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At least 37 records · Page 2

Positron lifetime spectroscopy in thin polymer coatings

Polymer coatings are finding increasing applications in aerospace industry. The effectiveness of coatings depends strongly on their microstructure and adhesion to the substrates. Currently, there is no technique for adequately monitoring the quality of the coatings. We adapted positron lifetime spectroscopy for the investigation of thin coatings. Results of measurements on 0.001-in-thick polyurethane coatings on aluminum and steel substrates and thicker (0.080-in.) self-standing polyurethane discs were compared. In all cases, we find positron lifetime groups centered around 560 ps, corresponding to the presence of 0.9 A exp 3 free volume cells. However, the number of free volume cells in thin coatings is larger, suggesting that the morphology of thin coatings is different from that of bulk polyurethane. These results and their structural implications are discussed.

Singh, Jag J.↗

Carbon Monoxide Accumulation in the Extravehicular Mobility Unit

Introduction: Life support technology in large closed systems like submarines and space stations catalyzes carbon monoxide (CO) to carbon dioxide, which is easily removed. However, in a small system like the Extravehicular Mobility Unit (EMU), spacesuit, CO from exogenous (contaminated oxygen (O (sub 2) supply) and endogenous (human metabolism) sources will accumulate in the free suit volume. The free volume becomes a sink for CO that is rebreathed by the astronaut. The accumulation through time depends on many variables: the amount absorbed by the astronaut, the amount produced by the astronaut (between 0.28 and 0.34 moles per hour per kilogram)[1], the amount that enters the suit from contaminated O (sub 2), the amount removed through suit leak, the free volume of the suit, and the O (sub 2) partial pressure[2], just to list a few. Contamination of the EMU O (sub 2) supply with no greater than 1 part per million CO was the motivation for empirical measurements from CO pulse oximetry (SpCO) as well as mathematical modeling of the EMU as a rebreather for CO. Methods: We developed a first-order differential mixing equation as well as an iterative method to compute CO accumulation in the EMU. Pre-post measurements of SpCO (Rad-57, Masimo Corporation) from EMU ground training and on-orbit extravehicular activities (EVAs) were collected. Results: Initial modeling without consideration of the astronaut as a sink but only the source of CO showed that after 8 hours breathing 100 percent O (sub 2) with a 10 milliliter per minute (760 millimeters Hg at 21 degrees Centigrade standard) suit leak, an endogenous production rate of 0.23 moles per hour per kilogram for a 70 kilogram person with 42 liters (1.5 cubic feet) free suit volume resulted in a peak CO partial pressure (pCO) of 0.047 millimeters Hg at 4.3 pounds per square inch absolute (222 millimeters Hg). Preliminary results based on a 2008 model[3] with consideration of the astronaut as a sink and source of CO suggests that most of the rebreathed CO stays bound to hemoglobin and myoglobin and; therefore, pCO only increased to 0.002 millimeters Hg in the EMU. Hemoglobin saturation after 8 hours was an insignificant 0.4 percent compared to about 4 percent for cigarette smokers in the general population. This preliminary modeling result supplements 11 pre-post index finger SpCO measurements from EMU ground training (mean 0.5 percent versus 1 percent, probability equal to 0.41 from paired t-test) and 10 on-orbit pre-post EVAs (mean 1.5 percent versus 1.1 percent, probability equal to 0.17 from paired t-test) that showed no consistent increase, at least no increase outside the accuracy of the oximeter (1 percent display resolution with plus or minus 3 percent Standard Deviation). Discussion: Simulations continue, but a preliminary conclusion is that rebreathing endogenous CO accumulating in the EMU is not a serious medical issue during EVA. The absence of CO poisoning signs or symptoms following hundreds of EVAs is also good empirical evidence that corroborates the limited SpCO measurements and preliminary modeling results.

Conkin, J.↗

Investigation of Polymer Liquid Crystals

The positron annihilation lifetime spectroscopy (PALS) using a low energy flux generator may provide a reasonably accurate technique for measuring molecular weights of linear polymers and characterization of thin polyimide films in terms of their dielectric constants and hydrophobity etc. Among the tested samples are glassy poly arylene Ether Ketone films, epoxy and other polyimide films. One of the proposed techniques relates the free volume cell size (V(sub f)) with sample molecular weight (M) in a manner remarkably similar to that obtained by Mark Houwink (M-H) between the inherent viscosity (eta) and molecular wieght of polymer solution. The PALS has also demonstrated that free-volume cell size in thermoset is a versatile, useful parameter that relates directly to the polymer segmental molecular weight, the cross-link density, and the coefficient of thermal expansion. Thus, a determination of free volume cell size provides a viable basis for complete microstructural characterization of thermoset polyimides and also gives direct information about the cross-link density and coefficient of expansion of the test samples. Seven areas of the research conducted are reported here.

Han, Kwang S.↗

Positron lifetime spectroscopy for investigation of thin polymer coatings

In the aerospace industry, applications for polymer coatings are increasing. They are now used for thermal control on aerospace structures and for protective insulating layers on optical and microelectronic components. However, the effectiveness of polymer coatings depends strongly on their microstructure and adhesion to the substrates. Currently, no technique exists to adequately monitor the quality of these coatings. We have adapted positron lifetime spectroscopy to investigate the quality of thin coatings. Results of measurements on thin (25-micron) polyurethane coatings on aluminum and steel substrates have been compared with measurements on thicker (0.2-cm) self-standing polyurethane discs. In all cases, we find positron lifetime groups centered around 560 psec, which corresponds to the presence of 0.9-A(exp 3) free-volume cells. However, the number of these free-volume cells in thin coatings is larger than in thick discs. This suggests that some of these cells may be located in the interfacial regions between the coatings and the substrates. These results and their structural implications are discussed in this report.

Singh, Jag J.↗

Morphology of Thermoset Polyimides by Positron Annihilation Spectroscopy

Thermoset polyimides have great potential for successfully meeting tough stress and temperature challenges in the advanced aircraft development program. However, studies of structure/property relationships in these materials have not been very successful so far. Positron annihilation spectroscopy has been used to investigate free volumes and associated parameters. It has been noted that the free volume correlates well with the molecular weight, cross-link density and thermal coefficient of expansion of these materials. Currently no other techniques are available for direct measurement of these parameters. Experimental results and their interpretations will be discussed.

Ranganathaiah, C.↗

Fundamental Insight on Developing Low Dielectric Constant Polyimides

Thermally stable, durable, insulative polyimides are in great demand for the fabrication of microelectronic devices. In this investigation dielectric and optical properties have been studied for several series of aromatic polyimides. The effect of polarizability, fluorine content, and free volume on dielectric constant was examined. In general, minimizing polarizability, maximizing free volume and fluorination all lowered dielectric constants in the polyimides studied.

Simpson, J. O.↗

Hot Gas Testing Results of Stagnant Volume Filling Through a Back-Filled RSRM Nozzle Joint

Silicone rubber is back-filled into RSW nozzle joints after assembly. A possible artifact of this process is the formation of small pathways through this filter leading to sensitive sealing materials within the joint. At motor ignition, hot gases fill the stagnant volumes within the joint through this path. A series of 14 test has been completed studying this scenario and providing anchoring data for thermal/flow models. Parameters such as gas path cross section, gas path length, gas path materials, fill volume size, and post path gas spreading prior to unpingement on seal material, have been investigated. Tests were accomplished using geometry similar to RSRM nozzle joint 4 with attached volumes replicating the free volume and flow friction in the actual hardware. The test hardware simulated 8 inches of the full-scale circumference. Testing has pointed to changes required in model boundary condition assumptions and gas dynamics corrections for gas paths of this size and geometry. Areas ,where this date has provided improvement in analysis models will be covered as well as model inadequacies that require separate specialized efforts. Questions remaining after this testing and a possible direction for future testing will be suggested.

Prince, Andrew S.↗

Lattice model theory of the equation of state covering the gas, liquid, and solid phases

The three stable states of matter and the corresponding phase transitions were obtained with a single model. Patterned after Lennard-Jones and Devonshires's theory, a simple cubic lattice model containing two fcc sublattices (alpha and beta) is adopted. The interatomic potential is taken to be the Lennard-Jones (6-12) potential. Employing the cluster variation method, the Weiss and the pair approximations on the lattice gas failed to give the correct phase diagrams. Hybrid approximations were devised to describe the lattice term in the free energy. A lattice vibration term corresponding to a free volume correction is included semi-phenomenologically. The combinations of the lattice part and the free volume part yield the three states and the proper phase diagrams. To determine the coexistence regions, the equalities of the pressure and Gibbs free energy per molecule of the coexisting phases were utilized. The ordered branch of the free energy gives rise to the solid phase while the disordered branch yields the gas and liquid phases. It is observed that the triple point and the critical point quantities, the phase diagrams and the coexistence regions plotted are in good agreement with the experimental values and graphs for argon.

Bonavito, N. L.↗

A Method for Characterizing Thermoset Polyimides

Thermoset polyimides have great potential for successfully meeting tough stress and temperature challenges in the advanced aircraft development program. However, studies of structure-property relationships in these materials have not been very successful so far. Positron lifetime spectroscopy (PLS) has been used to investigate free volumes and associated parameters in a series of variable, segmental molecular weight samples. The free volume correlates well with the molecular weight M(sub c), the cross-link density v, and the coefficient of thermal expansion (CTE) of these materials. Currently, no other techniques are available for direct measurement of these parameters, particularly for polymers in solid phase. Experimental results and their interpretations are presented.

Ranganathaiah, C.↗

Microstructural characterization of thin polymer films using Langley low energy positron flux generator

We have developed a highly efficient scheme for generating high fluxes of slow positrons. These positrons have been successfully used to measure lifetimes in thin test films. The lifetime data have been used to develop two structure-property models for the test films. The first model relates the free volume cell size to the molecular weight of the polymer repeat unit. The second model relates the free volume fraction to the dielectric constant of the polymer film.

Singh, Jag. J.↗

Rapid quenching effects in glassy polymers

Using a specially constructed microbalance for hydrostatic weighing, density changes in PVC thin film due to rapid quenching through the glass transition temperature were observed. The more severe the quench, the greater the free volume content. Isobaric volume recovery of PVC was also studied by volume dilatometry. Both show aging of relaxing molecular rearrangements taking place as a linear function of logarithmic aging time at room temperature. Distribution of retardation times and Primak's distributed activation energy spectra were applied to the volume recovery data. The concomitant changes in mechanical properties of PVC after quenching were monitored by tensile creep stress-stran to failure rates. All reflect the presence of excess free volume content due to rapid quenching.

Mcgarry, F. 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.↗

Rapid quenching effects in PVC films

Using a specially constructed microbalance for hydrostatic weighing, density changes in PVC thin films (with no additives, 30-100 micrometers thick), due to rapid quenching (approximately 300 C/sec) through the glass transition temperature, have been observed. The more severe the quench, the greater is the free volume content. Isobaric volume recovery of PVC has also been studied by volume dilatometry. Both show aging of relaxing molecular rearrangements takes place as a linear function of logarithmic aging time at room temperature. Distribution of retardation times and Primak's distributed activation energy spectra have been applied to the volume recovery data. The concomitant changes in mechanical properties of PVC after quenching have been monitored by tensile creep and stress-strain to failure. All reflect the presence of excess free volume content, due to rapid quenching.

Lee, H. D.↗

Colloidal Oxide Properties and Kinetic Studies

Silica based oxide particles prepared by various methods are compared in terms of their gellation kinetics, densification kinetics, and microable structural evolutions begin at very low temperature. Additional work reported in literature further suggested that the colloidal behaviors and the dried gel structures of the same oxide from different preparation techniques differ fundamentally. These differences significantly affect the densification kinetics and the product microstructure. Gravitational segregation of particles of different sizes in a gravitational field is modelled as a diffusion/segregation problem. A structural free volume model was used to describe the activation process of jump statistics. The sizes of the particles, the interstices, and their packing topology are accounted for in the estimation of the free volume. An attempt frequency is ascribed to particles to account for the vibrational rearrangement during powder packing.

Chen, I. W.↗

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.↗

Investigation of microstructural changes in polyetherether-ketone films at cryogenic temperatures by positron lifetime spectroscopy

Microstructural changes in Polyetherether-ketone (PEEK) films were investigated in the temperature ranges of 23 to -196 C, using Positron Lifetime Spectroscopy (PLS) technique. It was determined that the total free volume decreases by about 46 percent in amorphous PEEK samples and about 36 percent in semicrystalline PEEK samples when they are cooled down from room temperature to liquid nitrogen (LN2) temperature. If this trend in reduction in free volume with decreasing temperature continues, as expected, it is surmised that PEEK will be able to withstand cooling down to liquid hydrogen (LH2) temperature without any detrimental effect on its diffusivity for liquid hydrogen.

Singh, Jag J.↗

Performance model of a recirculating stack nickel hydrogen cell

A theoretical model of the nickel hydrogen battery cell has been utilized to describe the chemical and physical changes during charge and overcharge in a recirculating stack nickel hydrogen cell. In particular, the movement of gas and electrolyte have been examined as a function of the amount of electrolyte put into the cell stack during cell activation, and as a function of flooding in regions of the gas screen in this cell design. Additionally, a two-dimensional variation on this model has been utilized to describe the effects of non-uniform loading in the nickel-electrode on the movement of gas and electrolyte within the recirculating stack nickel hydrogen cell. The type of nonuniform loading that has been examined here is that associated with higher than average loading near the surface of the sintered nickel electrode, a condition present to some degree in many nickel electrodes made by electrochemical impregnation methods. The effects of high surface loading were examined primarily under conditions of overcharge, since the movement of gas and electrolyte in the overcharging condition was typically where the greatest effects of non-uniform loading were found. The results indicate that significant changes in the capillary forces between cell components occur as the percentage of free volume in the stack filled by electrolyte becomes very high. These changes create large gradients in gas-filled space and oxygen concentrations near the boundary between the separator and the hydrogen electrode when the electrolyte fill is much greater than about 95 percent of the stack free volume. At lower electrolyte fill levels, these gaseous and electrolyte gradients become less extreme, and shift through the separator towards the nickel electrode. Similarly, flooding of areas in the gas screen cause higher concentrations of oxygen gas to approach the platinum/hydrogen electrode that is opposite the back side of the nickel electrode. These results illustrate the need for appropriate pore size distributions, and the maintenance of both convective electrolyte and gas flow paths through the stack, if the recirculating stack nickel hydrogen cell design is to work properly.

Zimmerman, Albert H.↗

A study of physical properties of ODPA-p-PDA polyimide films

Physical properties were investigated of ODPA-p-PDA polyimide films, including their lower molecular weight versions with phthalimide endcaps. Free volume, determined by low energy positron annihilation in the test films, was the major parameter of interest since all other physical properties are ostensibly related to it. It affects the dielectric constant as well as the saturation moisture pickup of the test films. An empirical relation was developed between the free volume and molecular weight of the test films, comparable to the Mark-Houwink relation between the polymer solution viscosity and the molecular weight. Development of such a relation constitutes a unique achievement since it enables researchers to estimate the molecular weight of an intractable polymer in solid state for the first time.

Singh, Jag J.↗