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At least 73 records · Page 4

High Flow Addition Curing Polyimides

A new series of high flow PMR-type addition curing polyimides was developed, which employed the substitution of 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl (BTDB) for p-phenylenediamine (p -PDA) in a PMR-IL formulation. These thermoset polyimides, designated as 12F resins, were prepared from BTDB and the dimethyl ester of 4,4'- (hexafluo- roisopropylidene) -diphthalic acid (HFDE) with either nadic ester (NE) or p-aminostyrene (PAS) as the endcaps for addition curing. The 12F prepolymers displayed lower melting temperatures in DSC analysis, and higher melt flow in rheological studies than the cor- responding PMR-11 polyimides. Long-term isothermal aging studies showed that BTDB- based 12F resins exhibited comparable thermo-oxidative stability to P-PDA based PMR-11 polyimides. The noncoplanar 2- and 2'-disubstituted biphenyldiamine (BTDB) not only lowered the melt viscosities of 12F prepolymers, but also retained reasonable thermal sta- bility of the cured resins. The 12F polyimide resin with p-aminostyrene endcaps showed the best promise for long-term, high-temperature application at 343 C (650 F).

Chuang, Kathy C.↗

Aromatic Diamines and Polyimides Based on 4,4'-Bis-(4-Aminophenoxy)-2,2' or 2,2',6,6'- Substituted Biphenyl

This invention relates the novel diamines. the polyimide oligomers and the polyimides derived therefrom and to the method of preparing the diamines, oligomers and the polyimides. The thermoplastic polyimides derived from the aromatic diamines of this invention are characterized as having a high glass transition temperature. good mechanical properties and improved processability in the manufacture of adhesives. electronic and composite materials for use in the automotive and aerospace industry. The distinction of the novel aromatic diamines of this invention is the 2.2',6.6substituted biphenyl radicals which exhibit noncoplanar conformation that enhances the solubility of the diamine as well as the processability of the polyimides. while retaining a relatively high glass transition temperature and improved mechanical properties at useful temperature ranges.

Chuang, Chun-Hua K.↗

Aromatic Diamines and Polyimides Based on 4,4'-Bis-(4-Aminophenoxy)-2,2' or 2,2',6,6'- Substituted Biphenyl

This invention relates the novel diamines, the polyimide oligomers and the polyimides derived therefrom and to the method of preparing the diamines, oligomers and the polyimides. The thermoplastic polyimides derived from the aromatic diamines of this invention are characterized as having a high glass transition temperature, good mechanical properties and improved processability in the manufacture of adhesives, electronic and composite materials for use in the automotive and aerospace industry. The distinction of the novel aromatic diamines of this invention is the 2,2',6,6'-substituted biphenyl radicals which exhibit noncoplanar conformation that enhances the solubility of the diamine as well as the processability of the polyimides, while retaining a relatively high glass transition temperature and improved mechanical properties at useful temperature ranges.

Chun-Hua K Chuang↗

Structure-Property Relationship in High Tg Thermosetting Polyimides

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.

Chuang, Kathy C.↗

Triamine-Modified Polyimides Having Improved Processability and Low Melt Flow Viscosity

Addition-cured polyimides that contain the reaction product of an aromatic triamine or trianhydride analogue thereof, a reactive end group such as 5-norbornene-2, 3-dicarboxylic acid, ester derivatives of 5-norbornene-2, 3-dicarboxylic acid, anhydride derivatives of 5-norbornene-2, 3-dicarboxylic acid, or 4-phenylethynylphthalic anhydride, an aromatic diamine, and a dialkyl ester of an aromatic tetracarboxylic acid. The resultant starlike polyimides; exhibit lower melt flow viscosity than its linear counterparts, providing for improved processability of the polyimide. Also disclosed are methods for the synthesis of these polyimides as well as composite structures formed using these polyimides.

Michael A Meador↗

Surface Evaluation by X-Ray Photoelectron Spectroscopy of High Performance Polyimide Foams After Exposure to Oxygen Plasma

Aromatic polyimides have been attractive in the aerospace and electronics industries for applications such as cryogenic insulation, flame retardant panels and structural subcomponents. Newer to the arena of polyimides is the synthesis of polyimide foams and their applications. In the present work, three different, closely related, polyimide foams developed by NASA Langley Research Center (LaRC) are studied by X-ray Photoelectron Spectroscopy (XPS) after exposure to radio frequency generated Oxygen Plasma. Although polyimide films exposure to atomic oxygen and plasma have been studied previously and reported, the data relate to films and not foams. Foams have much more surface area and thus present new information to be explored. Understanding degradation mechanisms and properties versus structure, foam versus solid is of interest and fundamental to the application and protection of foams exposed to atomic oxygen in Low Earth Orbit (LEO).

Melendez, Orlando↗

Polyimides by Photochemical Cyclopolymerization

The polyimides of this invention are derived from a Diels-Alder cyclopolymerization of a photochemically generated bisdiene with dienophiles, such as bismaleimides, trismaleimides and mixtures thereof with maleimide end-caps. Irradiation of one or more diketones produces two distinct hydroxy o-quinodimethane (photoenol) intermediates. These intermediates are trapped via a Diels-Alder cycloaddition with appropriate dienophiles, e.g., bismaleimide and/or trismaleimides to give the corresponding polyimides in quantitative yields. When bismaleimides, trismaleimides or mixtures thereof with maleimide end-caps are used as the dienophile, the resulting polyimides have glass transition temperatures (Tg) as high as 300 C. Polyimide films can be prepared by ultraviolet irradiation of high solids content varnishes of the monomers in a small amount of solvent, e.g., cyclohexanone, dimethyl formamide, N-methylpyrollidone and the like. These polyimides are characterized as having high glass transition temperatures, good mechanical properties and improved processing in the manufacture of adhesives, electronic materials and films.

Michael A Meador↗

Design Analysis and Thermo-Mechanical Fatigue of a Polyimide Composite for Combustion Chamber Support

Polyimide composites are being evaluated for use in lightweight support structures designed to preserve the ideal flow geometry within thin shell combustion chambers of future space launch propulsion systems. Principles of lightweight design and innovative manufacturing techniques have yielded a sandwich structure with an outer face sheet of carbon fiber polyimide matrix composite. While the continuous carbon fiber enables laminated skin of high specific stiffness; the polyimide matrix materials ensure that the rigidity and durability is maintained at operation temperatures of 316 C. Significant weight savings over all metal support structures are expected. The protypical structure is the result of ongoing collaboration, between Boeing and NASA-GRC seeking to introduce polyimide composites to the harsh environmental and loads familiar to space launch propulsion systems. Design trade analyses were carried out using relevant closed form solutions, approximations for sandwich beams/panels and finite element analysis. Analyses confirm the significant thermal stresses exist when combining materials whose coefficients of thermal expansion (CTEs) differ by a factor of about 10 for materials such as a polymer composite and metallic structures. The ramifications on design and manufacturing alternatives are reviewed and discussed. Due to stringent durability and safety requirements, serious consideration is being given to the synergistic effects of temperature and mechanical loads. The candidate structure operates at 316 C, about 80% of the glass transition temperature T(sub g). Earlier thermomechanical fatigue (TMF) investigations of chopped fiber polyimide composites made this near to T(sub g), showed that cyclic temperature and stress promoted excessive creep damage and strain accumulation. Here it is important to verify that such response is limited in continuous fiber laminates.

Thesken, J. C.↗

DMBZ Polyimides Provide an Alternative to PMR-15 for High-Temperature Applications

PMR-15, a high-temperature polyimide developed in the mid-1970's at the NASA Lewis Research Center, offers the combination of ease of processing, low cost, and good stability and performance at temperatures up to 288 C (500 F). This material is widely regarded as one of the leading high-temperature matrix resins for polymer-matrix-composite aircraft engine components. PMR-15 is widely used in both military and civilian aircraft engines. The current worldwide market for PMR-15 is on the order of 50,000 lb, with a total sales of around $5 to $10 million. However, PMR-15 is made from methylene dianiline (MDA), a known animal mutagen and a suspected human mutagen. Recent concerns about the safety of workers involved in the manufacture and repair of PMR-15 components have led to the implementation of costly protective measures to limit worker exposure and ensure workplace safety. In some cases, because of safety and economic concerns, airlines have eliminated PMR-15 components from engines in their fleets. Current efforts at Lewis are focused on developing suitable replacements for PMR-15 that do not contain mutagenic constituents and have processability, stability, and mechanical properties comparable to that of PMR-15. A recent development from these efforts is a new class of thermosetting polyimides based on 2,2'-dimethylbenzidine (DMBZ). Autoclave processing developed for PMR-15 composites was used to prepare low-void-content T650-35 carbon-fiber-reinforced laminates from DMBZ-15 polyimides. The glass transition temperatures of these laminates were about 50 C higher than those of the T650- 35/PMR-15 composites (400 versus 348 C). In addition, DMBZ-15 polyimide composites aged for 1000 hr in air at 288 C (500 F) had weight losses close to those of comparable PMR-15 laminates (0.9 versus 0.7 percent). The elevated (288 C) and room temperature mechanical properties of T650-35-reinforced DMBZ-15 polyimide and PMR-15 laminates were comparable. Standard Ames tests are being conducted on this diamine to assess its mutagenicity.

Source record↗

Shelf Life of PMR Polyimide Monomer Solutions and Prepregs Extended

PMR (Polymerization of Monomeric Reactants) technology was developed in the mid-1970's at the NASA Glenn Research Center at Lewis Field for fabricating high-temperature stable polyimide composites. This technology allowed a solution of polyimide monomers or prepreg (a fiber, such as glass or graphite, impregnated with PMR polyimide monomers) to be thermally cured without the release of volatiles that cause the formation of voids unlike the non-PMR technology used for polyimide condensation type resins. The initial PMR resin introduced as PMR 15 is still commercially available and is used worldwide by aerospace industries as the state-of-the-art resin for high-temperature polyimide composite applications. PMR 15 offers easy composite processing, excellent composite mechanical property retention, a long lifetime at use temperatures of 500 to 550 F, and relatively low cost. Later, second-generation PMR resin versions, such as PMR II 50 and VCAP 75, offer improvements in the upper-use temperature (to 700 F) and in the useful life at temperature without major compromises in processing and property retention but with significant increases in resin cost. Newer versions of nontoxic (non-methylene dianiline) PMR resins, such as BAX PMR 15, offer similar advantages as originally found for PMR 15 but also with significant increases in resin cost. Thus, the current scope of the entire PMR technology available meets a wide range of aeronautical requirements for polymer composite applications.

Alston, William B.↗

Polyimides by Photochemical Cyclopolymerization

The novel polyimides of this invention are derived from Diels-Alder cyclopolymerization of photochemically generated bisdienes with dienophiles, such as bismaleimides, trismaleimides and mixtures thereof with maleimide endcaps. Irradiation of one or more diketones produces two distinct hydroxy o-quinodimethane (photoenol) intermediates. These intermediates are trapped via Diels-Alder cycloaddition with appropriate dienophiles, e.g., bismaleimide and/or trismaleimides to give the corresponding polyimides in quantitative yields. When bismaleimides, trismaleimides or mixtures thereof with maleimide end-caps are used as the dienophile, the resulting polyimides have glass transition temperatures (Tg) as high as 300 C. Polyimide films can be prepared by ultraviolet irradiation of high solids content varnishes of the monomers in a small amount of solvent, e.g., cyclohexanone, dimethyl formamide, N-methylpyrollidone and the like. These novel polyimides are characterized as having high glass transition temperatures, good mechanical properties and improved processing in the manufacture of adhesives, electronic materials and films.

Meador, Michael A.↗

Low-melt Viscosity Polyimide Resins for Resin Transfer Molding (RTM) II

A series of polyimide resins with low-melt viscosities in the range of 10-30 poise and high glass transition temperatures (Tg s) of 330-370 C were developed for resin transfer molding (RTM) applications. These polyimide resins were formulated from 2,3,3 ,4 -biphenyltetracarboxylic dianhydride (a-BPDA) with 4-phenylethynylphthalic anhydride endcaps along with either 3,4 - oxyaniline (3,4 -ODA), 3,4 -methylenedianiline, (3,4 -MDA) or 3,3 -methylenedianiline (3,3 -MDA). These polyimides had pot lives of 30-60 minutes at 260-280 C, enabling the successful fabrication of T650-35 carbon fiber reinforced composites via RTM process. The viscosity profiles of the polyimide resins and the mechanical properties of the polyimide carbon fiber composites will be discussed.

Chuang, Kathy C.↗

Polyimides based on 4,4'-bis (4-aminophenoxy)-2,2'or 2,2', 6,6'-substituted biphenyl

This invention relates the novel diamines, the polyimide oligomers and the polyimides derived therefrom and to the method of preparing the diamines, oligomers and the polyimides. The thermoplastic polyimides derived from the aromatic diamines of this invention are characterized as having a high glass transition temperature, good mechanical properties and improved processability in the manufacture of adhesives, electronic and composite materials for use in the automotive and aerospace industry. The distinction of the novel aromatic diamines of this invention is the 2,2',6,6'-substituted biphenyl radicals which exhibit noncoplanar conformation that enhances the solubility of the diamine as well as the processability of the polyimides, while retaining a realatively high glass transition temperature and improved mechanical properties at useful temperature ranges.

Chuang, Chun-Hua K.↗

Polyimides by photochemical cyclopolymerization

The novel polyimides of this invention are derived from Diels-Alder cyclopolymerization of photochemically generated bisdienes with dienophiles, such as bismaleimides, trismaleimides and mixtures thereof with maleimide end-caps. Irradiation of one or more diketones produces two distinct hydroxy o-quinodimethane (photoenol) intermediates. These intermediates are trapped via Diels-Alder cycloaddition with appropriate dienophiles, e.g., bismaleimide and/or trismaleimides to give the corresponding polyimides in quantitative yields. When bismaleimides, trismaleimides or mixtures thereof with maleimide end-caps are used as the dienophile, the resulting polyimides have glass transition temperatures (Tg) as high as 300? C. Polyimide films can be prepared by ultraviolet irradiation of high solids content varnishes of the monomers in a small amount of solvent, e.g., cyclohexanone, dimethyl formamide, N-methylpyrollidone and the like. These novel polyimides are characterized as having high glass transition temperatures, good mechanical properties and improved processing in the manufacture of adhesives, electronic materials and films.

Meador, Michael A.↗

Automated Solvent Seaming of Large Polyimide Membranes

A solvent-based welding process enables the joining of precise, cast polyimide membranes at their edges to form larger precise membranes. The process creates a homogeneous, optical-quality seam between abutting membranes, with no overlap and with only a very localized area of figure disturbance. The seam retains 90 percent of the strength of the parent material. The process was developed for original use in the fabrication of wide-aperture membrane optics, with areal densities of less than 1 kg/m2, for lightweight telescopes, solar concentrators, antennas, and the like to be deployed in outer space. The process is just as well applicable to the fabrication of large precise polyimide membranes for flat or inflatable solar concentrators and antenna reflectors for terrestrial applications. The process is applicable to cast membranes made of CP1 (or equivalent) polyimide. The process begins with the precise fitting together and fixturing of two membrane segments. The seam is formed by applying a metered amount of a doped solution of the same polyimide along the abutting edges of the membrane segments. After the solution has been applied, the fixtured films are allowed to dry and are then cured by convective heating. The weld material is the same as the parent material, so that what is formed is a homogeneous, strong joint that is almost indistinguishable from the parent material. The success of the process is highly dependent on formulation of the seaming solution from the correct proportion of the polyimide in a suitable solvent. In addition, the formation of reliable seams depends on the deposition of a precise amount of the seaming solution along the seam line. To ensure the required precision, deposition is performed by use of an automated apparatus comprising a modified commercially available, large-format, ink-jet print head on an automated positioning table. The printing head jets the seaming solution into the seam area at a rate controlled in coordination with the movement of the positioning table.

Rood, Robert↗

Validation of a Polyimide Foam Model for Use in Transmission Loss Applications

The work described in this paper was focused on the use of a new polyimide foam in a double wall sound transmission loss application. Recall that polyimide foams are functionally attractive, compared to polyurethane foams, for example, owing to their fire resistance. The foam considered here was found to have a flow resistivity that was too high for conventional acoustical applications, and as a result, it was processed by partial crushing to lower the flow resistivity into an acceptable range. Procedures for measuring the flow resistivity and Young s modulus of the material have been described, as was an inverse characterization procedure for estimating the remaining Biot parameters based on standing wave tube measurements of transmission loss and absorption coefficient. The inverse characterization was performed using a finite element model implementation of the Biot poro-elastic material theory. Those parameters were then used to predict the sound transmission loss of a double panel system lined with polyimide foam, and the predictions were compared with full-scale transmission loss measurements. The agreement between the two was reasonable, especially in the high and low frequency limits; however, it was found that the SEA model resulted in an under-prediction of the transmission loss in the mid-frequency range. Nonetheless, it was concluded that the performance of polyimide foam could be predicted using conventional poro-elastic material models and that polyimide foam may offer an attractive alternative to other double wall linings in certain situations: e.g., when fire resistance is a key issue. Future work will concentrate on reducing the density of the foam to values similar to those used in current aircraft sidewall treatments, and developing procedures to improve the performance of the foam in transmission loss applications.

Hong, Kwanwoo↗

Reinforced Thermoplastic Polyimide with Dispersed Functionalized Single Wall Carbon Nanotubes

Molecular pi-complexes were formed from pristine HiPCO single-wall carbon nanotubes (SWCNTs) and 1-pyrene- N-(4- N'-(5-norbornene-2,3-dicarboxyimido)phenyl butanamide, 1. Polyimide films were prepared with these complexes as well as uncomplexed SWCNTs and the effects of nanoadditive addition on mechanical, thermal, and electrical properties of these films were evaluated. Although these properties were enhanced by both nanoadditives, larger increases in tensile strength and thermal and electrical conductivities were obtained when the SWCNT/1 complexes were used. At a loading level of 5.5 wt %, the Tg of the polyimide increased from 169 to 197 C and the storage modulus increased 20-fold (from 142 to 3045 MPa). The addition of 3.5 wt % SWCNT/1 complexes increased the tensile strength of the polyimide from 61.4 to 129 MPa; higher loading levels led to embrittlement and lower tensile strengths. The electrical conductivities (DC surface) of the polyimides increased to 1 x 10(exp -4) Scm(exp -1) (SWCNT/1 complexes loading level of 9 wt %). Details of the preparation of these complexes and their effects on polyimide film properties are discussed.

Lebron-Colon, Marisabel↗

Results of All Polyimide, Etched Foil Heater Qualification and Failure Limit Testing

Standard FEP (Fluorinated Ethylene Propylene resin) polyimide (SFP) or Kapton film heaters—which have a long history of space flight—are output-power limited by the melting point of Teflon which is used as an adhesive and insulator between the encasing layers of Kapton. The limit is expressed as a power density or through maximum operating temperature limits. All-polyimide (AP) heaters (also known as adhesive-less heaters) do not contain FEP Teflon between the layers of Kapton so the heaters are unconstrained by the melting point of Teflon. Thus, AP heaters have a higher maximum power density and operating temperature. AP heaters have not been qualified or flown on JPL missions but could be useful in applications that require a higher power density (Watt density) than the SFP heaters can support. The purpose of this paper is to document the qualification and property testing of the AP heaters for flight purposes. JPL (Jet Propulsion Lab.) tested several varieties of all-polyimide heaters to determine their functional equivalence to the standard heater which has substantial flight heritage and to determine their maximum limits. Tests included standard in-air burn-in tests, maximum power testing, lead pull strength, process qualification verification (PQV), long duration thermal cycling, and electro-magnetic compatibility shielding properties for copper-cladded shielded heaters. The results show that the all-polyimide heater appears to be functionally equivalent to the standard heater and has a higher Watt density and maximum operating temperature limit. The tests, test articles, failure analysis of the test articles, and results are described herein. These test results indicate that the all-polyimide heater is ready for flight applications.

Cucullu, Gordon C., III↗