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At least 163 records · Page 9

Microstructural Characterization of Semi-Interpenetrating Polymer Networks by Positron Lifetime Spectroscopy

Thermoset and thermoplastic polyimides have complementary physical and mechanical properties. Whereas thermoset polyimides are brittle and generally easier to process, thermoplastic polyimides are tough but harder to process. A combination of these two types of polyimides may help produce polymers more suitable for aerospace applications. Semi-Interpenetrating Polymer Networks (S-IPN) of thermoset LaRC(TM)-RP46 and thermoplastic LaRC(TM)-IA polyimides were prepared in weight percent ratios ranging from 100:0 to 0:100. Positron lifetime measurements were made in these samples to correlate their free volume features with physical and mechanical properties. As expected, positronium atoms are not formed in these samples. The second lifetime component has been used to infer the positron trap dimensions. The 'free volume' goes through a minimum at a ratio of about 50:50, and this suggests that S-IPN samples are not merely solid solutions of the two polymers. These data and related structural properties of the S-IPN samples are discussed.

Singh, Jag J.↗

Nuclear Instruments and Methods in Physics Research: Microstructural Characterization of Semi-Interpenetrating Polymer Networks by Positron Lifetime Spectroscopy - Section B

Thermoset and thermoplastic polyimides have complementary physical/mechanical properties. Whereas thermoset polyimides are brittle and generally easier to process, thermoplastic polyimides are tough but harder to process. It is expected that a combination of these two types of polyimides may help produce polymers more suitable for aerospace applications. Semi-Interpenetrating Polymer Networks (S-IPNs) of thermoset LaRC(Trademark)-RP46 and thermoplastic LARC(Trademark)-IA polyimides were prepared in weight percent ratios ranging from 100:0 to 0: 100. Positron lifetime measurements were made in these samples to correlate their free volume features with physical/mechanical properties. As expected, positronium atoms are not formed in these samples. The second life time component has been used to infer the positron trap dimensions. The "free volume" goes through a minimum at about 50:50 ratio, suggesting that S-IPN samples are not merely solid solutions of the two polymers. These data and related structural properties of the S-IPN samples have been discussed in this paper.

Singh, Jag J.↗

Effects of Heating on Teflon(Registered Trademark) FEP Thermal Control Material from the Hubble Space Telescope

Metallized Teflon(Registered Trademark) FEP (fluorinated ethylene propylene) thermal control material on the Hubble Space Telescope (HST) is degrading in the space environment. Teflon(Registered Trademark) FEP thermal control blankets (space-facing FEP) retrieved during the first servicing mission (SM1) were found to be embrittled on solar facing surfaces and contained microscopic cracks. During the second servicing mission (SM2) astronauts noticed that the FEP outer layer of the multi-layer insulation (MLI) covering the telescope was cracked in many locations around the telescope. Large cracks were observed on the light shield, forward shell and equipment bays. A tightly curled piece of cracked FEP from the light shield was retrieved during SM2 and was severely embrittled, as witnessed by ground testing. A Failure Review Board (FRB) was organized to determine the mechanism causing the MLI degradation. Density, x-ray crystallinity and solid state nuclear magnetic resonance (NMR) analyses of FEP retrieved during SM1 were inconsistent with results of FEP retrieved during SM2. Because the retrieved SM2 material curled while in space, it experienced a higher temperature extreme during thermal cycling, estimated at 200 C, than the SM1 material, estimated at 50 C. An investigation on the effects of heating pristine and FEP exposed on HST was therefore conducted. Samples of pristine. SM1, and SM2 FEP were heated to 200 C and evaluated for changes in density and morphology. Elevated temperature exposure was found to have a major impact on the density of the retrieved materials. Characterization of polymer morphology of as-received and heated FEP samples by NMR provided results that were consistent with the density results. These findings have provided insight to the damage mechanisms of FEP in the space environment.

deGroh, Kim↗

Optical Spectroscopy of New Materials

Composites are currently used for a rapidly expanding number of applications including aircraft structures, rocket nozzles, thermal protection of spacecraft, high performance ablative surfaces, sports equipment including skis, tennis rackets and bicycles, lightweight automobile components, cutting tools, and optical-grade mirrors. Composites are formed from two or more insoluble materials to produce a material with superior properties to either component. Composites range from dispersion-hardened alloys to advanced fiber-reinforced composites. UV/VIS and FTIR spectroscopy currently is used to evaluate the bonding between the matrix and the fibers, monitor the curing process of a polymer, measure surface contamination, characterize the interphase material, monitor anion transport in polymer phases, characterize the void formation (voids must be minimized because, like cracks in a bulk material, they lead to failure), characterize the surface of the fiber component, and measure the overall optical properties for energy balances.

White, Susan M.↗

Synthesis and Luminescence of Yellow/Orange-Emitting Poly[tris(2,5-dihexyloxy-l,4-phenylenevinylene)-alt-(l,3-phenylenevinylene)]s

Soluble yellow/orange-emitting poly[tris(2,5-dihexyloxy-1,4-phenylenevinylene)-alt- (1,3-phenylenevinylene)] derivatives (6) have been synthesized and characterized. These polymers contain oligo(p-phenylene vinylene) chromophores of equal conjugation length, which are linked to a m-phenylene unit. Optical comparison between 6 and its model compound 8 at room and low temperature reveals the similarity in their absorption and fluorescence band structures. The vibronic band structure of 6 is assigned with the aid of the spectroscopic data for 8 at low temperature. Polymers 6 are electroluminescent with emission lambda (sub max), at approximately 565 nm. By using the device configuration of ITO/PEDOT/6/Ca, the polymer exhibits an external EL efficiency as high as 0.46%.

Liao, Liang↗

Atomic Oxygen Durability Evaluation of a UV Curable Ceramer Protective Coating

The exposure of most silicones to atomic oxygen in low Earth orbit (LEO) results in the oxidative loss of methyl groups with a gradual conversion to oxides of silicon. Typically there is surface shrinkage of oxidized silicone protective coatings which leads to cracking of the partially oxidized brittle surface. Such cracks widen and branch crack with continued atomic oxygen exposure ultimately allowing atomic oxygen to reach any hydrocarbon polymers under the silicone coating. A need exists for a paintable silicone coating that is free from such surface cracking and can be effectively used for protection of polymers and composites in LEO. A new type of silicone based protective coating holding such potential was evaluated for atomic oxygen durability in an RF atomic oxygen plasma exposure facility. The coating consisted of a UV curable inorganic/organic hybrid coating, known as a ceramer, which was fabricated using a methyl substituted polysiloxane binder and nanophase silicon-oxo-clusters derived from sol-gel precursors. The polysiloxane was functionalized with a cycloaliphatic epoxide in order to be cured at ambient temperature via a cationic UV induced curing mechanism. Alkoxy silane groups were also grafted onto the polysiloxane chain, through hydrosilation, in order to form a network with the incorporated silicon-oxo-clusters. The prepared polymer was characterized by H-1 and Si-29 NMR, FT-IR, and electrospray ionization mass spectroscopy. The paper will present the results of atomic oxygen protection ability of thin ceramer coatings on Kapton H as evaluated over a range of atomic oxygen fluence levels.

Banks, Bruce A.↗

Space Environmentally Stable Polyimides and Copolyimides

Polyimides with a unique combination of properties including low color in thin films, atomic oxygen (AO), ultra-violet (UV) radiation resistance, solubility in organic solvents in the imide form, high glass transition (T(sub g)) temperatures and high thermal stability have been prepared and characterized. The polymers were prepared by reacting a novel aromatic diamine with aromatic dianhydrides in a polar aprotic solvent. The solubility of the polymers in the imide form as well as the color density of thin films were dependent upon the chemical structure of the dianhydride. Several thin films (25-50 mm thick) prepared by solution casting of amide acid or imide solutions exhibited very low color and high optical transparency (approximately 90%) as determined by UV/visible spectroscopy. The polymers exhibited T(sub g)s >200 C depending upon the structure of the dianhydride and temperatures of 5% weight loss approximately 500C in air as determined by dynamic thermogravimetric analysis. Thin films coated with silver/inconel were exposed to a high fluence of AO and 1000 equivalent solar hours of UV radiation. The effects of these exposures on optical properties were minor. These space environmentally durable polymers are potentially useful in a variety of applications on spacecraft such as thin film membranes on antennas, second-surface mirrors, thermal/optical coatings and multi-layer thermal insulation (MLI) blanket materials. The chemistry, physical and mechanical properties of the polymers as well as their responses to AO and UV exposure will be discussed.

Watson, Kent A.↗

Gas Sensor Test Chip

A new test chip is being developed to characterize conducting polymers used in gas sensors. The chip, a seven-layer cofired alumina substrate with gold electrodes, contains 11 comb and U- bend test structures. These structures are designed to measure the sheet resistance, conduction anisotropy, and peripheral conduction of spin-coated films that are not subsequently patterned.

conducting polymers gas sensors test chipnd periph↗

Recent Advances in Thermoplastic Puncture-Healing Polymers

Self-healing materials provide a route for enhanced damage tolerance in materials for aerospace applications. In particular, puncture-healing upon impact has the potential to mitigate significant damage caused by high velocity micrometeoroid impacts. This type of material also has the potential to improve damage tolerance in load bearing structures to enhance vehicle health and aircraft durability. The materials being studied are those capable of instantaneous puncture healing, providing a mechanism for mechanical property retention in lightweight structures. These systems have demonstrated healing capability following penetration of fast moving projectiles -- velocities that range from 9 mm bullets shot from a gun (approx.330 m/sec) to close to micrometeoroid debris velocities of 4800 m/sec. In this presentation, we report on a suite of polymeric materials possessing this characteristic. Figure 1 illustrates the puncture healing concept. Puncture healing in these materials is dependent upon how the combination of a polymer's viscoelastic properties responds to the energy input resulting from the puncture event. Projectile penetration increases the temperature in the vicinity of the impact. Self-healing behavior occurs following puncture, whereby energy must be transferred to the material during impact both elastically and inelastically, thus establishing two requirements for puncture healing to occur: a.) The need for the puncture event to produce a local melt state in the polymer material and b.) The molten material has to have sufficient melt elasticity to snap back and close the hole. 1,2 Previous ballistic testing studies revealed that Surlyn materials warmed up to a temperature approx.98 C during projectile puncture (3 C higher than it s melting temperature). 1,2 The temperature increase produces a localized flow state and the melt elasticity to snap back thus sealing the hole. Table 1 lists the commercially polymers studied here, together with their physical properties. The polymers were selected based on chemical structure, tensile strengths, tensile moduli, glass transition temperature, melting temperatures, and impact strength. The thermal properties of the polymers were characterized by Differential Scanning Calorimetry (DSC) and Dynamic Mechanical Analysis (DMA). Mechanical properties were assessed by a Sintech 2W instron according to ASTM D1708 or D638 at crosshead speeds of 5.08 cm/min. 7.6 cm x 7.6 cm panels of the different materials were prepared and ballistic testing was performed at various temperatures. The panels were shot with a .223 caliber semiautomatic rifle from a distance of 23 meters at various temperatures. Chronographs were used to measure initial and final bullet velocity. Temperatures at the site of impact were measured using a FLIR ThermaCAM S60 thermal camera. A Vision Research model Phantom 9 high speed video camera was used to capture high speed video footage of ballistics testing.

Gordon, K. L.↗

Surface Characterization of Carbon Fiber Reinforced Polymers by Picosecond Laser Induced Breakdown Spectroscopy

Adhesive bonding of composite materials requires reliable monitoring and detection of surface contaminants as part of a vigorous quality control process to assure robust and durable bonded structures. Surface treatment and effective monitoring prior to bonding are essential in order to obtain a surface which is free from contaminants that may lead to inferior bond quality. In this study, the focus is to advance the laser induced breakdown spectroscopy (LIBS) technique by using pulse energies below 100 μJ (μLIBS) for the detection of low levels of silicone contaminants in carbon fiber reinforced polymer (CFRP) composites. Various CFRP surface conditions were investigated by LIBS using ∼10 ps, 355 nm laser pulses with pulse energies below 30 μJ. Time-resolved analysis was conducted to optimize the gate delay and gate width for the detection of the C I emission line at 247.9 nm to monitor the epoxy resin matrix of CFRP composites and the Si I emission line at 288.2 nm for detection of silicone contaminants in CFRP. To study the surface sensitivity to silicone contamination, CFRP surfaces were coated with polydimethylsiloxane (PDMS), the active ingredient in many mold release agents. The presence of PDMS was studied by inspecting the Si I emission lines at 251.6 nm and 288.2 nm. The measured PDMS areal densities ranged from 0.15 to 2 μg/cm(sup 2). LIBS measurements were performed before and after laser surface ablation. The results demonstrate the successful detection of PDMS thin layers on CFRP using picosecond μLIBS.

Rodolfo Ledesma↗

Control of polymer architectures by living ring-opening metathesis copolymerization

In an aspect, a method of synthesizing a graft copolymer comprises the steps of: copolymerizing a first macromonomer and a first reactive diluent; wherein said first macromonomer comprises a first backbone precursor directly or indirectly covalently linked to a first polymer side chain group; wherein said reactive diluent is provided in the presence of the first macromonomer at an amount selected so as to result in formation said graft copolymer having a first backbone incorporating said diluent and said first macromonomer in a first polymer block characterized by a preselected first graft density or a preselected first graft distribution of said first macromonomer. In some embodiments of this aspect, said preselected first graft density is any value selected from the range of 0.05 to 0.75. In some methods, the composition and amount of said diluent is selected to provide both a first preselected first graft density and a first preselected first graft distribution.

Grubbs, Robert H.↗

Small Angle X-Ray Scattering and Polymers

Polymers are some of the most versatile and useful materials on this planet. Properties of polymers are a result of their processing history, chemical makeup, and physical structure. Therefore, characterization is necessary to develop new polymer formulations and processes. Many established techniques for polymer characterization are destructive, and alternative methods that don’t destroy samples are in high demand. Thermal analysis techniques such as differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) yield important characteristic information for polymer samples while destroying the sample. Non-destructive strategies such as X ray diffraction (XRD) or small angle X-ray scattering (SAXS) can also find polymer characteristics while preserving a sample’s attributes. Sample preservation is desirable when investigating novel formulation and processing methods. SAXS analysis will be done on two different polymers: polyethylene, and a triblock copolymer. Using these two polymers allows for confidence between tests as polyethylene is very common, and well understood. Polyethylene analysis will be done first, and when methods have been refined so that the SAXS data matches accepted thermal analysis values for HDPE, there will be confidence to use the same analysis on block copolymers. Block copolymers remain relatively unexplored, so SAXS data will yield valuable information on their characteristics. Understanding the mechanical properties of these polymers is paramount to their application in upcycling, a process by which waste plastic can be converted into a higher value commodity. For this project, the upcycling process will be done via 3-dimensional (3d) printing.

36 MATERIALS SCIENCE↗

Dual-Stimuli Responsive Single-Chain Polymer Folding via Intrachain Complexation of Tetramethoxyazobenzene and β-Cyclodextrin

We synthesize and characterize a triblock polymer with asymmetric tetramethoxyazobenzene (TMAB) and β-cyclodextrin functionalization, taking advantage of the well-characterized azobenzene derivative-cyclodextrin inclusion complex to promote photoresponsive, self-contained folding of the polymer in an aqueous system. We use 1 H NMR to show the reversibility of (E)-to-(Z) and (Z)-to-(E) TMAB photoisomerization, and evaluate the thermal stability of (Z)-TMAB and the comparatively rapid acid-catalyzed thermal (Z)-to-(E) isomerization. Important for its potential use as a functional material, we show the photoisomerization cyclability of the polymeric TMAB chromophore and calculate isomerization quantum yields by extinction spectroscopy. To verify self-inclusion of the polymeric TMAB and cyclodextrin, we use two-dimensional 1 H NOESY NMR data to show proximity of TMAB and cyclodextrin in the (E)-state only; however, (Z)-TMAB is not locally correlated with cyclodextrin. Lastly, the observed decrease in photoisomerization quantum yield for the dual-functionalized polymer compared to the isolated chromophore in an aqueous solution confirms TMAB and β-cyclodextrin not only are in proximity to one another, but also form the inclusion complex.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ionene polymers. III

Dicationic crosslinking agents isolation and characterization and formation of polymers with ionic crosslinks

Keyzer, H.↗

Material Characterization of Hierarchical Tunable Pore Size Polymer Foams Used in the MARBLE Mix Morphology Experiment

One of the great challenges of inertial confinement fusion and high energy density experiments is understanding the effects of mix on thermonuclear burn. The MARBLE campaign, conceived at Los Alamos National Laboratory, aims to gather new insights into this issue by utilizing unique target capsules containing polymer foams of variable pore sizes, tunable over an order of magnitude. Such capsules allow the degree of initial heterogeneity to be controlled experimentally for the first time. Here, we describe the various characterization efforts used to gain understanding of the chemical structure and behavior of the foam. Previous experiments were not sensitive to foam physical properties, and the MARBLE platform has aided in the development of techniques to measure foam properties such as deuterium content, density variation, hydrogen adsorption, and pore size and volume distribution.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗