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Two thermoplastic polyimides - one amorphous, the other crystallizable -- were subjected to isothermal stretching just above their glass transition temperatures. Room-temperature strengths in the stretch direction were greatly improved and, moduli increased up to 3.6-fold. Optimum stretching conditions were determined.
A high T(sub g) thermosetting PMR-type polyimide, designated as DMBZ-15, was developed by replacing methylene dianline (MDA) in PMR-15 with 2,2'-dimethylbenzidine. Polyimide/carbon fiber (T650-35) composites were fabricated from a formulation of 3,3', 4,4'-benzophenonetetracarboxylic acid dimethyl ester (BTDE) and 2,2'-dimethylbenzidine (DMBZ), along with nadic ester (NE) as the endcap. DMBZ-15 displays a higher glass transition temperature (T(sub g) = 414 C) than PMR-15 (T(sub g) = 345 C), and thus retains better mechanical properties for brief exposure above 400 C. The physical properties and longterm thermo-oxidative stability of the DMBZ-15 polyimide/carbon fiber composites are also compared to that of PMR-15.
Mechanical testing of an advanced polyimide resin (LaRC(tm)-SI) with known variations in molecular weight was performed over a range of temperatures below the glass transition temperature. Elastic and inelastic properties were characterized as a function of molecular weight and test temperature. It was shown that notched tensile strength is a strong function of both temperature and molecular weight, whereas stiffness is only a strong function of temperature. The combined analysis of calculated yield stress and notched tensile strength indicated that low molecular weight materials tended to fail in a brittle manner, whereas high molecular weight materials exhibited ductile failure. The microphotographs of the failure surfaces also supported these findings.
The effect of molecular weight on the viscoelastic performance of an advanced polymer (LaRC-SI) was investigated through the use of creep compliance tests. Testing consisted of short-term isothermal creep and recovery with the creep segments performed under constant load. The tests were conducted at three temperatures below the glass transition temperature of five materials of different molecular weight. Through the use of time-aging-time superposition procedures, the material constants, material master curves and aging-related parameters were evaluated at each temperature for a given molecular weight. The time-temperature superposition technique helped to describe the effect of temperature on the timescale of the viscoelastic response of each molecular weight. It was shown that the low molecular weight materials have higher creep compliance and creep rate, and are more sensitive to temperature than the high molecular weight materials. Furthermore, a critical molecular weight transition was observed to occur at a weight-average molecular weight of M (bar) (sub w) 25000 g/mol below which, the temperature sensitivity of the time-temperature superposition shift factor increases rapidly. The short-term creep compliance data were used in association with Struik's effective time theory to predict the long-term creep compliance behavior for the different molecular weights. At long timescales, physical aging serves to significantly decrease the creep compliance and creep rate of all the materials tested.
The primary objective of this work was to prepare readily melt and solution processable phenylquinoxaline (PQ) oligomers that could be thermally crosslinked to solvent-resistant resins. Thus, a mixture of 2-(4-hydroxyphenyl)-3-phenyl-6-fluoroquinoxaline and 3-(4-hydroxyphenyl)-2-phenyl-6-fluoroquinoxaline (HPFQ) was used to prepare star-branched PQ oligomers end-capped with 4-fluoro-4-phenylethynylbenzophenone (FPEB). 1,1,1-Tris(4-hydroxyphenyl)ethane (THPE) was used as the branching unit. The oligomer number-average molecular weights (M (bar) (sub n) S) as determined by size exclusion chromatography (SEC) were close to the calculated values of 2922, 4698, 6474, and 13,578 g/mol, and their intrinsic viscosities ranged from 0.16 to 0.57 dl/g (m-cresol at 30 C). The oligomers, which were quite soluble in common organic solvents, had glass transition temperatures (T (sub g) S) that ranged from 181 to 233 C (DSC, DELTA T = 20 C/min). They also underwent an exothermic cure with maxima from 377 to 443 C. The T (sub g) S of the cured oligomers ranged from 259 to 284 C depending on the oligomer M (bar) (sub n) and the curing conditions. The oligomers had low melt viscosities, e.g. an oligomer (SPQ-46) with an M (bar) (sub n) of 4816 g/mol (SEC) had a melt viscosity of 150 Pa s at 348 C. A cured thin film of SPQ-46, which was insoluble in common organic solvents, had a room temperature (RT) tensile strength of 100 MPa, a RT modulus of 2358 MPa, and a RT elongation of 5.9%. A cured sample of SPQ-46 displayed a RT titanium-titanium lap shear tensile strength of 35.2 MPa. SPQ-46/carbon fiber(IM-7) composites, were prepared that displayed a RT flexural strength of 1902 MPa, a RT modulus of 1.38 GPa and a RT open hole compressive strength of 433 MPa.
Otto Fuel II contains a nitrate ester, plasticizer, and 2-NPDA as a stabilizer. Otto Fuel with stabilizers from three vendors was investigated by dynamic and isothermal differential scanning calorimetry (DSC) using samples sealed in a glass ampoule and by Isothermal Microcalorimetry (IMC) using 10 gram samples aged at 75 C for 35 days. DSC kinetics did not show differences between the stabilizer; the samples had an activation energy of 36.7 +/- 0.6 kcal/mol. However, IMC analysis was sensitive enough to detect small differences between the stabilizer, namely energy of interaction values of 7 to 14 Joules. DSC controlled cooling and heating at 5 C/min from 30 to -60 to 40 C experiments were similar and showed a crystallization peak at -48 +/- 1 C during cooling, and upon heating there was a glass transition temperature step at approx. -54 +/- 0.5 C and a melting peak at -28 +/- 0.4 C.
This paper discusses some of the properties of Viton that are relevant to its use as a pyrotechnic binder in a NASA standard initiator (NSI) propellant. Nearly every aspect of NSI propellant manufacture and use is impacted by the binder system. The effect of Viton's molecular weight on solubility, solution viscosity, glass transition temperature, and strength characteristics as applied to NSI production and performance are reviewed. Emphasis is placed on the Viton fractionation that occurs during the precipitation cycle and its impact on bridgewire functions. Special consideration is given to the production of bridgewire slurry mixtures.
Otto Fuel II contains a nitrate ester, plasticizer, and 2-NDPA as a stabilizer. Otto Fuel with stabilizers from three vendors was investigated by dynamic and isothermal DSC using samples sealed in a glass ampoule and by Isothermal Microcalorimetry (IMC) using 10 gram samples aged at 75 C for 35 days. DSC kinetics did not show differences between the stabilizer; the samples had an activation energy of 36.7 +/- 0.6 kcal/mol. However, IMC analysis was sensitive enough to detect small differences between the stabilizer, namely energy of interaction values of 7 to 14 Joules. DSC controlled cooling and heating at 5 C/min from 30 to -60 to 40 C experiments were similar and showed a crystallization peak at -48 +/- 1 C during cooling, and upon heating there was a glass transition temperature step at approx. -54 +/- 0.5 C and a melting peak at -28 +/- 0.4 C.
A mechanically undensified aromatic polyimide foam is made from an aromatic polyimide precursor solid residuum and has the following combination of properties: a density according to ASTM D-3574A of about 0.5 pounds/cu.ft to about 20 pounds/cu.ft; a compression strength according to ASTM D-3574C of about 1.5 psi to about 1500 psi; and a limiting oxygen index according to ASTM D-2863 of about 35% oxygen to about 75% oxygen at atmospheric pressure. The aromatic polyimide foam has no appreciable solid inorganic contaminants which are residues of inorganic blowing agents. The aromatic polyimide which constitutes the aromatic polyimide foam has a glass transition temperature (Tg) by differential scanning calorimetry of about 235 C to about 400 C; and a thermal stability of 0 to about 1% weight loss at 204 C as determined by thermogravinietric analysis (TGA). The aromatic polyimide foam has utility as foam insulation and as structural foam, for example, for aeronautical, aerospace and maritime applications.
Mechanical testing of the elastic and viscoelastic response of an advanced thermoplastic polyimide (LaRC-SI) with known variations in molecular weight was performed over a range of temperatures below the glass transition temperature. The notched tensile strength was shown to be a strong function of both molecular weight and temperature, whereas stiffness was only a strong function of temperature. A critical molecular weight was observed to occur at a weight average molecular weight of M, approx. 22,000 g/mol below which, the notched tensile strength decreases rapidly. This critical molecular weight transition is temperature-independent. Low, molecular weight materials tended to fail in a brittle manner, whereas high molecular weight materials exhibited ductile failure. Furthermore, low molecular weight materials have increased creep compliance and creep compliance rate, and are more sensitive to temperature than the high molecular weight materials. At long timescales (less than 1100 hours) physical aging serves to significantly decrease the creep compliance and creep rate of all the materials tested. Low molecular weight materials are less influenced by the effects of physical aging.
Durability and long-term performance are among the primary concerns for the use of advanced polymer matrix composites (PMCs) in modern aerospace structural applications. For a PMC subJected to long-term exposure at elevated temperatures. the viscoelastic nature of the polymer matrix will contribute to macroscopic changes in composite stiffness, strength and fatigue life. Over time. changes in the polymer due to physical aging will have profound effects on tile viscoelastic compliance of the material, hence affecting its long-term durability. Thus, the ability to predict material performance using intrinsic properties, such as crosslink density and molecular weight, would greatly enhance the efficiency of design and development of PMCs. The objective of this paper is to discuss and present the results of an experimental study that considers the effects of crosslink density, molecular weight and temperature on the viscoelastic behavior including physical aging of an advanced polymer. Five distinct variations in crosslink density were used to evaluate the differences in mechanical performance of an advanced polyimide. The physical aging behavior was isolated by conducting sequenced, short-term isothermal creep compliance tests in tension. These tests were performed over a range of sub-glass transition temperatures. The material constants, material master curves and physical aging-related parameters were evaluated as a function of temperature crosslink density and molecular weight using time-temperature and time-aging time superposition techniques.
This viewgraph presentation gives an overview of the structure-property relationship in high glass transition temperatures (T(sub g)) thermosetting polyimides. The objectives of this work are to replace MDA in PMR-15 with 2,2-substituted benzidine and to evaluate the thermo-oxidative stability and mechanical properties of DMBZ-15 against PMR-15. Details are given on the T(sub g) of polyimide resins, the x-ray crystal structure of 2,2-Bis(trifluoro)benzidine (BFBZ), the isothermal aging of polyimide resins at 288 C under 1 atm of circulating air, the compressive strength of polyimide composites, and a gas evaluation profile of DMBZ-15 polyimide resins.
The next generation of reusable launch vehicles will require technology development in several key areas. Of these key areas, the development of polymeric composite cryogenic fuel tanks promises to present one of the most difficult technical challenges. It is envisioned that a polymer matrix composite (PMC) tank would be a large shell structure capable of containing cryogenic fuels and carrying a range of structural loads. The criteria that will be imposed on such a design include reduced weight, conformal geometry, and impermeability. It is this last criterion, impermeability, that will provide the focus of this paper. The essence of the impermeability criterion is that the tank remains leak free throughout its design lifetime. To address this criterion, one of the first steps is to conduct a complete durability assessment of the PMC materials. At Langley Research Center, a durability assessment of promising new polyimide-based PMCs is underway. This durability program has focused on designing a set of critical laboratory experiments that will determine fundamental material properties under combined thermal-mechanical loading at cryogenic temperatures. The test program provides measurements of lamina and laminate properties, including strength, stiffness, and fracture toughness. The performance of the PMC materials is monitored as a function of exposure conditions and aging time. Residual properties after exposure are measured at cryogenic temperatures and provide quantitative values of residual strength and stiffness. Primary degradation mechanisms and the associated damage modes are measured with both destructive and nondestructive techniques. In addition to mechanical properties, a range of physical properties, such as weight, glass transition, and crack density, are measured and correlated with the test conditions. This paper will report on the progress of this research program and present critical results and illustrative examples of current findings.
Isothermal weight loss studies at the Glenn (Lewis) Research Center were conducted at four temperatures (204, 260, 288, and 316 C) with specimens of varied geometric shapes to investigate the mechanisms involved in the thermal degradation of PMR-15. Both neat resin behavior and composite behaviors were studied. Two points of interest in these studies are the role(s) of oxygen in the mechanisms involved in the thermo-oxidative degradation of these composite materials and the dimensional changes that occur during their useable lifetime. Specimen dimensional changes and surface layer growth were measured and recorded. It was shown that physical and chemical changes take place as a function of time and location in PMR-15 neat resin and composites as aging takes place in air at elevated temperatures. These changes initiate at the outer surfaces of both materials and progress inward following the oxygen as it proceeds by diffusion into the central core of each material. Microstructural changes cause changes in density, material shrinkage (strains), glass transition temperature, dimension, dynamic shear modulus, and compression properties. These changes also occur slowly dividing the polymer material into two distinct parts: a visibly undamaged core section between two visibly damaged surface layers. The surface layer has a significant effect on compression properties of thinner specimens, but the visibly undamaged core material controls these properties for specimens having eight or more plies. It was demonstrated that there are three different mechanisms involved in the degradation of PMR-15 during aging at elevated temperatures. These are a weight gain, a small weight fraction bulk material weight loss, and a large mass fraction weight loss concentrated at the surface of the polymer or composite. At the higher temperatures (260 C and above), the surface loss predominates. Below 260 C, the surface loss and the bulk core loss become more equivalent. Between 175 and 260 C, the initial weight change is due to a weight gain mechanism with a visible lifetime that diminishes as the aging temperature increases.
Prairie View A&M University using the NASA FAR grant has embarked on several paths to accomplish the initial goals of: (1) synthesizing three ring aromatic diamines to be used as monomers in the synthesis of polyamide resins; and (2) study hydrothermal aging behaviors and glass transition changes of composites synthesized at NASA Glenn Research Center. In establishing the synthesis of the three ring aromatic diamine, it has become necessary to conduct preliminary synthesis to include the nitration of diphenylmethane. The concentration and temperature were altered to assess the effect of purity of isomeric product distribution in such electrophilic aromatic substitution reaction. Products were analyzed using H and C-NMR, Thin Layer Chromatography, High Pressure Liquid Chromatography and GC-Mass Spectrometry (in progress). Results indicate that by varying the concentration of the reaction, a mixture of products can be obtained. Other electrophilic aromatic substitution reactions are also in progress such as Friedel-Craft acylation reaction using diphenylmethane with 4-nitrobenzoyl chloride to afford other diamine products. Furthermore, PVAMU has nearly completed the hydrothermal studies to assess the oxidative stability of DSP443B and DSP442A panels formulated at NASA Glenn Research Center.
In setting forth its strategic plan, NASA has indicated that low-cost access to space is the key to unleashing the commercial potential of space and greatly expanding space research and exploration. The development of advanced materials will be an enabling technology for this quest for low-cost space access. In this research program, we are attempting to address the need for new advanced materials by developing high-performance nanodispersed inorganic/organic and organic/organic polyimide composites utilizing specific interactions. Our goal is to systematically manipulate these interactions and investigate the resulting processing morphology-property relationships. Specifically, we will investigate three main parameters on these relationships. These include (1) the type of polyimide; (2) the structure of the inorganic nanoparticle being used; and (3) manipulation of the interfacial energy. During the first year of this effort, we have demonstrated the successful synthesis of PMR-15/layered silicate nanocomposites. Morphological studies indicate that exfoliated structures were obtained in most instances, with a mixture of exfoliated and intercalated structures being observed also. Significant enhancements of the onset of decomposition were obtained by varying the strength of the interaction between the nanoparticle and the polymer. Varying the amount of a specific nanoparticle also affected the decomposition temperatures. A slight catalytic effect of the nanoparticles on both the imidization and crosslinking reaction has been observed and will be presented. In addition, incorporation of the nanoparticles was found to increase the glass transition temperature and slightly broaden the breadth of this relaxation.
Montmorillonite clay was organically modified by co-exchange of an aromatic diamine and a primary alkyl amine. The clay was dispersed into a PMR (Polymerization of Monomer Reactants)-15 matrix and the glass transition temperature and thermal oxidative stability of the resulting nanocomposites were evaluated. PMR-15/ silicate nanocomposites were also investigated as a matrix material for carbon fabric reinforced composites. Dispersion of the organically modified silicate into the PMR-15 matrix enhanced the thermal oxidative stability, the flexural strength, flexural modulus, and interlaminar shear strength of the polymer matrix composite.
Studies were conducted to find an acceptable non-mutagenic diamine to replace 4,4'-methylenedianiline (MDA), a suspect carcinogen, which is currently being used in PMR-15 polyimide applications. Several diamines containing fluorine and trifluoromethyl substituent groups were synthesized. The diamines were polymerized with the dimethyl ester of 3,3',4,4'-benzophenone tetracarboxylic acid (BTDE), using the monomethyl ester of nadic acid (NE) as an endcap. The effect of diamine structure on rheological properties, glass transition temperature, and thermo-oxidative stability was investigated. Unidirectional laminates were fabricated from selected resins, using carbon fiber as the reinforcement. The results indicate that some of the diamines containing trifluoromethyl groups are non-mutagenic, and have potential to replace MDA in PMR polyimides for long-term applications at temperatures up to 300 C.