Development of DMBZ-15 High-Glass-Transition-Temperature Polyimides as PMR-15 Replacements Given R&D 100 Award

PMR-15, a high-temperature polyimide developed in the mid-1970s at the NASA Lewis Research Center,1 offers the combination of low cost, easy processing, and good high-temperature performance and stability. It has been recognized as the leading polymer matrix resin for carbon-fiber-reinforced composites used in aircraft engine components. The state-of-the-art PMR-15 polyimide composite has a glass-transition temperature (Tg) of 348 C (658 F). Since composite materials must be used at temperatures well below their glass-transition temperature, the long-term use temperatures of PMR-15 composites can be no higher than 288 C (550 F). In addition, PMR-15 is made from methylene dianiline (MDA), a known liver toxin. Concerns about the safety of workers exposed to MDA during the fabrication of PMR-15 components and about the environmental impact of PMR-15 waste disposal have led to the industry-wide implementation of special handling procedures to minimize the health risks associated with this material. These procedures have increased manufacturing and maintenance costs significantly and have limited the use of PMR-15 in commercial aircraft engine components

Low-Cost, High Glass-Transition Temperature, Thermosetting Polyimide Developed

PMR-15 polyimide, developed in the mid-1970's at the NASA Lewis Research Center, is recognized as a state-of-the-art high-temperature resin for composite applications in the temperature range of 500 to 550 F (260 to 288 C). PMR-15 offers easy processing and good property retention at a reasonable cost. For these reasons, it is widely used in both military and commercial aircraft engine components. Traditionally, polyimide composites have been designed for long-term use at 500 to 600 F over thousands of hours. However, new applications in reusable launch vehicles (RLV's) require lightweight materials that can perform for short times (tens of hours) at temperatures between 800 and 1000 F (425 and 538 C). Current efforts at Lewis are focused on raising the use temperature of polyimide composites by increasing the glass-transition temperature of the matrix resins. Achieving this dramatic increase in the upper use temperature without sacrificing polymer and composite processability is a major technical challenge

Effects of a noncoplanar biphenyldiamine on the processing and properties of addition polyimides

Addition curing polyimides, prepared from noncoplanar 2,2'-bis(trifluoromethyl) 4,4' diaminobiphenyl (BTDB) with various dianhydrides were evaluated as high temperature polymer matrix materials. T sub g of these polymers were measured by mechanical methods as well as by thermal mechanical analysis. Physical and mechanical properties as well as the thermo-oxidative stability of neat resins and the corresponding G40-600 graphite fiber reinforced composites were compared to that of PMR-II-50 and V-CAP-75

Polyimides Based on Asymmetric Dianhydrides (II) (a-BPDA vs a-BTDA) for Resin Transfer Molding (RTM)

A new series of low-melt viscosity imide resins (10-20 poise at 280 C) were formulated from asymmetric 2,3,3',4' -benzophenone dianhydride (a-BTDA) and 4-phenylethynylphthalic endcaps, along with 3,4' -oxydianiline, 3,3' -methylenedianiline and 3,3'- diaminobenzophenone, using a solvent-free melt process. a-BTDA RTM resins exhibited higher glass transition temperatures (Tg's = 330-400 C) compared to those prepared by asymmetric 2,3,3',4' -biphenyl dianhydride, (a-BPDA, Tg's = 320-370 C). These low-melt viscosity imide resins were fabricated into polyimide/T650-35 carbon fiber composites by a RTM process. Composites properties of a-BTDA resins, such as open-hole compression and short-beam shear strength, are compared to those of composites made from a-BPDA based resin at room temperature, 288 C and 315 C. These novel, high temperature RTM imide resins exhibit outstanding properties beyond the performance of conventional RTM resins, such as epoxy and BMI resins which have use-temperatures around 177 C and 232 C for aerospace applications

Polyimide Composites Based on Asymmetric Dianhydrides (a-ODPA vs a-BPDA)

RTM Resins based on a-ODPA and a-BPDA with kinked diamines exhibit low-melt viscosity (approximately 10 poise). Composites made from a-ODPA resins (T(sub g) = 265-330 C) by RTM display good mechanical properties at 288 C (550 F), but soften at 315 C (600 F). Composites of RTM370 based on a-BPDA retain excellent mechanical properties at 315 C, exceeding BMI-5270-1 capability

High-Glass-Transition-Temperature Polyimides Developed for Reusable Launch Vehicle Applications

Polyimide composites have been traditionally used for high-temperature applications in aircraft engines at temperatures up to 550 F (288 C) for thousands of hours. However, as NASA shifts its focus toward the development of advanced reusable launch vehicles, there is an urgent need for lightweight polymer composites that can sustain 600 to 800 F (315 to 427 C) for short excursions (hundreds of hours). To meet critical vehicle weight targets, it is essential that one use lightweight, high-temperature polymer matrix composites in propulsion components such as turbopump housings, ducts, engine supports, and struts. Composite materials in reusable launch vehicle components will heat quickly during launch and reentry. Conventional composites, consisting of layers of fabric or fiber-reinforced lamina, would either blister or encounter catastrophic delamination under high heating rates above 300 C. This blistering and delamination are the result of a sudden volume expansion within the composite due to the release of absorbed moisture and gases generated by the degradation of the polymer matrix. Researchers at the NASA Glenn Research Center and the Boeing Company (Long Beach, CA) recently demonstrated a successful approach for preventing this delamination--the use of three-dimensional stitched composites fabricated by resin infusion

Composite Properties of RTM370 Polyimide Fabricated by Vacuum Assisted Resin Transfer Molding (VARTM)

RTM370 imide resin based on 2,3,3?,4?-biphenyl dianhydride (a-BPDA), 3,4'-oxydianinline (3,4'-ODA) with the 4-phenylethynylphthalic (PEPA) endcap has been shown to exhibit a high cured T(sub g) (370 C) and low melt viscosity (10-30 poise) at 280 C with a pot-life of 1-2 h. Previously, RTM370 resin has been successfully fabricated into composites reinforced with T650-35 carbon fabrics by resin transfer molding (RTM). RTM370 composites exhibit excellent mechanical properties up to 327?C (620?F), and outstanding property retention after aging at 288?C (550?F) for 1000 h. In this work, RTM370 composites were fabricated by vacuum assisted resin transfer molding (VARTM), using vacuum bags on a steel plate. The mechanical properties of RTM370 composites fabricated by VARTM are compared to those prepared by RTM

Polyimide Composites Properties of RTM370 Fabricated by Vacuum Assisted Resins Transfer Molding (VARTM)

RTM370 imide resin based on 2,3,3 ,4 -biphenyl dianhydride ( a-BPDA), 3,4 -oxydianinline (3,4 -ODA) with 4-phenylethynylphthalic (PEPA) endcap has shown to exhibit high Tg (370 C) and low melt viscosity (10-30 poise) at 280 C with a pot-life of 1-2 h. Previously, RTM370 resin has been fabricated into composites with T650-35 carbon fabrics by resin transfer molding (RTM) successfully. RTM370 composites exhibit excellent mechanical properties up to 327 C (620 F), and outstanding property retention after aging at 288 C (550 F) for 1000 hrs. In this presentation, RTM 370 composites will be fabricated by vacuum assisted resins transfer molding (VARTM), using vacuum bags without mold. The mechanical properties of RTM370 composites fabricated by VARTM will be compared to those of RTM370 made by RTM

RTM370 Polyimide Braided Composites: Characterization and Impact Testing

RTM370 imide oligomer based on 2,3,3',4'-biphenyl dianhydride (a-BPDA), 3,4'-oxydianiline (3,4'-ODA) and terminated with the 4-phenylethynylphthalic (PEPA) endcap has been shown to exhibit a low melt viscosity (10-30 poise) at 280 C with a pot-life of 1-2 h and a high cured glass transition temperature (Tg) of 370 C. RTM370 resin has been successfully fabricated into composites reinforced with T650-35 carbon fabrics by resin transfer molding (RTM). RTM370 composites display excellent mechanical properties up to 327 C (620 F), and outstanding property retention after aging at 288degC (550 F) for 1000 h, and under hot-wet conditions. In ballistic impact testing, RTM370 triaxial braided T650-35 carbon fiber composites exhibited enhanced energy absorption at 288 C (550 F) compared to ambient temperature

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