Detection of organic vapors by polymer-composite coated quartz crystal microbalance: an experimental and modeling study
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Synthesis via aromatic nucleophilic displacement yields new high-molecular-weight polymers. Polymers exhibited good mechanical and thermal properties. Synthetic route provided high-molecular-weight POX of new chemical structure, potentially more economical. Availability of large variety of activated aromatic dihalides, facilitates variation of chemical structures. Exhibit properties making them useful as films. Also useful in coatings, adhesives, moldings, and composites.
Novel molecular-weight-controlled end-capped poly(arylene ether benzimidazole)s (PAEBI's) prepared by nucleophilic displacement reaction of di(hydroxyl)benzimidazole monomers with activated aromatic dihalides. Polymers prepared at various molecular weights by upsetting stoichiometry of monomers and end-capped with monohydroxybenzimidazole. Exhibit favorable physical and mechanical properties, improved solubility in polar aprotic solvents and better compression moldability. Potential applications as adhesives, coatings, films, fibers, membranes, moldings, and composite matrix resins.
Many popular and widely used paint stripping products now contain methylene chloride as their active ingredient. However, the Environmental Protection Agency (EPA) will critically curb the use of methylene chloride under an aerospace national emission standard for hazardous air pollutants (NESHAP) within the next 2-1/2 years. An effort is underway to identify and evaluate alternative depainting technologies emphasizing those believed to be both effective and environmentally benign. On behalf of the EPA and in cooperation with the U. S. Air Force (USAF), the National Aeronautics and Space Administration (NASA) is conducting a technical assessment of nine alternative technologies (i.e.: chemical stripping, two CO2 blasting processes, FLASHJET(TM) coating removal, laser stripping, plastic media blasting, sodium bicarbonate wet stripping, high-pressure water stripping, and wheat starch blasting). These depainting processes represent five removal method categories, namely abrasive, impact, cryogenic, thermal, and/or molecular bonding dissociation. This paper discusses the test plan and parameters for this interagency study. Several thicknesses of clad and non-clad aluminum substrates were used to prepare test specimens, which have been cut, cleaned, painted, and environmentally aged. Each depainting process has been assigned a specimen lot, which is now undergoing an initial strip cycle. Metallurgical impacts will be determined after these specimens complete five cycles of preparation and stripping.
Many popular and widely used paint stripping products have traditionally contained methylene chloride as their main active ingredient. However, the Environmental Protection Agency (EPA) has critically curved the allowable use of methylene chloride under the National Emission Standard for Hazardous Air Pollutants regulating Aerospace Manufacturing and Rework Facilities . Compliance with this rule was mandatory by September 1998 for affected facilities. An effort is underway to identify and evaluate alternative depainting technologies emphasizing those believed both effective and environmentally benign. On behalf of the EPA and in cooperation with the United States Air Force, the National Aeronautics and Space Administration is conducting a technical assessment of several alternative technologies ( i.e. : chemical stripping, two CO2 blasting processes, CO2 xenon lamp coating removal, CO2 Laser stripping, plastic media blasting, sodium bicarbonate wet stripping, high pressure water stripping, and wheat starch blasting). These depainting processes represent five removal method categories, namely abrasive, impact, cryogenic, thermal, and/or molecular bonding dissociation. This paper discusses the test plan and parameters for this interagency study. Several thicknesses of clad and non-clad aluminum substrates were used to prepare test specimens. Each depainting process has been assigned a specimen lot, all of which have completed three to five stripping cycles. Numerous metallurgical evaluations are underway to assess the impact of these alternative depainting processes upon the structural integrity of the substrate.
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.
ChemCam is an active remote sensing instrument which has operated successfully on MSL since landing in August, 2012. Its laser pulses remove dust and to profile through weathering coatings of rocks up to 7 m away. Laser-induced breakdown spectroscopy (LIBS) produces emission spectra of materials ablated from the samples in electronically excited states. As the plasma cools, elements can recombine and molecular emission lines are observed. Recent experiments have shown that some of these molecular emissions can be much brighter than the associated atomic lines, especially when halo-gens and rare earth elements are present. We observed these molecular emissions in some of the ChemCam spectra and report the first detection of chlorine and fluorine with ChemCam. It is also the first time ever that fluorine has been detected on the surface of Mars. Among all the F-bearing observations, one third are observed in the Kimberley outcrop. We will dis-cuss the potential mineralogies related to these observations as well as the related elemental correlations and propose interpretations.
The second, third, and fourth space transportation system missions are described including the location of the IECM in the payload bay and the shuttle coordinate systems used. Measurement results from the three flights are given for each instrument with comparisons to original goals for preflight environment and induced environment contamination. These results include very low levels of molecular mass accumulation rates, absence of molecular films on optical samples, outgassing species above 50 amu undetectable generally low levels of on-orbit particulates, and decay rates for early mission water dump particulates. Results of exposure of several optical materials and coatings to atomic oxygen are also presented. From these results, it is concluded that the space shuttle met the established induced environment contamination goals.
In ongoing investigations to map and archive the microbial footprints in various components of the spacecraft and its accessories, we have examined the microbial populations of the Jet Propulsion Laboratory's Spacecraft Assembly Facility (JPL-SAF). Witness plates made up of spacecraft materials, some painted with spacecraft qualified paints, were exposed for approximately 7 to 9 months at JPL-SAF and examined the particulate materials collected for the incidence of total cultivable aerobic heterotrophs and heat-tolerant (80 degrees C for 15-min.) spore-formers. The results showed that the witness plates coated with spacecraft qualified paints attracted more dust particles than the non-coated stainless steel witness plates. Among the four paints tested, witness plates coated with NS43G accumulated the highest number of particles, and hence attracted more cultivable microbes. The conventional microbiological examination revealed that the JPL-SAF harbors mainly Gram-positive microbes and mostly spore-forming Bacillus species. Most of the isolated microbes were heat resistant to 80 degrees C and proliferate at 60 degrees C. The phylogenetic relationships among 23 cultivable heat-tolerant microbes were examined using a battery of morphological, physiological, molecular and chemotaxonomic characterizations. By 16S rDNA sequence analysis, the isolates fell into seven clades: Bacillus licheniformis, B. pumilus, B. cereus, B. circulans, Staphylococcus capitis, Planococcus sp. and Micrococcus lylae. In contrast to the cultivable approach, direct DNA isolation, cloning and 16S rDNA sequencing analysis revealed equal representation of both Gram-positive and Gram-negative microorganisms.
Secondary electron emission (SEE) properties of polycrystalline diamond films grown by chemical vapor deposition (CVD) were measured. The total secondary yield (sigma) from as-grown samples was observed to be as high as 20 at room temperature and 48 while heating at 700 K in vacuum. Electron-beam-activated, alkali-terminated diamond films have shown stable values of sigma as high as 60 when coated with CsI and similarly high values when coated with other alkali halides. Diamond coated with BaF2 had a stable sigma of 6, but no enhancement of the SEE properties was observed with coatings of Ti or Au. Hydrogen was identified to give rise to this effect in as-grown films. However, electron beam exposure led to a reduction in sigma values as low as 2. Exposure to a molecular hydrogen environment restored sigma to its original value after degradation, and enabled stable secondary emission during electron beam exposure. Atomic hydrogen and hydrogen plasma treatments were performed on diamond/Mo samples in an attempt to increase the near-surface hydrogen concentration which might lead to increased stability in the secondary emission. Raman scattering analysis, scanning electron microscopy, and Auger electron spectroscopy (AES) confirmed that hydrogen plasma and atomic hydrogen treatments improved the quality of the CVD diamond significantly. Elastic recoil detection (ERD) showed that heating as-grown diamond targets to 7OO K, which was correlated with an increase in sigma, removed contaminants from the surface but did not drive hydrogen from the diamond bulk. ERD showed that the hydrogen plasma treatment produced an increase in the hydrogen concentration in the near-surface region which did not decrease while heating in vacuum at 700 K, but no improvement in the SEE properties was observed.
A simple, inexpensive method for bonding solid objects exploits hydroxide-catalyzed hydration and dehydration to form silicate-like networks in thin surface and interfacial layers between the objects. The method can be practiced at room temperature or over a wide range of temperatures. The method was developed especially to enable the formation of precise, reliable bonds between precise optical components. The bonds thus formed exhibit the precision and transparency of bonds formed by the conventional optical-contact method and the strength and reliability of high-temperature frit bonds. The method also lends itself to numerous non-optical applications in which there are requirements for precise bonds and/or requirements for bonds, whether precise or imprecise, that can reliably withstand severe environmental conditions. Categories of such non-optical applications include forming composite materials, coating substrates, forming laminate structures, and preparing objects of defined geometry and composition. The method is applicable to materials that either (1) can form silicate-like networks in the sense that they have silicate-like molecular structures that are extensible into silicate-like networks or (2) can be chemically linked to silicate-like networks by means of hydroxide-catalyzed hydration and dehydration. When hydrated, a material of either type features surface hydroxyl (-OH) groups. In this method, a silicate-like network that bonds two substrates can be formed either by a bonding material alone or by the bonding material together with material from either or both of the substrates. Typically, an aqueous hydroxide bonding solution is dispensed and allowed to flow between the mating surfaces by capillary action. If the surface figures of the substrates do not match precisely, bonding could be improved by including a filling material in the bonding solution. Preferably, the filling material should include at least one ingredient that can be hydrated to have exposed hydroxyl groups and that can be chemically linked, by hydroxide catalysis, to a silicate-like network. The silicate-like network could be generated in situ from the filling material and/or substrate material, or could be originally present in the bonding material.
Polyimides belong to a class of polymers known as polyheterocyclics. Unlike most other high temperature polymers, polyimides can be prepared from a variety of inexpensive monomers by several synthetic routes. The glass transition and crystalline melt temperature, thermooxidative stability, toughness, dielectric constant, coefficient of thermal expansion, chemical stability, mechanical performance, etc. of polyimides can be controlled within certain boundaries. This versatility has permitted the development of various forms of polyimides. These include adhesives, composite matrices, coatings, films, moldings, fibers, foams and membranes. Polyimides are synthesized through both condensation (step-polymerization) and addition (chain growth polymerization) routes. The precursor materials used in addition polyimides or imide oligomers are prepared by condensation method. High molecular weight polyimide made via polycondensation or step-growth polymerization is studied. The various synthetic routes to condensation polyimides, structure/property relationships of condensation polyimides and composite properties of condensation polyimides are all studied. The focus is on the synthesis and chemical structure/property relationships of polyimides with particular emphasis on materials for composite application.
The characterization of polymeric films and thermal control coatings which were exposed for five years and ten months to the low-Earth environment is reported. Changes in solar absorptance, thermal emittance, and transmission are compared to laboratory control specimens. Sputter-deposited metallic coatings are shown to eliminate atomic oxygen erosion of resin matrix composite materials. The effects of long-term atomic oxygen exposure to metallized FEP Teflon film is characterized. Chemical characterization of polymeric films indicates that although surface erosion occurs, the molecular structure of the basic polymeric film has not changed significantly in response to this exposure.
Bacteriophages producing endopolysaccharase-type enzymes used to produce, isolate, and purify high yields of modified polysaccharides from polysaccharides produced by, and incorporated into capsules of, certain bacteria. Bacteriophages used in conversion of native polysaccharide materials into polymers of nearly uniform high molecular weight or, alternatively, into highly pure oligosaccharides. Also used in genetic selection of families of polysaccharides structurally related to native polysaccharide materials, but having altered properties. Resulting new polysaccharides and oligosaccharides prove useful in variety of products, including pharmaceutical chemicals, coating materials, biologically active carbohydrates, and drag-reducing additives for fluids.
A phenylethynyl terminated imide oligomer formed from the reaction of benzophenone tetracarboxylic acid dianhydride, an 75:25 molar ratio of 4,4'-oxydianiline and meta-phenylenediamine and 4-phenylethynylphthalic anhydride as the endcapper at a theoretical number average molecular weight (Mn) of approximately 3,700 g/mol was evaluated as a composite resin matrix. A glass transition temperature (Tg) of 315 deg C was reached after 250 deg C/1 hr annealing of the matrix resin. Unidirectional prepreg was made by coating an N-methylpyrrolidinone solution of the amide acid oligomer onto unsized IM7 graphite fibers. The thermal and rheological properties and the solvent/volatile depletion rates of the amide acid/NMP system were determined. This information was used to successfully design a molding cycle for composite fabrication. Composites molded under 800 Psi at 371 C consistently yielded good consolidation as measured by C-scan and optical photomicrography. The composite's short beam shear strength (SBS), longitudinal and transverse flexural strengths and moduli were measured at various temperatures. These composites exhibited excellent room temperature (RT) longitudinal flexural strength and modulus and RT SBS strength retention at 177 C.
Broad area graded-index separate-confinement heterostructure single quantum well lasers grown by molecular-beam epitaxy (MBE) with threshold current density as low as 93 A/sq cm (520 microns long) have been fabricated. Buried lasers formed from similarly structured MBE material with liquid phase epitaxy regrowth had threshold currents at submilliampere levels when high reflectivity coatings were applied to the end facets. A CW threshold current of 0.55 mA was obtained for a laser with facet reflectivities of about 80 percent, a cavity length of 120 micron, and an active region stripe width of 1 micron. These devices driven directly with logic level signals have switch-on delays less than 50 ps without any current prebias. Such lasers permit fully on-off switching while at the same time obviating the need for bias monitoring and feedback control.
The "Next Generation Space Telescope" (NGST), the follow-on telescope to the Hubble Space Telescope, will carry on exploration of the early universe with a primary mirror 6-8 meters in diameter optimized to operate in the infrared. The mirror and its instruments will perform extremely deep exposures at near infra-red wavelengths (0.5-30 microns), and will operate for 5-10 years. In order to achieve the requirements, cryogenic temperatures between 30-60 Kelvin must be maintained on the telescope (OTA) and in the science module (SIM). A primary feature for passive cooling in the designs presented is that of an enormous, light-weight deployable sunshield. As a result, issues of contamination from the sunshield and space environmental effects on the sunshield itself present a critical matter: if the sunshield becomes a source of contamination, or if environmental effects damage the sunshield, the NGST mission could be compromised or could fail completely. A molecular redistribution analysis has been performed on the Goddard Space Flight Center (GSFC) design for NGST. The analysis revealed that because the shield will initially cool down faster than the OTA, the shield would not be a significant source of molecular contamination during the cooling phase. However, if the shield were ever to warm up, it would be a very large source of molecular contamination. The sunshield itself is susceptible to degradation from an external source of contamination: the space environment at L2 or at 1 x 3 AU. It is therefore necessary to design the sunshield to withstand the space environment. Thin films and coatings on the sunshield have been evaluated and testing has begun so that a suitable film and/or coating can be chosen or developed for the NGST mission. The evaluation and test results will be presented.
Phthalocyanine (Pc) films have been synthesized by vapor deposition on quartz substrates, some of which were coated with a very thin gold film before depositing Pc films. Electrical fields up to 6200 V/cm between a mech electrode and the substrate are introduced during film growth. These films have been characterized by x-ray diffraction and scanning electron microscopy. The molecular orientations and surface morphology of Pc films were changed under the electrical fields. The surface of these films grown without electrical field shows whisk-like morphology. When films are deposited under an electrical field, a dense film with flat surface is obtained.