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At least 703 records · Page 39

A creep apparatus to explore the quenching and ageing phenomena of PVC films

A creep apparatus has been constructed for an in situ determination of length and length change. Using this apparatus, the creep behavior of PVC thin films associated with quenching and aging was studied. The more severe the quench through the glass transition temperature, the greater is the instantaneous elastic deformation and the subsequent creep behavior. As aging proceeds, the quenched films gradually lose the ductility incurred by quenching. These results agree well with the well-known phenomena of physical aging. Thus, the changes reflecting molecular mobilities due to quenching and aging can be properly monitored by such a creep apparatus.

Lee, H. H. D.↗

Crosslinking-property relationships in PMR polyimide composites. I

The effect of the crosslink density of the matrix on physical and mechanical properties of a graphite-fiber-reinforced PMR (for polymerization of monomer reactants) polyimide composites during isothermal aging was investigated in experiments where unidirectional composite specimens of Celion 6000/PMR-P1 were isothermally exposed at 288 C in air for various time periods up to 5000 hrs. It was found that, as the crosslink density increased, the glass transition temperature, density, and elevated-temperature interlaminar shear strength of a composite increased, while the initial moisture absorption and the coefficient of thermal expansion decreased. However, after reaching the highest possible matrix crosslink density, several of the composite properties began to deteriorate rapidly.

Pater, R. H.↗

Acetylene-chromene terminated resins as high temperature thermosets

A novel phase transfer catalyzed process for the preparation of propargyl ethers has been developed. The propargyl ethers serve as precursors to a new class of thermosetting resins called acetylene-chromene terminated (ACT) resins. Heat treatment of a solution of propargyl ethers with various catalysts, followed by removal of solvent leads to the ACT resins via partial conversion of the propargyl ether groups to chromenes. This process reduces the energy content of the resin systems and reduces the amount of shrinkage found during cure. Due to the presence of the solvent the process is safe and gives rise to low viscosity products suitable for resin transfer molding and filament winding type applications. Due to the high glass transition temperature, high modulus, and low moisture uptake the cured resins display better than 232 C/wet performance. The thermal stability of the ACT resins in air at 204 C is superior to that of conventional bismaleimide resins. The resins also display excellent electrical properties.

Godschalx, J. P.↗

Synthesis and characterization of polyamide-imides

The synthesis and characterization of polyamide-imides (PAI) derived from four different dianhydrides and three isomers of diaminobenzanilide are discussed with emphasis on the effect of combining an amide linkage in the diamine portion with other bridging groups in the dianhydride portion of the polymer backbone. It is noted that all of the amide-imide polymers exhibit high-glass transition temperatures, high thermooxidative stability, and a relatively good solvent resistance. These aromatic PAIs are characterized by high thermal stability due to chain stiffness, crystallinity, and intermolecular hydrogen bonding, and are considered to be good candidates as high-temperature films, coatings, and fibers for aerospace applications.

Dezern, James F.↗

Structure-property study of keto-ether polyimides

As part of an on-going effort to develop an understanding of how changes in the chemical structure affect polymer properties, an empirical study was performed on polyimides containing only ether and/or carbonyl connecting groups in the polymer backbone. During the past two decades the structure-property relationships in linear aromatic polyimides have been extensively investigated. More recently, work has been performed to study the effect of isomeric attachment of keto-ether polyimides on properties such as glass transition temperature and solubility. However, little work has been reported on the relation of polyimide structure to mechanical properties. The purpose of this study was to determine the effect of structural changes in the backbone of keto-ether polyimides on their mechanical properties, specifically, unoriented thin film tensile properties. This study was conducted in two stages. The purpose of the initial stage was to examine the physical and mechanical properties of a representative group (four) of polyimide systems to determine the optimum solvent and cure cycle requirements. These optimum conditions were then utilized in the second stage to prepare films of keto-ether polyimides which were evaluated for mechanical and physical properties. All of the polyimides were prepared using isomers of oxydianiline (ODA) and diaminobenzophenone (DABP) in combination with 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA) and 4,4'-oxydiphthalic anhydride (ODPA).

Dezern, James F.↗

Polyimides with pendent ethynyl groups

Several new polyimides containing pendent ethynyl groups were prepared and characterized. The new polyimides were prepared from the following novel ethynyl containing diamines; 1,1-bis(p aminophenyl)-1-(p ethynylphenyl) 2,2,2-trifluoroethane, and 1,1-bis(p aminophenyl)-1-(p phenylethynylphenyl)-2,2,2 trifluoroethane, and 1,1-bis(p aminophenyl)-1-(p hexynylphenyl)-2,2,2 trifluoroethane by reacting with either 3,3',4,4' benzophenone tetracarboxylic dianhydride or 2,2-bis(3,4 dicarboxyphenyl) hexafluoropropane dianhydride (6FDA). Inherent viscosities for the polymers ranged from 0.26 to 0.94 dL/g. Three copolymers prepared by reacting 10 mole pct. of one of the ethynyl containing diamines and 90 mole pct. of 2,2-bis-(4-(4 aminophenoxy)phenyl) hexafluoropropane with 6FDA were also prepared and characterized. Inherent viscosities for these copolymers ranged from 1.08 to 1.54 dL/g. Original polyimide glass transition temperatures were approx. 265 C while curing at 300 to 350 C for 1 hr in air increased the Tgs by approx. 10 C. Film properties and thermal stability were also measured for these copolyimides.

Jensen, Brian J.↗

High temperature adhesives

The aerospace and electronics industries have an ever increasing need for higher performance materials. In recent years, linear aromatic polyimides have been proven to be a superior class of materials for various applications in these industries. The use of this class of polymers as adhesives is continuing to increase. Several NASA Langley developed polyimides show considerable promise as adhesives because of their high glass transition temperatures, thermal stability, resistance to solvents/water, and their potential for cost effective manufacture.

St.clair, Terry L.↗

Polyimides containing pendent siloxane groups

The incorporation of siloxane units into the backbone of aromatic polyimides has been shown to impart certain advantages over the unmodified polyimides. These include enhanced solubility, lower moisture adsorption, lower dielectric constant, improved toughness and surface modification. Also, when exposed to an atomic oxygen environment these materials form an in-situ silicate (SiO2) surface coating which protects the underlying material from further erosion. These unique advantages make polyimide-siloxanes useful in a variety of electronic and aerospace applications. As part of an effort on high performance polymeric materials for potential aerospace applications, polyimides containing pendent siloxane groups are under study. These materials were prepared by reacting a functionalized siloxane compound with polyimides containing benzhydrol groups. Thin films of the polymers exhibited glass transition temperatures ranging from 167 to 235 C. Tensile strengths and moduli measured at 23 C ranged from 11 to 14 ksi and 250 to 450 ksi, respectively. The dielectric constant was lowered substantially from that of the unmodified polyimide.

Connell, John W.↗

The study of the thermal behavior of a new semicrystalline polyimide

Thermal properties of a new semicrystalline polyimide synthesized from 3,3',4,4' benzophenone tetracarboxylic dianhydride (BTDA) and 2,2 dimethyl 1,2-(4 aminophenoxy) propane (DMDA) were studied. Heat capacities in the solid and liquid states of BTDA-DMDA were measured. The heat capacity increase at the glass transition temperature (T sub g = 230 C) is 145 J/(C mol) for amorphous BTDA-DMDA. The equilibrium heat of fusion of the BTDA-DMDA crystals was obtained using wide angle X ray diffraction and differential scanning calorimetry measurements, and it is 75.8 kJ/mol. Based on the information of crystallinity and the heat capacity increase at T sub g, a rigid amorphous fraction is identified in semicrystalline BTDA-DMDA samples. The rigid amorphous fraction represents an interfacial region between the crystalline and amorphous states. In particular, this fraction increases with the crystallinity of the sample which should be associated with crystal sizes, and therefore, with crystal morphology. It was also found that this polymer has a high temperature crystal phase upon annealing above its original melting temperature. The thermal degradation activation energies are determined to be 154 and 150 kJ/mol in nitrogen and air, respectively.

Cheng, Stephen Z. D.↗

Imide/arylene ether copolymers

Imide/arylene ether block copolymers are prepared by reacting anhydride terminated poly(amic acids) with amine terminated poly(arylene ethers) in polar aprotic solvents and by chemically or thermally cyclodehydrating the resulting intermediate poly(amic acids). The resulting block copolymers have one glass transition temperature or two, depending upon the particular structure and/or the compatibility of the block units. Most of these block copolymers form tough, solvent resistant films with high tensile properties.

Jensen, Brian J.↗

Isothermal aging of IM7/8320 and IM7/5260

Isothermal aging was conducted on two composite systems being considered as possible candidates for the next generation supersonic transport. The composite systems were IM7/5260, a carbon/thermoset, and IM7/8320, a carbon/amorphous thermoplastic. The materials were isothermally aged for a total of 5000 hours at 125 C and 175 C. These temperatures are approximately equivalent to the upper skin temperatures of an aircraft flying at Mach 2.0 and Mach 2.4, respectively. The variations of the following properties were determined as a function of aging time: weight loss, moduli, glass transition temperature, microcracking, and modulus and strength of a +/- 45 laminate. The difficulties and accuracy of strain measurements are also discussed.

Martin, Roderick H.↗

Free-volume characteristics of epoxies

Positron annihilation spectroscopy was used to measure free-volume characteristics of selected epoxies. Fluorene resins, a new family of high-temperature thermosetting resins, were selected as the test medium. Experimental results indicate that the free-volume cell size V sub f varies with the molecular weight between the cross-links M sub c according to an equation of the form V sub f = AM sub c sup B, where A and B are structural constants. In two of the samples, the concentration of bulky fluorene groups was increased in the network backbone by replacement of some of the conventional bisphenol A epoxy resin with fluorene-derived epoxy resin. This resulted in an increase in their glass transition temperature for a given level of cross-linking. It was found that in these samples, the Doppler broadening of the annihilation peak decreases with the increasing fluorene content, presumably due to enhanced damping of the chain motions.

Singh, Jag J.↗

Thermally stable, low dielectric polyquinolines for aerospace and electronics applications

Four new high molecular weight, linear chain polyquinolines have been synthesized and fabricated into high quality free standing films. These polymers are characterized by moderate to high glass transition temperatures, excellent thermal and thermooxidative stability, extremely low dielectric constants and good planarizing characteristics. The polymers absorb very low quantities of moisture. As a consequence, the dielectric constant of one new polyquinoline has been shown to be quite insensitive to exposure to warm/wet conditions. Isothermal aging of one new derivative in air has been carried out at elevated temperatures (250 C to 345 C). The results demonstrate truly outstanding thermooxidative stability. Additional characterizations include molecular weight determinations, solubilities and film-forming characteristics, density measurements, and UV-Vis spectroscopy. The data acquired to date suggest that the polymers may find use as refractive films and coatings and as interlevel planarizers in microelectronics applications.

Hendricks, Neil H.↗

New developments in thermally stable polymers

Advances in high-temperature polymers since 1985 are discussed with the emphasis on the chemistry. High-temperature polymers refer to materials that exhibit glass-transition temperatures greater than 200 C and have the chemical structure expected to provide high thermooxidative stability. Specific polymers or series of polymers were selected to show how the chemical structure influences certain properties. Poly(arylene ethers) and polyimides are the two principal families of polymers discussed. Recent work on poly(arylene ethers) has concentrated on incorporating heterocyclic units within the polymer backbone. Recent polyimide work has centered on the synthesis of new polymers from novel monomers, several containing the trifluoromethyl group strategically located on the molecule. Various members in each of these polymer families display a unique combination of properties, heretofore unattainable. Other families of polymers are also briefly discussed with a polymer from an AB maleimidobenzocyclobutene exhibiting an especially attractive combination of properties.

Hergenrother, Paul M.↗

Polyimides Containing Amide And Perfluoroisopropyl Links

New polyimides synthesized from reactions of aromatic hexafluoroisopropyl dianhydrides with asymmetric amide diamines. Soluble to extent of at least 10 percent by weight at temperature of about 25 degrees C in common amide solvents such as N-methylpyrrolidone, N,N-dimethylacetamide, and N,N-dimethylformamide. Polyimides form tough, flexible films, coatings, and moldings. Glass-transition temperatures ranged from 300 to 365 degrees C, and crystalline melting temperatures observed between 543 and 603 degrees C. Display excellent physical, chemical, and electrical properties. Useful as adhesives, laminating resins, fibers, coatings for electrical and decorative purposes, films, wire enamels, and molding compounds.

Dezem, James F.↗

Freeze-Drying Makes Improved IPN And Semi-IPN Polymers

Novel process developed for production of interpenetrating polymer networks (IPN's) or semi-IPN's with greater fracture toughness and resistance to microcracks. Process controls degree of phase separation in IPN's. In experiment, IPN's and semi-IPN's formed by dissolving constituents in another common solvent in traditional method. Resins and composite materials produced were tested for both traditional and freeze-drying processes. Glass-transition temperatures and data from dynamic mechanical tests of freeze-dried IPN's and semi-IPN's demonstrated freeze-drying process provided much improved IPN's and semi-IPN's.

Pater, Ruth H.↗

Effects of orbital exposure on Halar during the LDEF mission

Thermomechanical Analysis (TMA), Differential Scanning Calorimetry (DSC), and Thermogravimetric Analysis (TGA) were performed on samples of Halar exposed on the LDEF Mission for 6 years in orbit and unexposed Halar control samples. Sections 10-100 microns thick were removed from the exposed surface down to a depth of 1,000 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 differences between the LDEF and the control samples. TMA scans were run from ambient to 300 C; results were compared by a tabulation of the glass transition temperatures. DSC scans were run from ambient to 700 C; the enthalpy of melting was compared for the samples as a function of section depth with the sample. The TGA results, which arise from the surface of the sample initially, showed a sharp increase in the topmost 50 micron section (the exposed, discolored side) in the weight loss of 170 C in oxygen. This weight loss dropped to bulk values in the range of depth of 50-200 microns. The control sample showed only a slight increase in weight loss as the top surface was approached. The LDEF Halar sample appears to be mechanically undamaged, with a surface layer which oxidizes faster as a result of orbital exposure.

Brower, William E., Jr.↗

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↗