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At least 19 records

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NASA NTRS1988

Flexible backbone aromatic polyimide adhesives

Continuing research at Langley Research Center on the synthesis and development of new inexpensive flexible aromatic polyimides as adhesives has resulted in a material identified as LARC-F-SO2 with similarities to polyimidesulfone, PISO2, and other flexible backbone polyimides recently reported by Progar and St. Clair. Also prepared and evaluated was an endcapped version of PISO2. These two polymers were compared with LARC-TPI and LARC-STPI, polyimides research in our laboratory and reported in the literature. The adhesive evaluation, primarily based on lap shear strength (LSS) tests at RT, 177 C and 204 C, involved preparing adhesive tapes, conducting bonding studies and exposing lap shear specimens to 204 C air for up to 1000 hrs and to a 72-hour water boil. The type of adhesive failure as well as the Tg was determined for the fractured specimens. The results indicate that LARC-TPI provides the highest LSSs. LARC-F-SO2, LARC-TPI and LARC-STPI all retain their strengths after thermal exposure for 1000 hrs and PISO2 retains greater than 80 percent of its control strengths. After a 72-hr water boil exposure, most of the four adhesive systems showed reduced strengths for all test temperatures although still retaining a high percentage of their original strength (greater than 60 percent) except for one case. The predominant failure type was cohesive with no significant change in the Tgs.

Progar, Donald J.↗

NASA NTRS1989

Flexible backbone aromatic polyimide adhesives

Progar, Donald J.↗

NASA NTRS1990

LARC-IA: A flexible backbone polyimide

A new linear, aromatic, thermoplastic polyimide, prepared from oxydiphthalic anhydride (ODPA) and 3,4'-oxydianiline (ODA) in diglyme and identified as LARC-IA, was synthesized and evaluated. The monomers are relatively inexpensive and physiologically safe. Molecular weight was controlled by use of a monofunctional anhydride, phthalic anhydride (PA), in order to promote controlled flow and wetting properties. The polymer is considered a safe alternative to commercially available LARC-TPI which is prepared with an expensive diamine of uncertain carcinogenicity. The evaluation was based primarily on the polymer's adhesive properties as determined by thermal and water boil exposure of lap shear specimens. Strengths were determined at room temperature, 177, 204 and 232 C before and after exposure to determine the adhesive system's durability to adverse environments over a period of time. Other properties (FWT, G(1c), film and composite properties) were examined which were determined to be typical of a high temperature polyimide. Results of the study show a favorable comparison to LARC-TPI, a commercially available polyimide.

Progar, Donald J.↗

NASA NTRS1988

Flexibilized copolyimide adhesives

Two copolyimides, LARC-STPI and STPI-LARC-2, with flexible backbones were processed and characterized as adhesives. The processability and adhesive properties were compared to those of a commercially available form of LARC-TPI. Lap shear specimens were fabricated using adhesive tape prepared from each of the three polymers. Lap shear tests were performed at room temperature, 177 C, and 204 C before and after exposure to water-boil and to thermal aging at 204 C for up to 1000 hours. The three adhesive systems possess exceptional lap shear strengths at room temperature and elevated temperatures both before and after thermal exposure. LARC-STPI, because of its high glass transition temperature provided high lap shear strengths up to 260 C. After water-boil, LARC-TPI exhibited the highest lap shear strengths at room temperature and 177 C, whereas the LARC-STPI retained a higher percentage of its original strength when tested at 204 C. These flexible thermoplastic copolyimides show considerable potential as adhesives based on this study and because of the ease of preparation with low cost, commercially available materials.

Progar, Donald J.↗

NASA NTRS2022

Cable Decoupling and Cable-Based Stiffening of Continuum Robots

Cable-driven continuum robots, which are robots with a continuously flexible backbone and no identifiable joints that are actuated by cables, have shown great potential for many applications in unstructured, uncertain environments. However, the standard design for a cable-driven continuum robot segment, which bends a continuous backbone along a circular arc, has many compliant modes of deformation which are uncontrolled, and which may result in buckling or other undesirable behaviors if not ameliorated. In this paper, we detail an approach for using additional cables to selectively stiffen planar cable-driven robots with-out substantial coupling to the actuating cables. A mechanics-based model based on the planar Cosserat equations is used to find the design conditions under which additional cables can be routed without coupling of the cable lengths for small deformations. Simulations show that even for relatively large deformations, coupling remains small. A prototype is evaluated, and it is demonstrated that the compliance of the robot is substantially modified relative to the same robot without stiffening cables. Additional stiffening cables are shown to increase the end-effector output stiffness by a factor of approximately 10 over a typical design with actuating cables.

Tendon/wire mechanism↗

NASA NTRS2020

Flexible Polyimide Aerogels Derived From Use of Neopentyl Spacer in Backbone

Polyimide aerogels have gained much attention in the last decade due to their highly porous structure with low density, low dielectric constant, good mechanical properties and thermal stability. They are desirable for many aerospace and commercial applications including lightweight substrates for antennas for aerospace vehicles, due to the low dielectric constant, approaching one as density decreases. However, with only aromatic diamines in the backbone, the aerogels are flexible only as very thin films, nominally 0.5 mm thick. A more flexible aerogel substrate would allow them to be used as conformal antennas, which would reduce drag and also save space in aerospace vehicles. In this research, we demonstrate that the flexibility can be increased by substituting the aromatic diamines typically used in polyimide aerogels with 1,3-bis(4-aminophenoxy)-2, 2-dimethylpropane (BAPN), which contains a flexible neopentyl spacer group. Using the aliphatic diamine, BAPN, leads to aerogels with a high bend radius even when the aerogels are 2-3 mm thick. Twenty different formulations of polyimide aerogels were synthesized from 3,3’,4,4’-biphenyltetracarboxylic dianhydride (BPDA) and a combination of BAPN and 2,2’-dimethylbenxidine (DMBZ), and cross-linked with 1,3,5-triaminophenoxybenzene (TAB) to understand the effect of polymer concentration, oligomer chain length and concentration of BAPN on the properties of the aerogels. Aerogels made using 50 mol % BAPN with n of 45 and 7 wt % polymer possessed the best combination of properties conducive to use as a flexible substrate for conformal antennas, including low density, good hydrophobicity, low shrinkage with high surface area, a one-inch bend radius in aerogels up to 3 mm thickness, and a dielectric constant of 1.11.

polyimide aerogels↗

NASA NTRSDate not supplied

Increasing Flexibility of Polymers in the Application of Complex Space Craft Heat Shield Geometries

Highly crosslinked polymers, commonly utilized in spacecraft component fabrication, especially for heatshields, have historically encountered challenges due to their inherent brittleness. To overcome this issue, researchers have explored the incorporation of additives into the polymer backbone to enhance flexibility and durability. This study aims to improve the flexibility and durability of highly crosslinked polymers by introducing long-chain aliphatic silicon-based additives with varying molecular weights into the polymer backbone. By increasing the flexibility of these brittle polymers, they can be effectively employed in constructing intricate curvatures for heatshields, eliminating the need for gap fillers. In this study, we investigated six different additives, comparing them to a highly crosslinked high-temperature polymer used as a baseline. Various characterization techniques, including thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), dilatometry, dynamic mechanical analysis (DMA), nuclear magnetic resonance (NMR), and Fourier transform infrared spectroscopy (FTIR), were employed to assess the properties of the materials. The FTIR and NMR results indicated the successful incorporation of the silicon-based additives into the polymer backbone. Furthermore, thermal characterization results demonstrated that certain additives exhibited superior flexibility and lower densities compared to the baseline polymer.

Tane Boghozian↗

NASA NTRS2019

Increased Flexibility in Polyimide Aerogel Substrates for Conformal, Lightweight Antennas

Polyimide aerogels are desirable for many aerospace applications due to their high porosity, low density, low thermal conductivity, and superior mechanical properties. They have also been demonstrated as lightweight substrates for antennas since they possess very low dielectric constants, approaching one as density decreases. Increasing the flexibility of the aerogel would allow them to be used as conformal antennas for use on aerospace vehicles, leading to significant space and weight savings. In this research, we demonstrate that the flexibility can be increased depending on the polyimide oligomer backbone structures. We have substituted up to 75 mol % of the aromatic diamines typically used in polyimide aerogels with 1, 3-bis (4-aminophenoxy)-2, 2-dimethylpropane (BAPN). Twenty different formulations of polyimide aerogels were synthesized from 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) and a combination of BAPN and 2,2'-dimethylbenxidine (DMBZ) and cross-linked with 1, 3, 5 triaminophenoxybenzene (TAB). The polymer concentration, n-value, and molar concentration of BAPN and DMBZ were varied to determine an ideal formulation that has both a high bend radius and low dielectric constant. With only aromatic diamines in the backbone, the aerogels are flexible only as very thin films, nominally 0.5 mm thick. Samples containing at least 25 mol % BAPN have higher flexibility in substrates as thick as 2-3 mm and dielectric constants ranging from 1.11-1.26.

Cashman, Jessica↗

NASA NTRS2021

Effect of Urea Links in the Backbone of Polyimide Aerogels

Flexible, conformal polyimide aerogels with low density, good mechanical properties and high surface areas have attracted much attention for many potential applications such as lightweight antenna substrates, insulating materials for launch vehicles, inflatable structures, aircraft or space suits. Development and improvements to fabrication of polyimide aerogel thin films have been reported over the last decade to meet the needs of many of these applications. However, most starting materials are expensive. In this research, we utilized commercially available, low cost monomers including 4,4’-bis(4-aminophenoxy)propane (BAPP) and 3,3’,4,4’-benzophenone tetracarboxylic dianhydride (BTDA), and 4,4-methylene diphenyl di-isocyanate (MDI) in fabricating polyimide (PI) and polyimide-urea (PIU), which were then cross-linked with 1,3,5-tris(4-aminophenoxy)benzene (TAB). It was found that the addition of MDI into the PI chains not only maintained the flexibility of the aerogel films, but also enhanced the film casting, allowing the production on pilot scale. With the capability in producing robust films at affordable cost, application of the PIU aerogel films can be expanded to terrestrial goods such as winter clothing, or pipe wrapping, etc. In addition, the presence of only a small addition of the urea links in the polyimide chains in PIU aerogels led to lower shrinkage when compared to the corresponding PI aerogels, leading to lower density

Baochau N. Nguyen↗

NASA NTRS1987

Siloxane-modified polyethersulfideimide

BDSDA/APB, a novel linear polyethersulfideimide, was synthesized using siloxane units as flexible linkages in the backbone in an attempt to improve use properties and processability. The effect of these flexible linkages on molecular weight buildup, flexural strength and modulus, glass transition temperature, and melt-flow properties was determined.

Burks, Harold D.↗

NASA NTRS2003

Electrostrictive Graft Elastomers

An electrostrictive graft elastomer has a backbone molecule which is a non-crystallizable, flexible macromolecular chain and a grafted polymer forming polar graft moieties with backbone molecules. The polar graft moieties have been rotated by an applied electric field, e.g., into substantial polar alignment. The rotation is sustained until the electric field is removed. In another embodiment, a process for producing strain in an elastomer includes: (a) providing a graft elastomer having a backbone molecule which is a non-crystallizable, flexible macromolecular chain and a grafted polymer forming polar graft moieties with backbone molecules; and (b) applying an electric field to the graft elastomer to rotate the polar graft moieties, e.g., into substantial polar alignment.

Su, Ji↗

NASA NTRS1999

Modified Phenylethynyl Containing Imides for Secondary Bonding: Non-Autoclave, Low Temperature Processable Adhesives

As part of a program to develop structural adhesives for high performance aerospace applications, research continued on the development of modified phenylethynyl containing imides, LaRC(trademark)MPEIs. In previous reports, the polymer properties were controlled by varying the molecular weight, the amount of branching, and the phenylethynyl content and by blending with low molecular weight materials. This research involves changing the flexibility in the copolyimide backbone of the branched, phenylethynyl terminated adhesives. These adhesives exhibit excellent processability at pressures as low as 15 psi and temperatures as low as 288 C. The Ti/Ti lap shear specimens are processable in an autoclave or a temperature programmable oven under a vacuum bag at 288-300 C without external pressure. The cured polymers exhibit high mechanical properties and excellent solvent resistance. The chemistry and properties of these adhesives are presented.

Dezern, James F.↗

NASA NTRS1999

An Approach to Processable Polyimides

The use of polymer matrix composites (PMC's) in aircraft engines can lead to substantial weight savings over metals. This weight reduction correlates into better fuel economy, increased speed, and increased passenger load. Typically, high performance PMC's possess high thermal-oxidative stabilities (TOS) and high glass transition temperatures (Tg's) to withstand temperatures up to 316 C (600 F). One of the leading high temperature resins system available today is PMR-15 (Polymerization of Monomeric Reactants, MW=1500). This thermosetting polyimide utilizes addition curing through polymer endcaps which enables hand lay-up processing of carbon fiber composite parts with low void contents. However, the large amount of hand labor raises manufacturing costs and prohibits the use of PMR-15 in many aerospace applications. Resin Transfer Molding (RTM) provides an economical alternative, but it requires a melt Viscosity of less than 10(exp 3) centipoise (cP). This is much lower than the minimum melt viscosity of PMR-15 (about 10(exp 6) cP). To improve the processability of polyimides, the polymer backbone can be modified by incorporating flexible linkages, such as branching. bulky pendant groups, kinked structures, and twisted or non-coplanar moietes . The focus of this paper will be the introduction of non-coplanar biaryls into the PMR polyimide backbone to increase processability while maintaining high temperature performance.

Gariepy, Christopher A.↗

NASA NTRS1987

Copolyimides With Flexibilizing Groups

Copolymers improved flexibility, processability and melt-flow characteristics. Copolyimide of new type exhibits synergistic improvements in flow properties due to flexibilized diamine-derived units incorported into polymer backbone. Technique produces copolyimides with combination of flexible linkage that cause polymers to exhibit flow properties particularly well suited for use in wide range of products including adhesives, molding resins, laminating resins, dielectric and protective coatings. Improved properties make copolymers especially useful as thermoplastic hot-melt adhesives.

St. Clair, Terry L.↗

NASA NTRS2008

Di-Isocyanate Crosslinked Aerogels with 1, 6-Bis (Trimethoxysilyl) Hexane Incorporated in Silica Backbone

Silica aerogels are desirable materials for many applications that take advantage of their light weight and low thermal conductivity. Addition of a conformal polymer coating which bonds with the amine decorated surface of the silica network improves the strength of the aerogels by as much as 200 times. Even with vast improvement in strength they still tend to undergo brittle failure due to the rigid silica backbone. We hope to increase the flexibility and elastic recovery of the silica based aerogel by altering the silica back-bone by incorporation of more flexible hexane links. To this end, we investigated the use of 1,6-bis(trimethoxysilyl)hexane (BTMSH), a polysilsesquioxane precursor3, as an additional co-reactant to prepare silica gels which were subsequently cross-linked with di-isocyanate. Previously, this approach of adding flexibility by BTMSH incorporation was demonstrated with styrene cross-linked aerogels. In our study, we varied silane concentration, mol % of silicon from BTMSH and di-isocyanate concentration by weight percent to attempt to optimize both the flexibility and the strength of the aerogels.

Vivod, Stephanie L.↗

NASA NTRS1989

Copolyimide with a combination of flexibilizing groups

Copolyimides are prepared by reacting one or more aromatic dianhydrides with a meta-substituted phenylene diamine and an aromatic bridged diamine. The incorporation of meta-substituted phenylene diamine derived units and bridged aromatice diamine derived units into the linear aromatic polymer backbone results in a copolyimide of improved flexibility, processability, and melt-flow characteristics. The copolyimides are especially useful as thermoplastic hot-melt adhesives.

Stclair, Terry L.↗

NASA NTRS2008

New Materials for the Repair of Polyimide Electrical Wire Insulation

Two viable polyimide backbone materials have been identified that will allow the repair of polyimide electrical wire insulation found on the Space Shuttle and other aging aircraft. This identification is the outcome of ongoing efforts to assess the viability of using such polyimides and polyimide precursors (polyamic acids [PAAs]) as repair materials for aging polyimide electrical wire insulation. These repair materials were selected because they match the chemical makeup of the underlying wire insulation as closely as possible. This similarity allows for maximum compatibility, coupled with the outstanding physical properties of polyimides. The two polyimide backbone materials allow the polymer to be extremely flexible and to melt at low temperatures. A polymer chain end capping group that allows the polymer to crosslink into a nonflowable repair upon curing at around 200 C was also identified.

Source record↗

NASA NTRS2017

Flexible Proteins at the Origin of Life

Almost all modern proteins possess well-defined, relatively rigid scaffolds that provide structural preorganization for desired functions. Such scaffolds require the sufficient length of a polypeptide chain and extensive evolutionary optimization. How ancestral proteins attained functionality, even though they were most likely markedly smaller than their contemporary descendants, remains a major, unresolved question in the origin of life. On the basis of evidence from experiments and computer simulations, we argue that at least some of the earliest water-soluble and membrane proteins were markedly more flexible than their modern counterparts. As an example, we consider a small, evolved in vitro ligase, based on a novel architecture that may be the archetype of primordial enzymes. The protein does not contain a hydrophobic core or conventional elements of the secondary structure characteristic of modern water-soluble proteins, but instead is built of a flexible, catalytic loop supported by a small hydrophilic core containing zinc atoms. It appears that disorder in the polypeptide chain imparts robustness to mutations in the protein core. Simple ion channels, likely the earliest membrane protein assemblies, could also be quite flexible, but still retain their functionality, again in contrast to their modern descendants. This is demonstrated in the example of antiamoebin, which can serve as a useful model of small peptides forming ancestral ion channels. Common features of the earliest, functional protein architectures discussed here include not only their flexibility, but also a low level of evolutionary optimization and heterogeneity in amino acid composition and, possibly, the type of peptide bonds in the protein backbone.

Flexible protein↗