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At least 109 records · Page 6

Zinc Oxide Nanowire Interphase for Enhanced Lightweight Polymer Fiber Composites

The objective of this work was to increase the interfacial strength between aramid fiber and epoxy matrix. This was achieved by functionalizing the aramid fiber followed by growth of a layer of ZnO nanowires on the fiber surface such that when embedded into the polymer, the load transfer and bonding area could be substantially enhanced. The functionalization procedure developed here created functional carboxylic acid surface groups that chemically interact with the ZnO and thus greatly enhance the strength of the interface between the fiber and the ZnO.

Sodano, Henry A.↗

Prediction of In-Space Durability of Protected Polymers Based on Ground Laboratory Thermal Energy Atomic Oxygen

The probability of atomic oxygen reacting with polymeric materials is orders of magnitude lower at thermal energies (greater than O.1 eV) than at orbital impact energies (4.5 eV). As a result, absolute atomic oxygen fluxes at thermal energies must be orders of magnitude higher than orbital energy fluxes, to produce the same effective fluxes (or same oxidation rates) for polymers. These differences can cause highly pessimistic durability predictions for protected polymers and polymers which develop protective metal oxide surfaces as a result of oxidation if one does not make suitable calibrations. A comparison was conducted of undercut cavities below defect sites in protected polyimide Kapton samples flown on the Long Duration Exposure Facility (LDEF) with similar samples exposed in thermal energy oxygen plasma. The results of this comparison were used to quantify predicted material loss in space based on material loss in ground laboratory thermal energy plasma testing. A microindent hardness comparison of surface oxidation of a silicone flown on the Environmental Oxygen Interaction with Materials-III (EOIM-III) experiment with samples exposed in thermal energy plasmas was similarly used to calibrate the rate of oxidation of silicone in space relative to samples in thermal energy plasmas exposed to polyimide Kapton effective fluences.

Banks, Bruce A.↗

Repair of oxidation protection coatings on carbon-carbon using preceramic polymers

The paper describes a field-applicable technique for the repair of damage to SiC protective coatings on carbon/carbon composites, using commercial preceramic polymers, such as perhydropolysilazane developed by the Southwest Research Institute and several commercial polymers (NICALON, PS110, PS116, PS117, NCP-200, and PHPS were tested). After being applied on the damaged panel and oxidized at 1400 C, these polymers form either SiC or Si3N4 (or a mixture of both). It was found that impact damaged carbon/carbon specimens repaired with perhydropolysilazane exhibit substantial oxidation resistance. Many of the other tested preceramic polymer were found to be unsuitable for the purpose of repair due to either low ceramic yield, foaming, or intumescence.

Schwab, Stuart T.↗

A Brief Study on Toxic Combustion Products of the Polymers Used in High-Pressure Oxygen Systems

One likely cause of polymer ignition in a high-pressure oxygen system is the adiabatic-compression heating of polymers caused by pneumatic impact. Oxidative pyrolysis or combustion of polymers in a high-pressure oxygen system could generate toxic gases. This paper investigates the feasibility of using the NASA pneumatic-impact system to conduct adiabatic-compression combustion tests and determines the toxic combustion products produced from the burning of five selected polymers. Five polymers commonly used in high-pressure oxygen systems, Zytel(Registered TradeMark) 42 (Nylon 6/6), Buna N (nitrile rubber), Witon(Registered TradeMark) A (copolymer of vinylidene fluoride and hexafluoropropylene), Neoflon(Registered TradeMark) (polychlorotrifluoroethylene), and Teflon(Registered TradeMark) (polytetrafluoroethylene), were tested in the NASA pneumatic-impact test system at 17.2-MPa oxygen pressure. The polymers were ignited and burned; combustion products were collected in a stainless-steel sample bottle and analyzed using various methods. The results show that the NASA pneumatic-impact system is an appropriate test system to conduct adiabatic-compression combustion tests and to collect combustion products for further chemical analysis. The composition of the combustion product gas generated from burning the five selected polymers are presented and discussed.

Hshieh, Fu-Yu↗

A Preliminary Study on the Toxic Combustion Products Testing of Polymers Used in High-Pressure Oxygen Systems

One likely cause of polymer ignition in a high-pressure oxygen system is adiabatic-compression heating of polymers caused by pneumatic impact. Oxidative _ pyrolysis or combustion of polymers in a high-pressure oxygen system could generate toxic gases. This paper reports the preliminary results of toxic combustion product testing of selected polymers in a pneumatic-impact test system. Five polymers commonly used in high-pressure oxygen systems, Nylon 6/6, polychlorotrifluoroethylene (CTFE), polytetrafluoroethylene (PTFE), fluoroelastomer (Viton(TradeMark) A), and nitrile rubber (Buna N), were tested in a pneumatic-impact test system at 2500- or 3500-psia oxygen pressure. The polymers were ignited and burned, then combustion products were collected in a stainless-steel sample bottle and analyzed by GC/MS/IRD, GC/FID, and GC/Methanizer/FID. The results of adiabatic-compression tests show that combustion of hydrocarbon polymers, nitrogen-containing polymers, and halogenated polymers in high-pressure oxygen systems are relatively complete. Toxicity of the combustion product gas is presumably much lower than the combustion product gas generated from ambient-pressure oxygen (or air) environments. The NASA-Lewis equilibrium code was used to determine the composition of combustion product gas generated from a simulated, adiabatic-compression test of nine polymers. The results are presented and discussed.

Hshieh, Fu-Yu↗

Polyether-polyester graft copolymer

Described is a polyether graft polymer having improved solvent resistance and crystalline thermally reversible crosslinks. The copolymer is prepared by a novel process of anionic copolymerization. These polymers exhibit good solvent resistance and are well suited for aircraft parts. Previous aromatic polyethers, also known as polyphenylene oxides, have certain deficiencies which detract from their usefulness. These commercial polymers are often soluble in common solvents including the halocarbon and aromatic hydrocarbon types of paint thinners and removers. This limitation prevents the use of these polyethers in structural articles requiring frequent painting. In addition, the most popular commercially available polyether is a very high melting plastic. This makes it considerably more difficult to fabricate finished parts from this material. These problems are solved by providing an aromatic polyether graft copolymer with improved solvent resistance and crystalline thermally reversible crosslinks. The graft copolymer is formed by converting the carboxyl groups of a carboxylated polyphenylene oxide polymer to ionic carbonyl groups in a suitable solvent, reacting pivalolactone with the dissolved polymer, and adding acid to the solution to produce the graft copolymer.

Bell, Vernon L.↗

An ESR study of the UV degradation of FEP

Spacecraft in low earth orbit are subjected to significant levels of high energy radiation, including ultraviolet (UV) and visible ultraviolet (VUV) wavelengths. The effects of UV radiation are enhanced over those at the surface of the earth, where the only incident wavelengths are greater than 290 nm. In low earth orbit the incident UV wavelengths extend below 290 nm into the VUV region, where the Lyman alpha-emissions of atomic hydrogen occur at 121 nm. In addition to electromagnetic radiation, in low earth orbit polymer materials may also be subjected to atomic oxygen particle radiation, which will result in direct oxidation of the polymer.

George, G. A.↗

Polyurethane Microparticles for Stimuli Response and Reduced Oxidative Degradation in Highly Porous Shape Memory Polymers

Shape memory polymers (SMPs) have been found to be promising biomaterials for a variety of medical applications; however, the clinical translation of such technology is dependent on tailorable properties such as gravimetric changes in degradation environments. For SMPs synthesized from amino-alcohols, oxidation resulting in rapid mass loss may be problematic in terms of loss of material functionality as well as toxicity and cytocompatibility concerns. Control of gravimetric changes was achieved through the incorporation of small molecule antioxidants, either directly into the polymer matrix or included in microparticles to form a SMP composite material. Direct incorporation of small molecule antioxidants, such as phenolic alcohols, was found to alter shape memory attributes and increase elastic modulus at the expense of the strain to failure. Such changes could not ensure retention of the antioxidants and therefore did not increase oxidative stability. However, the inclusion of antioxidants in microparticles was found to produce materials with similar thermomechanical and shape memory properties while increasing oxidative resistance compared to controls. The microparticle composite SMPs also act as a platform for environmental sensing, such as pH-dependent fluorescence shifts and payload release, as demonstrated by fluorescent dyes and the release of antioxidants. The use of polyurethane-urea microparticles in porous SMPs is demonstrated to increase biostability of the materials, by approximately 25%, and ultimately extend their lifespan for use in aneurysm occlusion as determined through calculated in vivo degradation rates corresponding to a porcine aneurysm environment.

Weems, A. C.↗

Oxidative peptide /and amide/ formation from Schiff base complexes

One hypothesis of the origin of pre-modern forms of life is that the original replicating molecules were specific polypeptides which acted as templates for the assembly of poly-Schiff bases complementary to the template, and that these polymers were then oxidized to peptide linkages, probably by photo-produced oxidants. A double cycle of such anti-parallel complementary replication would yield the original peptide polymer. If this model were valid, the Schiff base between an N-acyl alpha mino aldehyde and an amino acid should yield a dipeptide in aqueous solution in the presence of an appropriate oxidant. In the present study it is shown that the substituted dipeptide, N-acetyl-tyrosyl-tyrosine, is produced in high yield in aqueous solution at pH 9 through the action of H2O2 on the Schiff-base complex between N-acetyl-tyrosinal and tyrosine and that a great variety of N-acyl amino acids are formed from amino acids and aliphatic aldehydes under similar conditions.

Strehler, B. L.↗

Prebiotic Oxidative Polymerization of 2,3 Dimercaptopropanol on the Surface of Iron(III) Hydroxide Oxide

The oxidation of 2,3-Dimercapto-1-propanol by ferric ions on the surface of iron (III) hydroxide oxide yielded polydisulfide polymers. This polymerization occured readily at low dithiol concentration under mild aqueous conditions. Polydisulfide polymers up to the 15-mer were synthesized from 1 mM dithiol in 5 ml water reacted with iron (III) hydroxide oxide (20 mg, 160 micro mole Fe) for 3 days under anaerobic conditions at 40 C and pH 4. About 91% of the dithiol was converted to short soluble oligomers and 9% to insoluble larger oligomers that were isolated with the mineral phase. Reactions at higher dithiol concentrations with the same ratio of dithiol to mineral gave a higher yield of the larger insoluble oligomers. The relationship of these results to prebiotic polymer synthesis will be discussed.

Weber, Arthur L.↗

Long-lasting solid-polymer electrolytic hygrometer

Device consists of hollow tube node of oxidation-resistant sulfonated fluorocarbon polymer. Tube absorbs moisture from air passing across inner and outer surfaces, causing change in polymer conductance. Change is related to change in water content in gas sample.

Lawson, D. D.↗

Vapor Phase Infiltration of Titanium Oxide into P3HT to Create Organic–Inorganic Hybrid Photocatalysts

Herein, we report for the first time the use of vapor phase infiltration (VPI) to infuse conducting polymers with inorganic metal oxide clusters that together form a photocatalytic material. While vapor infiltration has previously been used to electrically dope conjugated polymers, this is the first time, to our knowledge, that the resultant hybrid material has been demonstrated to have photocatalytic properties. The system studied is poly(3-hexylthiophene-2,5-diyl) (P3HT) vapor infiltrated with TiCl 4 and H 2 O to create P3HT-TiO x organic–inorganic hybrid photocatalytic materials. X-ray photoelectron spectroscopy analysis shows that P3HT-TiO x VPI films consist of a partially oxidized P3HT matrix, and the infiltrated titanium inorganic is in a 4+ oxidation state with mostly oxide coordination. Upon visible light illumination, these P3HT-TiO x hybrids degrade methylene blue dye molecules. The P3HT-TiO x hybrids are 4.6× more photocatalytically active than either the P3HT or TiO 2 individually or when sequentially deposited (e.g., P3HT on TiO 2 ). On a per surface area basis, these hybrid photocatalysts are comparable or better than other best in class polymer semiconductor photocatalysts. VPI of TiCl 4 + H 2 O into P3HT makes a unique hybrid structure and idealized photocatalyst architecture by creating nanoscale TiO x clusters concentrated toward the surface achieving extremely high catalytic rates. The mechanism for this enhanced photocatalytic rate is understood using photoluminescence spectroscopy, which shows significant quenching of excitons in P3HT-TiO x as compared to neat P3HT, indicating that P3HT acts as a photosensitizer for the TiO x catalyst sites in the hybrid material. This work introduces a new approach to designing and synthesizing organic–inorganic hybrid photocatalytic materials, with expansive opportunities for further exploration and optimization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Analytical methods for toxic gases from thermal degradation of polymers

Toxic gases evolved from the thermal oxidative degradation of synthetic or natural polymers in small laboratory chambers or in large scale fire tests are measured by several different analytical methods. Gas detector tubes are used for fast on-site detection of suspect toxic gases. The infrared spectroscopic method is an excellent qualitative and quantitative analysis for some toxic gases. Permanent gases such as carbon monoxide, carbon dioxide, methane and ethylene, can be quantitatively determined by gas chromatography. Highly toxic and corrosive gases such as nitrogen oxides, hydrogen cyanide, hydrogen fluoride, hydrogen chloride and sulfur dioxide should be passed into a scrubbing solution for subsequent analysis by either specific ion electrodes or spectrophotometric methods. Low-concentration toxic organic vapors can be concentrated in a cold trap and then analyzed by gas chromatography and mass spectrometry. The limitations of different methods are discussed.

Hsu, M.-T. S.↗

Atomic Oxygen Erosion Yield Dependence Upon Texture Development in Polymers

The atomic oxygen erosion yield (volume of a polymer that is lost due to oxidation per incident atom) of polymers is typically assumed to be reasonably constant with increasing fluence. However polymers containing ash or inorganic pigments, tend to have erosion yields that decrease with fluence due to an increasing presence of protective particles on the polymer surface. This paper investigates two additional possible causes for erosion yields of polymers that are dependent upon atomic oxygen. These are the development of surface texture which can cause the erosion yield to change with fluence due to changes in the aspect ratio of the surface texture that develops and polymer specific atomic oxygen interaction parameters. The surface texture development under directed hyperthermal attack produces higher aspect ratio surface texture than isotropic thermal energy atomic oxygen attack. The fluence dependence of erosion yields is documented for low Kapton H (DuPont, Wilmington, DE) effective fluences for a variety of polymers under directed hyperthermal and isotropic thermal energy attack.

oxygen atoms↗

Polyphenylene ethers with imide linking groups

Novel polyphenylene ethers with imide linking units are disclosed. These polymers incorporate the solvent and thermal resistance of polyimides and the processability of polyphenylene ethers. Improved physical properties over those of the prior art are obtained by incorporating meta linked ethers and/or polyphenylene oxides into the polymer backbone. A novel process for making polymers of this type is also disclosed. The process is unique in that the expected need of high process temperatures and/or special atmospheres are eliminated.

St.clair, T. L.↗