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Development of polymers with improved heat transfer coefficients for use in encapsulating electronic modules is discussed. Chemical reactions for synthesizing the polymers are described and thermodynamic and physical properties are analyzed.
Advance in polymer technology yields composites having relatively low dielectric constants. Reduction achieved by reducing interactions between linear polyimide chains and by incorporation of fluorine into polymer backbones. Further reductions obtained by physically incorporating selected diamic acid additives into polyimides. Strong potential for use in microelectronics industry for fabrication of printed-circuit boards and fabrication of components for military aircraft.
Classical hard spheres have long served as a paradigm for our understanding of the structure of liquids, crystals, and glasses and the transitions between these phases. Ground-based experiments have demonstrated that suspensions of uniform polymer colloids are near-ideal physical realizations of hard spheres. However, gravity appears to play a significant and unexpected role in the formation and structure of these colloidal crystals. In the microgravity environment of the Space Shuttle, crystals grow purely via random stacking of hexagonal close-packed planes, lacking any of the face-centered cubic (FCC) component evident in crystals grown in 1 g beyond melting and allowed some time to settle. Gravity also masks 33-539 the natural growth instabilities of the hard sphere crystals which exhibit striking dendritic arms when grown in microgravity. Finally, high volume fraction "glass" samples which fail to crystallize after more than a year in 1 g begin nucleation after several days and fully crystallize in less than 2 weeks on the Space Shuttle.
Walls from frozen-thawed cucumber (Cucumis sativus L.) hypocotyls extend for many hours when placed in tension under acidic conditions. This study examined whether such "creep" is a purely physical process dependent on wall viscoelasticity alone or whether enzymatic activities are needed to maintain wall extension. Chemical denaturants inhibited wall creep, some acting reversibly and others irreversibly. Brief (15 s) boiling in water irreversibly inhibited creep, as did pre-incubation with proteases. Creep exhibited a high Q10 (3.8) between 20 degrees and 30 degrees C, with slow inactivation at higher temperatures, whereas the viscous flow of pectin solutions exhibited a much lower Q10 (1.35). On the basis of its temperature sensitivity, involvement of pectic gel-sol transitions was judged to be of little importance in creep. Pre-incubation of walls in neutral pH irreversibly inactivated their ability to creep, with a half-time of about 40 min. At 1 mM, Cu2+, Hg2+ and Al3+ were strongly inhibitory whereas most other cations, including Ca2+, had little effect. Sulfhydryl-reducing agents strongly stimulated creep, apparently by stabilizing wall enzyme(s). The physical effects of these treatments on polymer interactions were examined by Instron and stress-relaxation analyses. Some treatments, such as pH and Cu2+, had significant effects on wall viscoelasticity, but others had little or no apparent effect, thus implicating an enzymatic creep mechanism. The results indicate that creep depends on relatively rugged enzymes that are firmly attached to or entangled in the wall. The sensitivity of creep to SH-reducing agents indicates that thiol reduction of wall enzymes might provide a control mechanism for endogenous cell growth.
A process for growing protein crystals encapsulated within membranes has been invented. This process begins with the encapsulation of a nearly saturated aqueous protein solution inside semipermeable membranes to form microcapsules. The encapsulation is effected by use of special formulations of a dissolved protein and a surfactant in an aqueous first liquid phase, which is placed into contact with a second, immiscible liquid phase that contains one or more polymers that are insoluble in the first phase. The second phase becomes formed into the semipermeable membranes that surround microglobules of the first phase, thereby forming the microcapsules. Once formed, the microcapsules are then dehydrated osmotically by exposure to a concentrated salt or polymer solution. The dehydration forms supersaturated solutions inside the microcapsules, thereby enabling nucleation and growth of protein crystals inside the microcapsules. By suitable formulation of the polymer or salt solution and of other physical and chemical parameters, one can control the rate of transport of water out of the microcapsules through the membranes and thereby create physicochemical conditions that favor the growth, within each microcapsule, of one or a few large crystals suitable for analysis by x-ray diffraction. The membrane polymer can be formulated to consist of low-molecular-weight molecules that do not interfere with the x-ray diffraction analysis of the encapsulated crystals. During dehydration, an electrostatic field can be applied to exert additional control over the rate of dehydration. This protein-crystal-encapsulation process is expected to constitute the basis of protein-growth experiments to be performed on the space shuttle and the International Space Station. As envisioned, the experiments would involve the exposure of immiscible liquids to each other in sequences of steps under microgravitational conditions. The experiments are expected to contribute to knowledge of the precise conditions under which protein crystals form. By enhancing the ability to grow crystals suitable for x-ray diffraction analysis, this knowledge can be expected to benefit not only the space program but also medicine and the pharmaceutical industry.
Thermoset and thermoplastic polyimides have complementary physical and mechanical properties. Whereas thermoset polyimides are brittle and generally easier to process, thermoplastic polyimides are tough but harder to process. A combination of these two types of polyimides may help produce polymers more suitable for aerospace applications. Semi-Interpenetrating Polymer Networks (S-IPN) of thermoset LaRC(TM)-RP46 and thermoplastic LaRC(TM)-IA polyimides were prepared in weight percent ratios ranging from 100:0 to 0:100. Positron lifetime measurements were made in these samples to correlate their free volume features with physical and mechanical properties. As expected, positronium atoms are not formed in these samples. The second lifetime component has been used to infer the positron trap dimensions. The 'free volume' goes through a minimum at a ratio of about 50:50, and this suggests that S-IPN samples are not merely solid solutions of the two polymers. These data and related structural properties of the S-IPN samples are discussed.
The development and fabrication of a quantity of long life magnetic tape with properties selected specifically for unattended operation in spacecraft tape recorders was studied. A detailed analytical consideration of various binder systems was undertaken. This included the chemical aspects of the binders, cohesion and adhesion effects, stability and the mechanical and physical properties. The ability to form free films of these polymers and their combination with various oxide loadings and other additives allowed a rapid selection of four polymer candidates for a five year magnetic tape. Samples were evaluated under actual running conditions which included physical, magnetic, and extensive life testing. These sample tapes withstood 50,000 bidirectional tape passes under fairly harsh operating conditions.
Thermal and elastic properties of polymers, and electronic properties of glasses and metals
When amorphous materials are quenched below their glass transition temperature, excess enthalpy is trapped in the glassy material because the viscosity is too great to allow the material to remain in volumetric equilibrium. Over time, this excess free volume is reduced as the material slowly approaches its equilibrium configuration. This process, known as physical aging, leads to substantial changes in the constitutive behavior of polymers, as has been widely discussed in the literature. Less is known about the effects of this physical aging process on fracture and fatigue properties of aged materials. The original goal of the summer was to investigate the effects of physical aging on the fracture and fatigue behavior of LaRC-TPI, a thermoplastic polyimide developed at NASA-Langley. Preliminary results are reported, although a lack of equipment availability prevented completion of this task. In the process of making specimens, the current LaRC-TPI was observed to be extremely susceptible to environmental stress cracking. A study of the unique failure patterns resulting from this degradation process in bonded joints was conducted and is also reported herein.
Polymer solutions, containing clay sheets, were electrospun into nanofibers and microfibers that contained clay sheets inside. Controllable removal of polymer by plasma etching from the surface of fibers revealed the arrangement of clay. The shape, flexibility, size distribution and arrangement of clay sheets were observed by transmission and scanning electron microscopy. The clay sheets were partially aligned in big fibers with normal direction of clay sheets perpendicular to fiber axis. Crumpling of clay sheets inside fibers was observed when the fiber diameter was comparable to the lateral size of clay sheets. Single sheets of clay were observed both by catching clay sheets dispersed in water with electrospun nanofiber mats and by the deliberate removal of most of the polymer in the fibers. Thin, flexible gas barrier films, that are reasonably strong, were assembled from clay sheets and polymer nanofibers. Structure of composite films was characterized with scanning electron microscopy. Continuous film of clay sheets were physically attached to the surface of fiber mats. Spincoating film of polymer and clay sheets was reinforced by electrospun fiber scaffold. Certain alignment of clay sheets was observed in the vicinity of fibers.
The volume examines the scientific interfaces and technological applications of physics. Twelve areas are dealt with: biological physics-biophysics, the brain, and theoretical biology; the physics-chemistry interface-instrumentation, surfaces, neutron and synchrotron radiation, polymers, organic electronic materials; materials science; geophysics-tectonics, the atmosphere and oceans, planets, drilling and seismic exploration, and remote sensing; computational physics-complex systems and applications in basic research; mathematics-field theory and chaos; microelectronics-integrated circuits, miniaturization, future trends; optical information technologies-fiber optics and photonics; instrumentation; physics applications to energy needs and the environment; national security-devices, weapons, and arms control; medical physics-radiology, ultrasonics, MNR, and photonics. An executive summary and many chapters contain recommendations regarding funding, education, industry participation, small-group university research and large facility programs, government agency programs, and computer database needs.
Flame retardant elastomeric compositions comprised of either spandex type polyurethane having halogen containing polyols incorporated into the polymer chain, conventional spandex type polyurethanes in physical admixture with flame retardant additives, or fluoroelastomeric resins in physical admixture with flame retardant additives were developed. Methods are described for preparing fibers of the flame retardant elastomeric materials and manufactured articles as well as nonelastic materials such as polybenzimidazoles, fiberglass, and nylons, for high oxygen environments.
Report compiles data on effects of radiation on physical properties of synthetic organic materials. Emphasis on materials of interest to nuclear-equipment and nuclear-reactor designers. Data covers five categories of polymeric materials: Insulators, elastomeric seals and gaskets, lubricants, adhesives, and coatings. More than 250 materials represented.
The Aerospace Industry is experiencing growing demand for high performance polymer foam. The X-33 program needs structural foam insulation capable of retaining its strength over a wide range of environmental conditions. The High Speed Research Program has a need for low density core splice and potting materials. This paper reviews the state of the art in foam materials and describes experimental work to fabricate low density, high shear strength foam which can withstand temperatures from -220 C to 220 C. Commercially available polymer foams exhibit a wide range of physical properties. Some with densities as low as 0.066 g/cc are capable of co-curing at temperatures as high as 182 C. Rohacell foams can be resin transfer molded at temperatures up to 180 C. They have moduli of elasticity of 0.19 MPa, tensile strengths of 3.7 Mpa and compressive strengths of 3.6 MPa. The Rohacell foams cannot withstand liquid hydrogen temperatures, however Imi-Tech markets Solimide (trademark) foams which withstand temperatures from -250 C to 200 C, but they do not have the required structural integrity. The research activity at NASA Langley Research Center focuses on using chemical blowing agents to produce polyimide thermoplastic foams capable of meeting the above performance requirements. The combination of blowing agents that decompose at the minimum melt viscosity temperature together with plasticizers to lower the viscosity has been used to produce foams by both extrusion and oven heating. The foams produced exhibit good environmental stability while maintaining structural properties.
An alternative to the conventional approach to synthesis of polyimides involves the use of single monomers that are amenable to photopolymerization. Heretofore, the synthesis of polyimides has involved multiple-monomer formulations and heating to temperatures that often exceed 250 C. The present alternative approach enables synthesis under relatively mild conditions that can include room temperature. The main disadvantages of the conventional approach are the following: Elevated production temperatures can lead to high production costs and can impart thermal stresses to the final products. If the proportions of the multiple monomeric ingredients in a given batch are not exactly correct, the molecular weight and other physical properties of the final material could be reduced from their optimum or desired values. To be useful in the alternative approach, a monomer must have a molecular structure tailored to exploit Diels-Alder trapping of a photochemically generated ortho-quinodimethane. (In a Diels-Alder reaction, a diene combines with a dienophile to form molecules that contain six-membered rings.) In particular, a suitable monomer (see figure) contains ortho-methylbenzophenone connected to a dienophile (in this case, a maleimide) through a generic spacer group. Irradiation with ultraviolet light gives rise to a photochemical intermediate the aforementioned ortho-quinodimethane from the ortho-methylbenzophenone. This group may react with the dienophile on another such monomer molecule to produce an oligomer that, in turn may react in a stepgrowth manner to produce a polyimide. This approach offers several advantages in addition to those mentioned above: The monomer can be stored for a long time because it remains unreactive until exposed to light. Because the monomer is the only active starting ingredient, there is no need for mixing, no concern for ensuring correct proportions of monomers, and the purity of the final product material is inherently high. The use of solvents is optional: The synthesis can be performed using the neat monomer or the monomer mixed with one or more solvent(s) in dilute or concentrated solution. The solubility of the monomer and the physical and chemical properties of the final polymer can be tailored through selection of the spacer group.
Described herein are associative polymers capable of controlling one or more physical and/or chemical properties of non-polar compositions and related compositions, methods and systems.