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At least 145 records · Page 8

Applying state diagrams to food processing and development

The physical state of food components affects their properties during processing, storage, and consumption. Removal of water by evaporation or by freezing often results in formation of an amorphous state (Parks et al., 1928; Troy and Sharp, 1930; Kauzmann, 1948; Bushill et al., 1965; White and Cakebread, 1966; Slade and Levine, 1991). Amorphous foods are also produced from carbohydrate melts by rapid cooling after extrusion or in the manufacturing of hard sugar candies and coatings (Herrington and Branfield, 1984). Formation of the amorphous state and its relation to equilibrium conditions are shown in Fig. 1 [see text]. The most important change, characteristic of the amorphous state, is noticed at the glass transition temperature (Tg), which involves transition from a solid "glassy" to a liquid-like "rubbery" state. The main consequence of glass transition is an increase of molecular mobility and free volume above Tg, which may result in physical and physico-chemical deteriorative changes (White and Cakebread, 1966; Slade and Levine, 1991). We have conducted studies on phase transitions of amorphous food materials and related Tg to composition, viscosity, stickiness, collapse, recrystallization, and ice formation. We have also proposed that some diffusion-limited deteriorative reactions are controlled by the physical state in the vicinity of Tg (Roos and Karel, 1990, 1991a, b, c). The results are summarized in this article, with state diagrams based on experimental and calculated data to characterize the relevant water content, temperature, and time-dependent phenomena of amorphous food components.

Non-NASA Center↗

Effect of substituted phenylnadimides on processing and properties of PMR polyimide composites

Three nitrophenylnadimide cure initiators and two phenylnadimides (without nitros) were evaluated as additives to PMR-15 resins and Celion 6000 graphite fiber composites. The results of a resin screening study eliminated all of the additives except 3-nitrophenylnadimide (NO2PN) for use as a low temperature curing additive for PMR-15. Thus, NO2PN and the two control additives were investigated in PMR-15 formulations from which Celion 6000 graphite fiber/PMR-15 composites were processed both with low temperature (274 C) and normal (316 C) cure cycles. Comparisons of the two processing cycles, the resultant glass transition temperatures (Tg), the ambient, 274 and 316 C composite mechanical properties determined before and after 316 C postcure, the 316 C thermo-oxidative weight losses and the retention of 316 C composite mechanical properties are presented. Empirical correlations of the type and amount of nadimide additives with processing parameters, Tg, composite mechanical properties, composite thermo-oxidative stability and long term retention of 316 C composite mechanical properties are also presented.

Alston, W. B.↗

Effect of substituted phenylnadimides on processing and properties of PMR polyimide composites

Three nitrophenylnadimide cure initiators and two phenylnadimides (without nitros) were evaluated as additives to PMR-15 resins and Celion 6000 graphite fiber composites. The results of a resin screening study eliminated all of the additives except 3-nitrophenylnadimide (NO2PN) for use as a low temperature curing additive for PMR-15. Thus, NO2PN and the two control additives were investigated in PMR-15 formulations from which Celion 6000 graphite fiber/PMR-15 composites were processed both with low temperature (274 C) and normal (316 C) cure cycles. Comparisons of the two processing cycles, the resultant glass transition temperatures (Tg), the ambient, 274 and 316 C composite mechanical properties determined before and after 316 C postcure, the 316 C thermo-oxidative weight losses and the retention of 316 C composite mechanical properties are presented. Empirical correlations of the type and amount of nadimide additives with processing parameters, Tg, composite mechanical properties, composite thermo-oxidative stability and long term retention of 316 C composite mechanical properties are also presented.

Alston, W. B.↗

Liquid-Crystal Thermosets, a New Generation of High-Performance Liquid-Crystal Polymers

One of the major challenges for NASA's next-generation reusable-launch-vehicle (RLV) program is the design of a cryogenic lightweight composite fuel tank. Potential matrix resin systems need to exhibit a low coefficient of thermal expansion (CTE), good mechanical strength, and excellent barrier properties at cryogenic temperatures under load. In addition, the resin system needs to be processable by a variety of non-autoclavable techniques, such as vacuum-bag curing, resin-transfer molding (RTM), vacuum-assisted resin-transfer molding (VaRTM), resin-film infusion (RFI), pultrusion, and advanced tow placement (ATP). To meet these requirements, the Advanced Materials and Processing Branch (AMPB) at NASA Langley Research Center developed a new family of wholly aromatic liquid-crystal oligomers that can be processed and thermally cross-linked while maintaining their liquid-crystal order. All the monomers were polymerized in the presence of a cross-linkable unit by use of an environmentally benign melt-condensation technique. This method does not require hazardous solvents, and the only side product is acetic acid. The final product can be obtained as a powder or granulate and has an infinite shelf life. The obtained oligomers melt into a nematic phase and do not exhibit isotropization temperatures greater than the temperatures of decomposition (Ti > T(sub dec)). Three aromatic formulations were designed and tested and included esters, ester-amides, and ester-imides. One of the major advantages of this invention, named LaRC-LCR or Langley Research Center-Liquid Crystal Resin, is the ability to control a variety of resin characteristics, such as melting temperature, viscosity, and the cross-link density of the final part. Depending on the formulation, oligomers can be prepared with melt viscosities in the range of 10-10,000 poise (100 rad/s), which can easily be melt-processed using a variety of composite-processing techniques. This capability provides NASA with custom-made matrix resins that meet the required processing conditions for the fabrication of textile composites. Once the resin is in place, the temperature is raised to 375 C and the oligomers are cross-linked into a high-glass-transition-temperature (Tg) nematic network without releasing volatiles. The mechanical properties of the fully crosslinked, composite articles are comparable to typical composites based on commercially available epoxy resins.

Dingemans, Theo↗

Tough, Microcracking-Resistant, High-Temperature Polymer

Simultaneous synthesis from thermosetting and thermoplastic components yields polyimide with outstanding properties. Involves process in which one polymer cross-linked in immediate presence of other, undergoing simultaneous linear chain extension. New material, LaRC-RP40 synthesized from high-temperature thermosetting imide prepolymer and from thermoplastic monomer. Three significantly improved properties: toughness, resistance to microcracking, and glass-transition temperature. Shows promise as high-temperature matrix resin for variety of components of aircraft engines and for use in other aerospace structures.

Pater, Ruth H.↗

Process for crosslinking methylene-containing aromatic polymers with ionizing radiation

A process for crosslinking aromatic polymers containing radiation-sensitive methylene groups (-CH2-) by exposing the polymers to ionizing radiation thereby causing crosslinking of the polymers through the methylene groups is described. Crosslinked polymers are resistant to most organic solvents such as acetone, alcohols, hydrocarbons, methylene, chloride, chloroform, and other halogenated hydrocarbons, to common fuels and to hydraulic fluids in contrast to readily soluble uncrosslinked polymers. In addition, the degree of crosslinking of the polymers depends upon the percentage of the connecting groups which are methylene which ranges from 5 to 50 pct and preferably from 25 to 50 pct of the connecting groups, and is also controlled by the level of irradiation which ranges from 25 to 1000 Mrads and preferably from 25 to 250 Mrads. The temperature of the reaction conditions ranges from 25 to 200 C and preferably at or slightly above the glass transition temperature of the polymer. The crosslinked polymers are generally more resistant to degradation at elevated temperatures such as greater than 150 C, have a reduced tendency to creep under load, and show no significant embrittlement of parts fabricated from the polymers.

Bell, Vernon L.↗

Polyimides containing the cyclobutene-3,4-dione moiety

In the present invention, linear aromatic polyimides containing the cyclobutene-3,4-dione moiety were produced from the reaction of a substituted or unsubstituted 1,2-bis(4-aminoanilino) cyclobutene-3,4-dione (SQDA) with various aromatic dianhydrides. These polymers had high molecular weights and their glass transition temperatures (Tgs) were greater than 500 C. Despite the very high Tg, these polymers exhibited excellent adhesion to glass. In addition, the films of these polyimides increased in flexibility with increasing cure temperatures. The novelty of this invention lies in the linear aromatic polyimide containing the cyclobutene-3,4-dione moiety. The presence of this moiety causes such changes in properties as Tgs greater than 500 C, excellent adhesion to glass, and increased flexibility with increasing cure temperatures.

St.clair, Terry L.↗

Sol-gel synthesis and densification of aluminoborosilicate powders. Part 2: Densification

Aluminoborosilicate (ABS) powders, high in alumina content, were synthesized by the sol-gel process utilizing four different methods of synthesis. The effect of these methods on the densification behavior of ABS powder compacts was studied. Five regions of shrinkage in the temperature range 25-1184 C were identified. In these regions, the greatest shrinkage occurred between the gel-to-glass transition temperature (T sub g approximately equal to 835 C) and the crystallization transformation temperature (T sub t approximately equal 900 C). The dominant mechanism of densification in this range was found to be viscous sintering. ABS powders were amorphous to x-rays up to T sub t at which a multiphasic structure crystallized. No 2Al2O3.B2O3 was found in these powders as predicted in the phase diagram. Above T sub t, densification was the result of competing mechanisms including grain growth and boria fluxed viscous sintering. Apparent activation energies for densification in each region varied according to the method of synthesis.

Bull, Jeffrey↗

Dynamic mechanical analysis of polymeric materials

Polymeric materials exhibit mechanical behavior which is dependent on temperature. Dynamic mechanical analysis measures the mechanical damping and resonant frequency of a material over a temperature range. Values of the dynamic loss modulus, storage modulus, and loss tangent can be calculated from these data. The glass transition temperature and onset temperature are obtained from curves of the dynamic moduli versus temperature.

Kern, Kristen T.↗

Thermal Contributions to the Degradation of Ground Laboratory and Space Irradiated Teflon

The aluminized Teflon fluorinated ethylene propylene outer most layer of the multilayer insulation blankets on the Hubble Space Telescope has become embrittled resulting in severe on-orbit cracking. During the second servicing mission, a piece of aluminized fluorinated ethylene propylene was retrieved that had curled, exposing the back-surface aluminum to space. This extremely embrittled piece reached 200 C on-orbit, 150 C higher than the nominal temperature extreme. Therefore, experiments have been conducted to determine the effect of heating on the degradation of fluorinated ethylene propylene that has been irradiated in a ground laboratory facility or in space on Hubble Space Telescope. Samples of pristine, x-ray irradiated and Hubble Space Telescope retrieved fluorinated ethylene propylene were heat treated from 50 to 200 C at 25 C intervals in a high vacuum facility and tensile tested. Density measurements were also obtained. Results indicate that heating does not embrittle non-irradiated Teflon. However, there is a significant dependence of the embrittlement of irradiated Teflon on heating temperature, with near complete loss of elongation at 100 C and higher. Rate of degradation changes, which were consistent with the glass transition temperature for fluorinated ethylene propylene, were present in the data. The results support chain scission as the primary mechanism of degradation of fluorinated ethylene propylene on Hubble Space Telescope, and indicate the significance of the on-orbit temperature of fluorinated ethylene propylene with respect to its degradation in the space environment.

deGroh, Kim K.↗

High Temperature Transfer Molding Resins: Preliminary Composite Properties of PETI-375

As part of an ongoing effort to develop materials for resin transfer molding (RTM) of high performance/high temperature composites, a new phenylethynyl containing imide designated as PETI-375 has been under evaluation. PETI-375 was prepared using 2,3,3 ,4 - biphenyltetracarboxylic dianhydride (a-BPDA), 1,3-bis(4-aminophenoxy)benzene and 2,2 - bis(trifluoromethyl)benzidine and endcapped with 4-phenylethynylphthalic anhydride. This material exhibited a stable melt viscosity of 0.1-0.4 Pa sec at 280 C. High quality, void-free laminates were fabricated by high temperature RTM using unsized T-650 carbon fabric and evaluated. After curing for 1 hour at 371 C, the laminates exhibited a glass transition temperature of approx. 375 C by thermomechanical analysis. The laminates were essentially void and microcrack free as evidenced by optical microscopic examination. The chemistry, physical, and composite properties of PETI-375 will be discussed.

Connell, J. W.↗

Dynamic Mechanical Analysis of Post-Cured Bismaleimide Resins for Composite-Overwrapped Combustion Chambers Cycled From Cryogenic to High Temperatures

In support of the Rapid Analysis and Manufacturing Propulsion Technology (RAMPT) project, samples made of polybismaleimide (BMI) resin were made and tested under cryogenic conditions. Neat resin samples were tested for multiple cycles, from high temperature (300°C) to cryogenic temperature (-150°C), to replicate the conditions a rocket engine assembly would experience in a test campaign and in operation. To increase the glass transition temperature (and thus mechanical stability), samples were exposed to different post-cure temperatures and were tested using a dynamic mechanical analysis (DMA) instrument. Consistent with expectations, the BMI samples post-cured at higher temperatures generally resulted in higher storage modulus under high temperature test conditions but at the expense of storage modulus values at low temperature test conditions.

Christopher Stelter↗

Bulk Formation of Metallic Glasses and Amorphous Silicon from the Melt

By using metallic glass compositions with a high relative glass transition temperature, such as Pd40Ni40P20, homogeneous nucleation also becomes negligible. Large (5g) masses of this alloys were obtained using a molten B2O3 flux. Presently, bulk glass formation in iron based glasses is being investigated. It is expected that if an undercooling of about 250K can be achieved in a Ge or Si melt, formation of the amorphous semiconductor phase (rather than the crystal) may be kinetically favored. The volumetric behavior of undercooled liquid Ga droplet dispersion is investigated by dilatometry. A theoretical model (both analytical and numerical) was developed for transient nucleation in glass forming melts. The model, originally designed for isothermal conditions, was extended to continuous quenching. It is being applied to glass formation in various metallic and oxide systems. A further refinement will be the inclusion of diffusion controlled interfacial rearrangements governing the growth of the crystal embryos.

Spaepen, F.↗

Characterization of Adhesives for Attaching Reusable Surface Insulation on Space Shuttle Vehicles

An extensive development and testing program on adhesive systems shows that: (1) A closed cell silicone rubber sponge bonded to substrates with thin bond lines of glass filled adhesive exhibits density and modulus values approximately one third that of solid silicone adhesives; (2) utilization of glass or phenolic microballoons as fillers in silicone adhesives reduces density but increases moduli of the vulcanized materials; (3) the silicone elastomer based adhesives appear to be complex systems rather than homogeneous, isotropic materials. Tensile, shear, and compression properties plotted versus temperature verify this conjecture; and (4) constant strain-stress relaxation tests on glass-filled adhesive show that stress relaxation is most pronounced near the glass transition temperature.

Owen, H. P.↗

Effects of orbital exposure on RTV during the LDEF mission

Thermomechanical analysis (TMA), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA) were performed on samples of RTV 511 exposed on the Long Duration Exposure Facility (LDEF) mission for 6 years in orbit and unexposed RTV 511 control samples. Slices 20- to 400-microns thick were removed from the exposed surface down to a depth of 1,500 microns through the 3-mm thick samples. The TMA and DSC results, which arise from the entire slice and not just its surface, showed no significant differences between the LDEF exposed and the control samples. TMA scans were run from ambient to 500 C; results were compared by a tabulation of the onset temperatures for flow. DSC scans were run from ambient to 600 C; no endotherms or exotherms occurred over the range observed. What appear to be glass transition temperatures were compared for the samples as a function of section depth within the sample and between the exposed and control samples. The TGA scans from 25 to 900 C, which arise from the surface of the sample initially, showed a slight increase in the top most 105-micron slice (the exposed, discolored side) in the weight loss at 600 C in oxygen. This weight loss dropped to bulk values at the next slice below the top section, a mean depth of 258 microns. The control sample also showed an increase in weight loss as the top surface was approached, but the 600 C weight losses were very inconsistent. The LDEF RTV sample appears to be mechanically undamaged, with a surface layer which oxidizes slightly faster as a result of orbital exposure.

Brower, William E., Jr.↗

Effects of Aging-Time Reference on the Long Term Behavior of the IM7/K3B Composite

An analytical study was undertaken to investigate the effects of the time-based shift reference on the long term behavior of the graphite reinforced thermoplastic polyimide composite IM7/K3B at elevated temperature. Creep compliance and the effects of physical aging on the time dependent response was measured for uniaxial loading at several isothermal conditions below the glass transition temperature (T(sub g). Two matrix dominated loading modes, shear and transverse, were investigated in tension and compression. The momentary sequenced creep/aging curves were collapsed through a horizontal (time) shift using the shortest, middle and longest aging time curve as the reference curve. Linear viscoelasticity was used to characterize the creep/recovery behavior and superposition techniques were used to establish the physical aging related material constants. The use of effective time expressions in a laminated plate model allowed for the prediction of long term creep compliance. The effect of using different reference curves with time/aging-time superposition was most sensitive to the physical aging shift rate at lower test temperatures. Depending on the loading mode, the reference curve used can result in a more accurate long term prediction, especially at lower test temperatures.

Veazie, David R.↗

A thermally modified polymer matrix composite material with structural integrity to 371 C

The potential for utilizing surface coatings to inhibit the thermal oxidation of polymer matrix composites was studied. Isothermal, inert gas exposures of graphite/PMR-15 composites indicated that after an initial loss of weight, no significant amounts of thermal degradation products are given off during high temperature exposures in the absence of oxygen. As long as a coating remains effective, the composite material should remain stable. It was also found that the glass transition temperature T sub g of the matrix resin could be increased to values in excess of 400 C. This resulted in measured short beam shear strengths of 75.9 MPa (11 Ksi), flexural strengths of 1172 MPa (170 Ksi) and flexural moduli of 141 GPa (20.5 Msi) for the material at a test temperature of 371 C. The treatment that was used caused a decrease in the PMR-15 resin density from 1.31 to 1.29 gm/cc. It was concluded that state-of-the-art composites, protected by oxygen-impervious coatings, can be used as materials of construction with structural integrity to at least 371 C and possibly above.

Bowles, Kenneth J.↗

A thermally modified polymer matrix composite material with structural integrity to 371 C

The potential for utilizing surface coatings to inhibit the thermal oxidation of polymer matrix composites was studied. Isothermal, inert gas exposures of graphite/PMR-15 composites indicated that after an initial loss of weight, no significant amounts of thermal degradation products are given off during high temperature exposures in the absence of oxygen. As long as a coating remains effective, the composite material should remain stable. It was also found that the glass transition temperature T sub g of the matrix resin could be increased to values in excess of 400 C. This resulted in measured short beam shear strengths of 75.9 MPa (11 Ksi), flexural strengths of 1172 MPa (170 Ksi) and flexural moduli of 141 GPa (20.5 Msi) for the material at a test temperature of 371 C. The treatment that was used caused a decrease in the PMR-15 resin density from 1.31 to 1.29 gm/cc. It was concluded that state-of-the-art composites, protected by oxygen-impervious coatings, can be used as materials of construction with structural integrity to at least 371 C and possibly above.

Bowles, Kenneth J.↗