorocarbon refrigerant (R32) molecule. The identified sorbent materials were synthesized, characterized, and tested towards R32 using various spectroscopic technique. Next, the sorbent material was coated on a SAW sensor as a thin film using vapor deposition and drop coating methods. The coated thin film was further characterized and tested towards the detection of pure R32 and R32 in ambient air at room temperature to demonstrate the SAW response towards R32 in presence of other competing gases and vapors in air.

42 ENGINEERING↗

Texturing polymer surfaces by transfer casting

A technique for fabricating textured surfaces on polymers without altering their surface chemistries is described. A surface of a fluorocarbon polymer is exposed to a beam of ions to texture it. The polymer which is to be surface-roughened is then cast over the textured surface of the fluorocarbon polymer. After curing, the cast polymer is peeled off the textured fluorocarbon polymer, and the peeled off surface has negative replica of the textured surface. The microscopic surface texture provides large surface areas for adhesive bonding. In cardiovascular prosthesis applications the surfaces are relied on for the development of a thin adherent well nourished thrombus.

Banks, B. A.↗

Development of an all-metal thick film cost effective metallization system for solar cells

Electrodes made with pastes produced under the previous contract were analyzed and compared with raw materials. A needle-like structure observed on the electroded solar cell was identified as eutectic copper-silicon, a phase considered to benefit the electrical and metallurgical properties of the contact. Electrodes made from copper fluorocarbon and copper silver fluoride also contained this phase but had poor adhesion. A liquid medium, intended to provide transport during carbon fluoride decomposition was incorporated into the paste resulting in better adhesion. The product survived preliminary environmental tests. A 2 cm by 2 cm solar cell made with fluorocarbon activated copper electrodes and gave 7% AMI efficiency (without AR coating). Both silver fluoride and fluorocarbon screened paste electrodes can be produced for approximately $0.04 per watt.

Ross, B.↗

The liquid-vapor interface of a binary liquid mixture near the consolute point

The present investigation is concerned with measurements of the reflectance of polarized light by the liquid-vapor interface above liquid mixtures of a fluorocarbon and an alcohol in the vicinity of the consolute point of the liquid mixture. The denser fluorocarbon is preferentially adsorbed at the interface. The denser fluorocarbon is preferentially adsorbed at the interface. The data are consistent with a simple model of the dielectric constant vs height profile in the interface region. Liquid mixtures of isopropanol (i-C3H7OH) and perfluoromethylcyclohexane (C7F14) near their consolute point (Tc = 363 K) are utilized in the conducted experiments. The primary quantity measured is the ellipticity as a function of temperature and liquid composition. Attention is given to details regarding the experimental techniques, model dielectric constant profiles, and the calculation of the ellipticity.

Schmidt, J. W.↗

Sensitivity of an atmospheric photochemistry model to chlorine perturbations including consideration of uncertainty propagation

Models of stratospheric photochemistry are generally tested by comparing their predictions for the composition of the present atmosphere with measurements of species concentrations. These models are then used to make predictions of the atmospheric sensitivity to perturbations. Here the problem of the sensitivity of such a model to chlorine perturbations ranging from the present influx of chlorine-containing compounds to several times that influx is addressed. The effects of uncertainties in input parameters, including reaction rate coefficients, cross sections, solar fluxes, and boundary conditions, are evaluated using a Monte Carlo method in which the values of the input parameters are randomly selected. The results are probability distributions for present atmosheric concentrations and for calculated perturbations due to chlorine from fluorocarbons. For more than 300 Monte Carlo runs the calculated ozone perturbation for continued emission of fluorocarbons at today's rates had a mean value of -6.2 percent, with a 1-sigma width of 5.5 percent. Using the same runs but only allowing the cases in which the calculated present atmosphere values of NO, NO2, and ClO at 25 km altitude fell within the range of measurements yielded a mean ozone depletion of -3 percent, with a 1-sigma deviation of 2.2 percent. The model showed a nonlinear behavior as a function of added fluorocarbons. The mean of the Monte Carlo runs was less nonlinear than the model run using mean value of the input parameters.

Stolarski, R. S.↗

Detection of Chamber Conditioning Through Optical Emission and Impedance Measurements

During oxide etch processes, buildup of fluorocarbon residues on reactor sidewalls can cause run-to-run drift and will necessitate some time for conditioning and seasoning of the reactor. Though diagnostics can be applied to study and understand these phenomena, many of them are not practical for use in an industrial reactor. For instance, measurements of ion fluxes and energy by mass spectrometry show that the buildup of insulating fluorocarbon films on the reactor surface will cause a shift in both ion energy and current in an argon plasma. However, such a device cannot be easily integrated into a processing system. The shift in ion energy and flux will be accompanied by an increase in the capacitance of the plasma sheath. The shift in sheath capacitance can be easily measured by a common commercially available impedance probe placed on the inductive coil. A buildup of film on the chamber wall is expected to affect the production of fluorocarbon radicals, and thus the presence of such species in the optical emission spectrum of the plasma can be monitored as well. These two techniques are employed on a GEC (Gaseous Electronics Conference) Reference Cell to assess the validity of optical emission and impedance monitoring as a metric of chamber conditioning. These techniques are applied to experimental runs with CHF3 and CHF3/O2/Ar plasmas, with intermediate monitoring of pure argon plasmas as a reference case for chamber conditions.

Cruden, Brett A.↗

Insight into the nanostructure of “water in salt” solutions: A SAXS/WAXS study on imide-based lithium salts aqueous solutions

"Water-in-salt " electrolyte (WISE) series have been studied for lithium-ion batteries and supercapacitor applications, but so far, most of the focus has been on the LiTFSI salt-based systems. Herein, we used small-angle X-ray scattering/wide-angle X-ray scattering (SAXS/WAXS) and molecular dynamics (MD) simulation to investigate the solvation structure of a series of lithium salts with four different symmetric anions: (bis(fluoro sulfonyl)imide (FSI), bis(trifluoromethane sulfonyl)imide (TFSI), bis(pentafluoroethane sulfonyl) imide (BETI) and bis(nonafluorobutane sulfonyl)imide (BNTI)), which have similar parent structures but different lengths of the fluorocarbon chains. Two competing structures were found in the four lithium salts aqueous solutions: anion solvated structure and anion network. The anion network plays a crucial role in obtaining a stable and enlarged electrochemical window. The d spacing of the anion solvated structure follows a linear correlation with the number of carbons in the fluorocarbon chains and an exponential correlation with the concentrations. Further, we also observed that the transition from one structure to another is predominantly controlled by the salt volume fraction for all imide-based aqueous solutions. This work provides a systematic study of the atomistic scale structures of a series of imide-based lithium salt aqueous solutions that could extend the knowledge of WIS electrolytes.

25 ENERGY STORAGE↗

An infrared spectral database for gas-phase quantitation of volatile per- and polyfluoroalkyl substances (PFAS)

We report the construction of a database of vetted infrared spectra specifically targeting volatile fluorocarbon gases that may be emitted during thermal treatment of per- and polyfluoroalkyl substances (PFAS) to assist understanding of treatment processes and improve quantification. To populate this database, protocols derived from the Pacific Northwest National Laboratory (PNNL) infrared spectral database are used, curtailing the species selection for this data set. Each spectrum in the database is a weighted average derived from 10 or more individual measurements at different partial pressures (static method) or flow rates (dissemination method) to yield good fidelity of both strong and weak infrared signatures, with each composite spectrum ranging from = 6500 cm-1 to = 600 cm-1 with an apodized resolution of 0.112 cm-1. This resolution was chosen to fully resolve all spectral features, recognizing that atmospheric pressure broadening results in nearly all ro-vibrational lines having linewidths = 0.1 cm-1. As an example case, application of the database is demonstrated via identification and quantification of dominant 1H-perfluoroheptane and perfluorohept-1-ene fluorocarbon products resulting from thermal decomposition of perfluorooctanoate (PFOA) below 450 °C.

Infrared, Gas-phase spectra, FTIR, Spectral databa↗

Transition-Metal Nitroprussides Examined for Water Harvesting and Sorption Cooling

Transition metal pentacyanonitrosylferrates, commonly known as nitroprussides, have a long and documented history. Here we synthesize cobalt and nickel nitroprussides (NPs) in order to probe their use as sorbents for water and fluorocarbon uptake. These NPs show stable and reversible equilibrium sorption iso-therms at room temperature with peak uptake values of ~40 wt% for H2O and ~30 wt% for fluorocarbon R134a. At water-harvesting conditions, a working capacity of ~23 wt% was ob-tained for both cobalt and nickel NP. Given the advantages of an easy, in-expensive and scalable synthesis, this study demon-strates the potential for using nitroprussides for future water harvesting and adsorption cooling systems.

Barpaga, Dushyant↗

Evaluating the Effect of Electrolyte Additive Functionalities on NMC622/Si Cell Performance

Unstable electrode/electrolyte interface is the major cause of degradation for silicon (Si)-based anodes for lithium (Li)-ion batteries. Development of functional electrolyte additives can provide a viable path toward stabilizing the dynamic Si/electrolyte interface, which will benefit the development of high energy density Li-ion batteries. Here, we evaluate polymerizable electrolyte additives with varying functional groups (fluorocarbon, thiophosphate, and fluorophosphazene). The additives are examined using LiNi 0.6 Mn 0.2 Co 0.2 O 2 /Si full cells where the cycle performance and impedance are measured. Electrochemical tests show that the fluorine-containing additives provide better passivation at the Si electrode, leading to enhanced full cell performance. Here, among the three additives examined, best electrochemical performance is observed from the fluorocarbon-containing compound, followed by fluorophosphazene- and thiophosphate-containing compounds. Characterization of the solid electrolyte interphase (SEI) on cycled electrodes using Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), and attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) reveal that higher concentration of fluorine and lithium oxide, and lower concentration of carbonate and organic species correlate with enhanced electrochemical performance.

25 ENERGY STORAGE↗