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Chemical research projects office functions accomplishments programs

Basic and applied research in the fields of polymer chemistry, polymeric composites, chemical engineering, and biophysical chemistry is summarized. Emphasis is placed on fire safety and human survivability as they relate to commercial and military aircraft, high-rise buildings, mines and rapid transit transportation. Materials systems and other fire control systems developed for aerospace applications and applied to national domestic needs are described along with bench-scale and full-scale tests conducted to demonstrate the improvements in performance obtained through the utilization of these materials and fire control measures.

Heimbuch, A. H.↗

Chemical and Thermal Analysis

Work has included significant research in several areas aimed at further clarification of the aging and chemical failure mechanism of thermoplastics (PVDF or Tefzel) for pipes. Among the areas investigated were the crystallinity changes associated with both the Coflon and Tefzel after various simulated environmental exposures using X-Ray diffraction analysis. We have found that significant changes in polymer crystallinity levels occur as a function of the exposures. These crystallinity changes may have important consequences on the fracture, fatigue, tensile, and chemical resistance of the materials. We have also noted changes in the molecular weight distribution of the Coflon material using a dual detector Gel Permeation Analysis. Again these changes may result in variation in the mechanical and chemical properties in the material. We conducted numerous analytical studies with methods including X-Ray Diffraction, Gel Permeation Chromatography, Fourier Transform Infrared Spectroscopy, Thermogravimetric Analysis, and Differential Scanning Calorimetry. We investigated a number of aged samples of both Tefzel and Coflon that were forwarded from MERL. Pressurized tests were performed in a modified Fluid G, which we will call G2. In this case the ethylene diamine concentration was increased to 3 percent in methanol. Coflon pipe sections and powdered Coflon were exposed in pressure cells at 1700 psi at three separate test temperatures, 70 C, 110 C, and 130 C. The primary purpose of the pressure tests in Fluid G2 was to further elucidate the aging mechanism of PVDF degradation.

Bulluck, J. W.↗

Alternative Electrochemical Systems for Ozonation of Water

Electrochemical systems that are especially well suited for the small-scale generation of ozone and ozonated water for local use have been invented. These systems can operate with very little maintenance, and the only inputs needed during operation are electric power and water. Ozonated water produced by these systems can be used in diverse industrial applications: A few examples include sterilization in the brewing industry, general disinfection, and treatment of sewage and recycled water. The basic principle of operation admits of several alternative system configurations. The heart of the system is a stack of electrolytic cells, each containing a proton-exchange membrane (which serves as a solid electrolyte) sandwiched between a catalytic anode and a catalytic cathode. Preferably, the proton-exchange membrane is made of a perfluorinated sulfonic acid polymer. During electrolysis, a mixture of O2 and O3 gases is generated at the anode and H2 is generated at the cathode. Some of the O3 generated at the anode becomes dissolved in the water. The proportion of O3 in the O2/O3 mixture can be maximized by the selection of suitable electrode materials and the use of a high overpotential. Although the proton-exchange membrane conducts protons, it does not conduct electrons. It is also impermeable by gases; consequently, it maintains separation between the O2/O3 mixture evolved at the anode and the H2 evolved at the cathode.

Andrews, Craig C.↗

Soluble and colorless polyimides

Results are reported in the form of reaction diagrams, graphs, and tables of research being conducted to synthesize and characterize linear aromatic polyimides which are soluble in common organic solvents and optically transparent in the 400-600 nm spectral range. These flexible and high-temperature polymeric films and coatings are needed for specific applications on space components such as antennas, solar cells, and thermal control coating systems. Several series of these polyimide films have been produced by making variations in the polymer molecular structure aimed at reducing the electronic interactions between the polymer chains.

St. Clair, Anne K.↗

Examination of Scanning Electron Microscope and Computed Tomography Images of PICA

Micrographs of PICA (Phenolic Impregnated Carbon Ablator) taken using a Scanning Electron Microscope (SEM) and 3D images taken with a Computed Tomography (CT) system are examined. PICA is a carbon fiber based composite (Fiberform ) with a phenolic polymer matrix. The micrographs are taken at different surface depths and at different magnifications in a sample after arc jet testing and show different levels of oxidative removal of the charred matrix (Figs 1 though 13). CT scans, courtesy of Xradia, Inc. of Concord CA, were captured for samples of virgin PICA, charred PICA and raw Fiberform (Fig. 14). We use these images to calculate the thermal conductivity (TC) of these materials using correlation function (CF) methods. CF methods give a mathematical description of how one material is embedded in another and is thus ideally suited for modeling composites like PICA. We will evaluate how the TC of the materials changes as a function of surface depth. This work is in collaboration with ETH-Zurich, which has expertise in high temperature materials and TC modeling (including CF methods).

Lawson, John W.↗

Shear Stress Sensing with Elastic Microfence Structures

In this work, elastic microfences were generated for the purpose of measuring shear forces acting on a wind tunnel model. The microfences were fabricated in a two part process involving laser ablation patterning to generate a template in a polymer film followed by soft lithography with a two-part silicone. Incorporation of a fluorescent dye was demonstrated as a method to enhance contrast between the sensing elements and the substrate. Sensing elements consisted of multiple microfences prepared at different orientations to enable determination of both shear force and directionality. Microfence arrays were integrated into an optical microscope with sub-micrometer resolution. Initial experiments were conducted on a flat plate wind tunnel model. Both image stabilization algorithms and digital image correlation were utilized to determine the amount of fence deflection as a result of airflow. Initial free jet experiments indicated that the microfences could be readily displaced and this displacement was recorded through the microscope.

Cisotto, Alexxandra↗

Photothermal degradation of ethylene/vinylacetate copolymer

Photothermal degradation studies were conducted on a 'stabilized' formulation of ethylene/vinyl acetate copolymer (EVA) in the temperature range 25-105 C under three different oxygen environments (in open air, with limited access to O2, and in a dark closed stagnant oven). These studies were performed in order to evaluate the utility of EVA as an encapsulation material for photovoltaic modules. Results showed that at low temperature (25 C), slow photooxidation of the polymer occurred via electronic energy transfer involving the UV absorber incorporated in the polymer. However, no changes in the physical properties of the bulk polymer were detected up to 1500 hours of irradiation. At elevated temperatures, leaching and evaporation of the additives occurred, which ultimately resulted in the chemical crosslinking of the copolymer and the formation of volatile photoproducts such as acetic acid.

Liang, R. H.↗

Chemical and Thermal Analysis

Work during the past three years has included significant research in several areas aimed at further clarification of the aging and chemical failure mechanism of thermoplastics (PVDF or Tefzel) for pipes. Among the areas investigated were the crystallinity changes associated with both the Coflon and Tefzel after various simulated environmental exposures using X-Ray diffraction analysis. We have found that significant changes in polymer crystallinity levels occur as a function of the exposures. These crystallinity changes may have important consequences on the fracture, fatigue, tensile, and chemical resistance of the materials. We have also noted changes in the molecular weight distribution and the increased crosslinking of the Coflon material using Gel Permeation Chromatographic Analysis. Again these changes may result in variations in the mechanical and chemical properties in the material. We conducted numerous analytical studies with methods including X-ray Diffraction, Gel Permeation Chromatography, Fourier Transform Infrared Spectroscopy, and Differential Scanning Calorimetry. We investigated a plethora of aged samples of both Tefzel and Coflon that were forwarded from MERL. Pressurized tests were performed on powdered PVDF in a modified Fluid A, which we will call A-2. In this case the ethylene diamine concentration was increased to 3 percent in methanol. Coflon pipe sections and powdered Coflon were exposed in pressure cells at 1700 psi at three separate test temperatures.

Bulluck, J. W.↗

Validity Using Pump-Probe Pulses to Determine the Optical Response of Niobate Crystals

A variety of niobate crystals have found their places in nonlinear optical applications as well as in laser devices. In recent years much attention has been paid to study the ultrafast optical response in a variety of photorefractive crystals such as KTa(1-x)Nb(x)O3 and KNbO3 crystals, glasses, semiconductors and polymers for applications in optical switching, information processing, optical computing, and all-optical device systems. Third-order optical nonlinearity is the most important property for realization of all-optical switching. Therefore experiments have been performed on the third order susceptibility using a variety of techniques such as the third-order harmonic generation, EFISH and degenerate four-wave mixing(DFWM). The latter has been conducted with a variety of pump wavelengths and with nanosecond, picosecond and femtosecond pulses. Niobate crystals, such as potassium niobate KNbO3, potassium tantalate niobate KTN family (KTa(1-x)Nb(x)O3), strontium barium niobate SBN (Sr(x)Ba(1-x)Nb2O6) and potassium-sodium niobate SBN (KNSBN) are attractive due to their photorefractive properties for application in optical storage and processing. The pulsed probe experiments performed on theses materials have suggested two types of time responses. These responses have been associated with an coherent response due to Chi(sup 3), and a long lived component due to excited state population. Recent study of DFWM on KNbO3 and KTN family reveals that the long lived component of those crystals depends on the crystal orientation. A slowly decaying signal is observable when the grating vector K(sub g) is not perpendicular to the C-axis of those photorefractive crystals', otherwise the optical response signal would be only a narrow coherent peak with FWHM equal to the cross-correlation width of the write beam pulses. Based on this understanding, we study the photodynamical process of a variety of niobate crystals using DFWM in a Kg perpindicular to C geometry with a ps-YAG: Nd laser operating at 532nm. However, the discrepancies in numerical estimations of Chi(sup 3) in these materials and other nonlinear optical media have resulted in a number of discussions. In order to better understand the photodynamical process of niobate crystals after an short pulse excitation we analyze the factors governing the coherent signal and present the DFWM spectra of niobate crystals.

Liu, Huimin↗

Morphologies, Processing and Properties of Ceramic Foams and Their Potential as TPS Materials

The current research is focused on processing ceramic foams with compositions that have potential as a thermal protection material. The use of pre-ceramic polymers with the addition of sacrificial blowing agents or sacrificial fillers offers a viable approach to form either open or closed cell insulation. Our work demonstrates that this is a feasible method to form refractory ceramic foams at relatively low processing temperatures. It is possible to foam complex shapes then pyrolize the system to form a ceramic while retaining the shape of the unfired foam. Initial work focused on identifying suitable pre-ceramic polymers with desired properties such as ceramic yield and chemical make up of the pyrolysis product after firing. We focused on making foams in the Si system (Sic, Si02, Si-0-C), which is in use in current acreage TPS systems. Ceramic foams with different architectures were formed from the pyrolysis of pre-ceramic polymers at 1200 C in different atmospheres. In some systems a sacrificial polyurethane was used as the blowing agent. We have also processed foams using sacrificial fillers to introduce controlled cell sizes. Each sacrificial filler or blowing agent leads to a unique morphology. The effect of different fillers on foam morphologies and the characterization of these foams in terms of mechanical and thermal properties are presented. We have conducted preliminary arc jet testing on selected foams with the materials being exposed to typical re-entry conditions for acreage TPS and these results will be discussed. Foams processed using these approaches have bulk densities ranging from 0.15 to 0.9 g/cm3 and cell sizes ranging from 5 to 500 pm. Compression strengths ranged from 2 to 7 MPa for these systems. Finally, preliminary oxidation studies have been conducted on selected systems and will be discussed.

Stackpoole, Mairead↗

Selective Reinforcement to Enhance the Structural Performance of Metallic Compression Panels

An experimental and analytical investigation of the influence of selective reinforcement on metallic panels with cutouts was conducted. Selective reinforcement was shown to be a weight effective concept for increasing structural performance of panels with cutouts designed to carry loads into the post-buckled regime. For instance, a selectively reinforced aluminum panel under shear load exhibited a 68 percent increase in specific-buckling load as compared to a geometrically comparable unreinforced aluminum panel. In comparison, a quasi-isotropic carbon-fiber-reinforced-polymer composite panel only produced a 45 percent higher specific-buckling load than the same unreinforced aluminum panel. Selective reinforcement offers the potential to tailor structural response through local strengthening and stiffening the structure for a broad range of structural application.

Farley, Gary L.↗

Effect of Water on the Thermo-Mechanical Behavior of Carbon Cloth Phenolic

The results of thermo-mechanical experiments, which were conducted previously by one of the authors, are reviewed. The strain in the direction normal to the fabric plane was measured as a function of temperature for a variety of initial moisture contents and heating rates. In this paper, the general features of the thermo-mechanical response are discussed and the effect of heating rate and initial moisture content are highlighted. The mechanical interaction between the phenolic polymer and water trapped within its free volumes as the polymer is heated to high temperatures is discussed. An equation for the internal stresses which are generated within the polymer due to trapped water is obtained from the total stress expression for a binary mixture of polymer and water. Numerical solutions for moisture diffusion in the thermo-mechanical experiments were performed and the results of these solutions are presented. The results of the moisture diffusion solutions help to explain the effects of heating rate and moisture content on the strain behavior normal to the fabric plane.

Sullivan, Roy M.↗

Multifunctional Polymers and Composites for Aerospace Applications

System needs and challenges for commercial aviation and space exploration are constantly changing. Multifunctional materials are ideal for aerospace applications because their integration into structural components has potential to not only improve efficiency, but it can also increase payload and mission capabilities without the burden of significant additions to mass and volume. Multi-constituent materials will play an important role in enabling structures with the potential to demonstrate true multi-functionality; however, modifications to many mature polymer processing methods may be necessary. This presentation will cover multifunctional materials development efforts underway at the NASA Glenn Research Center related to formulating and characterizing novel electrical insulation for high voltage aircraft. Incorporating functionality into the reinforcement material is another materials development technique that will be discussed, which includes braiding with hybrid fibers to enhance toughness in composite structures, stitching with carbon nanotube yarns to make durable electrically conductive textiles, and treating fabrics with shear thickening fluid suspensions to produce impact-resistant inflatable habitats.

multi-functional composites↗

Friction and morphology of magnetic tapes in sliding contact with nickel-zinc ferrite

Friction and morphological studies were conducted with magnetic tapes containing a Ni-Zn ferrite hemispherical pin in laboratory air at a relative humidity of 40 percent and at 23 C. The results indicate that the binder plays a significant role in the friction properties, morphology, and microstructure of the tape. Comparisons were made with four binders: nitrocellulose; poly (vinyledene) chloride; cellulose acetate; and hydroxyl-terminated, low molecular weight polyester added to the base polymer, polyester-polyurethane. The coefficient of friction was lowest for the tape with the nitrocellulose binder and increased in the order hydroxylterminated, low molecular weight polyester resin; poly (vinyledene) chloride; and cellulose acetate. The degree of enclosure of the oxide particles by the binder was highest for hydroxyl-terminated, low molecular weight polyester and decreased in the order cellulose acetate, poly (vinyledene) chloride, and nitrocellulose. The nature of deformation of the tape was a factor in controlling friction. The coefficient of friction under elastic contact conditions was considerably lower than under conditions that produced plastic contacts.

Miyoshi, K.↗

Polymer Matrix Composites Fabrication and Testing

This project involves two separate processes for fabricating carbon fiber composite parts using Hexcel’s RTM6 resin system and Kaneka’s IR-6070 toughened resin system to impregnate carbon fiber tow and weave. These two resins were chosen to model microcracking in parts using RTM6 compared to parts using IR-6070. Plies of the composites were made by painting resin onto 8 harness satin weave or impregnating IM7 12k tow in a prepregging machine. Plies were consolidated using an out-of-autoclave oven or a heat press. Fabrication of the composite parts were conducted with the end goal of sending the composites to be tested and modeled for microcracking. The data will be used for computer modeling in the future.

Miller, Sandi↗

Space shuttle seal material and design development for earth storable propellant systems

The results of a program to investigate and characterize seal materials suitable for space shuttle storable propellant systems are given. Two new elastomeric materials were identified as being potentially superior to existing state-of-the art materials for specific sealing applications. These materials were AF-E-124D and AF-E-411. AF-E-124D is a cured perfluorinated polymer suitable for use with dinitrogen tetroxide oxidizer, and hydrazine base fuels. AF-E-411 is an ethylene propylene terpolymer material for hydrazine base fuel service. Data are presented relative to low and high temperature characteristics as well as propellant exposure effects. Types of data included are: mechanical properties, stress strain curves, friction and wear characteristics, compression set and permeability. Sealing tests with a flat poppet-seal valve were conducted for verification of sealing capability. A bibliography includes over 200 references relating to seal design or materials and presents a concise tabulation of the more useful seal design data sources.

Source record↗

Innovative Electrostatic Adhesion Technologies

Developing specialized Electro-Static grippers (commercially used in Semiconductor Manufacturing and in package handling) will allow gentle and secure Capture, Soft Docking, and Handling of a wide variety of materials and shapes (such as upper-stages, satellites, arrays, and possibly asteroids) without requiring physical features or cavities for a pincher or probe or using harpoons or nets. Combined with new rigid boom mechanisms or small agile chaser vehicles, flexible, high speed Electro-Static Grippers can enable compliant capture of spinning objects starting from a safe stand-off distance. Electroadhesion (EA) can enable lightweight, ultra-low-power, compliant attachment in space by using an electrostatic force to adhere similar and dissimilar surfaces. A typical EA enabled device is composed of compliant space-rated materials, such as copper-clad polyimide encapsulated by polymers. Attachment is induced by strong electrostatic forces between any substrate material, such as an exterior satellite panel and a compliant EA gripper pad surface. When alternate positive and negative charges are induced in adjacent planar electrodes in an EA surface, the electric fields set up opposite charges on the substrate and cause an electrostatic adhesion between the electrodes and the induced charges on the substrate. Since the electrodes and the polymer are compliant and can conform to uneven or rough surfaces, the electrodes can remain intimately close to the entire surface, enabling high clamping pressures. Clamping pressures of more than 3 N/cm2 in shear can be achieved on a variety of substrates with ultra-low holding power consumption (measured values are less than 20 microW/Newton weight held). A single EA surface geometry can be used to clamp both dielectric and conductive substrates, with slightly different physical mechanisms. Furthermore EA clamping requires no normal force be placed on the substrate, as conventional docking requires. Internally funded research and development has demonstrated that EA can function effectively in space, even in the presence of strong ultraviolet radiation, atomic oxygen, and free electrons. We created a test setup in an existing vacuum chamber to simulate low-Earth-orbit conditions. An EA mechanism was fabricated and installed in the chamber, instrumented, operated in a vacuum, and subjected to ultraviolet photons and free electrons generated by an in-chamber multipactor electron emitter. Extensions to EA that can add value include proximity and contact sensing and transverse motion or rotation, both of which could enhance docking or assembly applications. Possible next steps include development of targeted applications for ground investigation or on-orbit subsystem performance demonstrations using low cost access to space such as CubeSats.

Bryan, Tom↗

Sample Processor for Life on Icy Worlds (SPLIce): Design and Test Results

We report the design, development, and testing of the Sample Processor for Life on Icy Worlds (SPLIce) system, a microfluidic sample processor to enable autonomous detection of signatures of life and measurements of habitability parameters in Ocean Worlds. This monolithic fluid processing-and-handling system (Figure 1; mass 0.5 kg) retrieves a 50-L-volume sample and prepares it to supply a suite of detection instruments, each with unique preparation needs. SPLIce has potential applications in orbiter missions that sample ocean plumes, such as found in Saturns icy moon Enceladus, or landed missions on the surface of icy satellites, such as Jupiters moon Europa. Answering the question Are we alone in the universe? is captivating and exceptionally challenging. Even general criteria that define life very broadly include a significant role for water [1,2]. Searches for extinct or extant life therefore prioritize locations of abundant water whether in ancient (Mars), or present (Europa and Enceladus) times. Only two previous planetary missions had onboard fluid processing: the Viking Biology Experiments [3] and Phoenixs Wet Chemistry Laboratory (WCL) [4]. SPLIce differs crucially from those systems, including its capability to process and distribute L-volume samples and the integration autonomous control of a wide range of fluidic functions, including: 1) retrieval of fluid samples from an evacuated sample chamber; 2) onboard multi-year storage of dehydrated reagents; 3) integrated pressure, pH, and conductivity measurement; 4) filtration and retention of insoluble particles for microscopy; 5) dilution or vacuum-driven concentration of samples to accommodate instrument working ranges; 6) removal of gas bubbles from sample aliquots; 7) unidirectional flow (check valves); 8) active flow-path selection (solenoid-actuated valves); 9) metered pumping in 100 nL volume increments. The SPLIce manifold, made of three thermally fused layers of precision-machined cyclo-olefin polymer, supports all fluidic components (Figure 1) and integrated microchannels (125 x 250 m). Fluid is pumped by a stepper-motor-driven pump (Lee Co.). The functionality of the integrated MEMS pressure sensor (Honeywell) and passive check valves (Figure 2) were tested in conjunction with our newly designed integral bubble traps (Figure 3) and hydrophobic membrane-based concentrator (Figure 4). The concentrator (initially tested as a standalone component) demonstrated 5-fold vacuum-evaporative concentration. Polyethylene fused bead beds (PEFBBs; 50 porosity) store drylyophilized buffers, calibrants, and fluorescent dyes, and also promote mixing of sample with calibrant, dye, or H2O. Software-controlled automated tests demonstrated successful 1) fluid delivery to each component 2) valve and pump synchronization 3) sample aliquot delivery to instrument interface ports, and 4) rehydration of vacuum-dried fluorescent dye. In Figure 5, fluorescein on PEFBBs was rehydrated for 15 min using a pump-delivered water aliquot; it is displaced as H2O enters the bottom of the channel and pushes the dye into a check valve. Ultimately, SPLIce will fluorescently label amino acids in the sample for microchip-based electrophoretic (MCE) chiral separation and detection to seek and quantify key organic bio-signatures [5]; it will also deliver sample to a microfluidic version of WCL (mWCL) to measure soluble ions and redox-active species.

Life detection↗