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At least 199 records · Page 11

Adhesive Properties of Cured Phenylethynyl Containing Imides

Considerable attention has been directed towards acetylene terminated oligomers over the last 20 years' and recent work has focused on phenylethynyl terminated imide (PETI) oligomers. These reactive oligomers possess several features which make them attractive candidates for use as composite matrices and adhesives. The phenylethynyl group can be readily incorporated into many different functionalized oligomers. The reactive oligomers possess relatively low melt viscosities and thermally cure without the evolution of volatile by-products. Once cured, they typically display high glass transition temperatures (Tgs), excellent solvent resistance and high mechanical properties. new modified phenylethynyl-terminated imide (LaRC MPEI) oligomers were synthesized at various molecular weights utilizing a small amount of trifunctional amine. As long as the amount of triamine is relatively small, this approach produces a mixture of linear, star-shaped and branched polymer chains that has lower melt and solution viscosity than an equivalent molecular weight linear phenylethynyl terminated imide oligomers. The work reported herein involves the synthesis and characterization of a copolymer using this approach and the preparation of blends utilizing a phenylethynyl containing reactive plasticizer of lower molecular weight called LaRC LV-121. The chemistry and properties of this new MPEI as well as some blends of MPEI with LV-121, are presented and compared to the linear version, LARC-PETI-5.

Jensen, Brian J.↗

Literature Review of Thermomechanical Analysis, Its Instrument Components and Applications

Thermomechanical analysis (TMA) is used to measure the dimensional changes in a sample as a function of temperature. TMA allows for several modes of analysis, with expansion and compression being the most common. TMA is based on the theory of dilatometry and relies on the fact that polymers are viscoelastic materials, possessing both viscous and elastic properties. TMA yields information about the thermal effects on a polymer such as shrinkage, expansion, softening, melting, glass transition temperature and allows for the calculation of the coefficient of thermal expansion (CTE), which can be useful for many applications of polymers.

36 MATERIALS SCIENCE↗

Literature Review of Thermomechanical Analysis, Its Instrument Components and Applications

Thermomechanical analysis (TMA) is used to measure the dimensional changes in a sample as a function of temperature. TMA allows for several modes of analysis, with expansion and compression being the most common. TMA is based on the theory of dilatometry and relies on the fact that polymers are viscoelastic materials, possessing both viscous and elastic properties. TMA yields information about the thermal effects on a polymer such as shrinkage, expansion, softening, melting, glass transition temperature and allows for the calculation of the coefficient of thermal expansion (CTE), which can be useful for many applications of polymers.

36 MATERIALS SCIENCE↗

Thermodynamics and Structure of Poly[n]catenane Melts.

Motivated by recent achievements in the synthesis of interlocking polymers, the structural features of poly[n]catenanes, polymers composed entirely of interlocking rings (or macrocycles), are studied by extensive molecular dynamics simulations in the melt state. The degree of polymerization (number of links) is varied from n = 1 25 and the number of beads per macrocycle is varied from m = 15-50; the results are compared to linear chains of degrees of polymerization N = 15-175. The mechanical bonds in the system cause significant topological contributions to the pressure and potential energy density not seen in other polymer systems. The polymers themselves possess many unusual structural features at short and intermediate length scales, which can be attributed to density inhomogeneities along the polymer contour. Furthermore, the conformations of the individual macrocycles within poly[n]catenanes are quite different from those of ordinary ring polymers and depend on the topology of the macrocycle, that is, whether it is threaded by one ring (chain end) or two (chain center). At larger length scales, the poly[n]catenanes are conformationally similar to ideal linear chains, but unlike traditional (covalent) polymers, they are highly globular at low degrees of polymerization and are extremely flexible relative to their size, which inhibits interchain entanglement. Implications for poly[n]catenane material properties and synthesis are discussed.

Rauscher, Phillip M.↗

Characterization of crystalline LARC-TPI powder

LARC-TPI, a linear aromatic polyimide, developed by NASA Langley Research Center in the late 1970's had thermoplastic character, but its melt-flow properties were much lower than those of conventional thermoplastics. An imidized version of the LARC-TPI molding powder was submitted to NASA-Langley for evaluation. The initial broad melt of this material occurs in the 270 C range and reorders to higher melting forms, depending on the physical and thermal treatments. Rheological characterization of this polymer shows it to have a very low melt viscosity, which increases as the melted specie transforms to other crystalline forms with higher melting temperatures.

Burks, Harold D.↗

Methods of enhancing conductivity of a polymer-ceramic composite electrolyte

Methods for enhancing conductivity of polymer-ceramic composite electrolytes are provided which include forming a polymer-ceramic composite electrolyte film by a melt casting technique and uniaxially stretching the film from about 5 to 15% in length. The polymer-ceramic composite electrolyte is also preferably annealed after stretching such that it has a room temperature conductivity of from 10.sup.-4 S cm.sup.-1 to 10.sup.-3 S cm.sup.-1. The polymer-ceramic composite electrolyte formed by the methods of the present invention may be used in lithium rechargeable batteries.

Kumar, Binod↗

Assessment of relative flammability and thermochemical properties of some thermoplastic materials

The thermochemical and flammability characteristics of some typical thermoplastic materials currently in use and others being considered for use in aircraft interiors are described. The properties studied included (1) thermal mechanical properties such as glass transition and melt temperature, (2) changes in polymer enthalpy by differential scanning calorimetry, (3) thermogravimetric analysis in an anaerobic and oxidative environment, (4) oxygen index, (5) smoke evolution, (6) relative toxicity of the volatile products of pyrolysis, and (7) selected physical properties. The generic polymers which were evaluated included: acrylonitrile-butadiene-styrene, bisphenol A polycarbonate, bisphenol fluorenone carbonatedimethylsiloxane block polymer, phenolphthalein-bisphenol A polycarbonate, phenolphthalein polycarbonate, polyether sulfone, polyphenylene oxide, polyphenylene sulfide, polyaryl sulfone, chlorinated polyvinyl chloride homopolymer, polyvinyl fluoride, and polyvinylidene fluoride. Processing parameters including molding characteristics of some of the advanced polymers are described. Test results and relative rankings of some of the flammability, smoke and toxicity properties are presented.

Kourtides, D. A.↗

Additives Improve Processing Of Polyimides

Melt-processable polyimides maintain desirable polymer properties prepared by adding small amounts of certain low-molecular-weight, thermally stable additives. Useful in preparing void-free polyimide composites from higher flow resins that wet out fibers at lower processing temperatures. Applied to preparing high-temperature polyimide adhesives allowing enhanced wetting of adherends and ultimately better adhesion. Improvement to processing polyimides and potential application for production of films, coatings, adhesives, and composites.

St. Clair, Terry L.↗

Flexible thermoset towpregs by electrostatic powder fusion coating

Thermoset prepregs of expoxy and polyimide have been produced by electrostatic deposition of charged fluidized polymer powders on spread continuous fiber tows. The powders are melted onto the fibers by radiant heating to adhere the polymer to the fiber. This process produces towpreg uniformly and rapidly without imposing severe stresses on the fibers. The towpregs produced by this novel process were consolidated to make unidirectional laminates for mechanical testing. Low void content samples have been made and demonstrated by C-scan and scanning electron microscopy. The mechanical properties of unidirectional laminates are equivalent to composites fabricated by conventional techniques.

Yang, Pei-Hua↗

Reusable Hot-Wire Cable Cutter

During the early development stage of balloon deployment systems for missions, nichrome wire cable cutters were often used in place of pyro-actuated cutters. Typically, a nichrome wire is wrapped around a bundle of polymer cables with a low melting point and connected to a relay-actuated electric circuit. The heat from the nichrome reduces the strength of the cable bundle, which quickly breaks under a mechanical load and can thus be used as a release mechanism for a deployment system. However, the use of hand-made heated nichrome wire for cutters is not very reliable. Often, the wrapped nichrome wire does not cut through the cable because it either pulls away from its power source or does not stay in contact with the cable being cut. Because nichrome is not readily soldered to copper wire, unreliable mechanical crimps are often made to connect the nichrome to an electric circuit. A self-contained device that is reusable and reliable was developed to sever cables for device release or deployment. The nichrome wire in this new device is housed within an enclosure to prevent it from being damaged by handling. The electric power leads are internally connected within the unit to the nichrome wire using a screw terminal connection. A bayonet plug, a quick and secure method of connecting the cutter to the power source, is used to connect the cutter to the power leads similar to those used in pyro-cutter devices. A small ceramic tube [0.25-in. wide 0.5-in. long (.6.4-mm wide 13-mm long)] houses a spiraled nichrome wire that is heated when a cable release action is required. The wire is formed into a spiral coil by wrapping it around a mandrel. It is then laid inside the ceramic tube so that it fits closely to the inner surface of the tube. The ceramic tube provides some thermal and electrical insulation so that most of the heat generated by the wire is directed toward the cable bundle in the center of the spiral. The ceramic tube is cemented into an aluminum block, which holds it in position. The leads of the nichrome wire are attached to screw terminals that connect them to power leads. A bayonet plug mounted at the bottom of the rectangular block connects the power leads to a relay circuit. A thin aluminum shell encloses the entire structure, leaving access points to attach to the bayonet plug and to feed a cable into the cylinder. The access holes for the deployment cable are a smaller diameter than the nichrome coil to prevent the cable from coming in direct contact with the nichrome when loaded. It uses the same general method of severing a cable with a heated wire as was used previously, but implements it in such a way that it is more reliable and less prone to failure. It creates a mechanism to create repeatability that was nonexistent in the previous method.

Pauken, Michael T.↗

Engineered Interfaces in Extruded Polyphenylsulfone- Boron Nitride Composite Insulation

Improving matrix-filler interactions is critical for optimizing dielectric performance in composite insulation; however, the technique used to an introduce inorganic filler into organic matrices varies in its ability to satisfactorily reduce the size of cavities and interfaces. This study reports how sample rheology influenced the dielectric performance and thermal conductivity of extruded polyphenylsulfone (PPSU) – hexagonal boron nitride (BN) composite insulation through changing the BN incorporation strategy. Depending on the technique used to introduce BN into the host matrix, the low melt viscosity, torque, and melt viscosity temperature of the polymer were reduced, enabling better mixing, heat transfer, and smaller voids. This corresponded to an increase in dielectric strength compared to other formulations; however, the thermal conductivity shifted further away from the thermal conductivity target of 1 W/m·K target, which was an indication of a larger separation distance between the particles in samples with smaller interfaces. A trade-off between dielectric strength and thermal conductivity may exist when maximizing thermal conduction without sacrificing dielectric strength.

polyphenylsulfone↗

Engineered Interfaces in Extruded Polyphenylsulfone-Boron Nitride Composite Insulation

Improving matrix-filler interactions is critical for optimizing dielectric performance in composite insulation; however, the technique used to introduce inorganic fillers into an organic matrix varies in its ability to satisfactorily reduce the size of cavities and interfaces. This study reports effects from changing the filler incorporation strategy on the rheology, dielectric performance and thermal conductivity of extruded polyphenylsulfone (PPSU) – hexagonal boron nitride (hBN) composite insulation. Depending on the technique used to introduce BN into the host matrix, the viscosity, torque, and melt viscosity temperature of the polymer were reduced, enabling better mixing, heat transfer, and smaller voids. This corresponded to an increase in dielectric strength compared to other formulations at either a similar or lower filler loading. On the other hand, the thermal conductivity in these specimens shifted further away from the thermal conductivity target of 1 W/m·K, which was an indication of a larger separation distance between the particles in samples with smaller interfaces. A trade-off between dielectric strength and thermal conductivity may exist when maximizing thermal conduction without sacrificing dielectric strength.

Polyphenylsulfone↗

Molecular-Weight-Dependent Infiltration and Adsorption of Polymers into Nanochannels

The mesoporous silica shell coating hydrogenolysis nano-catalysts alters the molecular weight distributions of cleaved polymer chains compared to catalysts without a shell. The shell, composed of radially aligned narrow cylindrical nanopores, reduces the formation of low-valued gaseous products and increases the median molecular weight of the product, thus enhancing the value of the products for polymer upcycling. Here, to understand the role of the mesoporous shell, we have studied the spatial distribution of polystyrene chains, used as a model polymer, in the nanochannels in both the melt phase and solution phase. In the melt, we observed from small-angle X-ray scattering experiments that the infiltration rate of the polymer into the nanochannels is inversely proportional to the molecular weight, which is consistent with theory. In theta solution experiments using UV–vis spectroscopy, we found that the shell significantly enhances polymer adsorption compared to nanoparticles without pores. In addition, the degree of polymer adsorption is not a monotonic function of molecular weight but initially increases with the molecular weight before eventually decreasing. The molecular weight for the peak adsorption increases with the pore diameter. This adsorption behavior is rationalized as resulting from a balance between the mixing entropy gain by surface adsorption and the conformational entropy penalty incurred by chains confined in the nanochannels. The spatial distribution of polymer chains in the nanochannels is visualized by energy-dispersive X-ray spectroscopy (EDX), and inverse Abel-transformed data reveals a less uniform polymer distribution along the primary pore axis for longer chains.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Iron-Catalyzed Cross-[2 + 2] Cycloaddition of Butadiene and α,ω-Dienes for Ductile and Chemically Recyclable Poly(oligocyclobutanes)

Poly(divinyloligocyclobutanes) (pDVOCBs) are a distinct class of butadiene-derived, chemically recyclable polyolefins prepared from iron-catalyzed [2 + 2] cycloaddition followed by ruthenium-catalyzed ADMET polymerization. These polymers are highly crystalline, with high melting temperatures and unique rotator phases. The high degree of crystallinity in these materials not only leads to high stiffness over a broad temperature range but also results in brittle failure for polymers of modest molecular weights. Iron-catalyzed cross-[2 + 2] cycloaddition of butadiene and α,ω-dienes was accomplished, where the number of methylene units between the four-membered rings was systematically varied. Subsequent ADMET polymerization of the resulting telechelic oligomers provided a new class of chemically recyclable polyolefins that exhibit distinct thermomechanical properties. Specifically, methylene units induce changes in crystallinity that, in combination with the increased molecular weight, favored the formation of stable necks upon tensile deformation, with ∼10× enhanced ductility and improved toughness compared to pDVOCB. Through combined experimental and computational studies, the effects of methylene spacers on the crystal-to-rotator transition of the cyclobutane polymers were established. Ultimately, these methylene-modified cyclobutane polymers expand the range of properties and potential applications of this class of recyclable polyolefins.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Macro-level mechanical interlocking: A rapid joining approach for additively manufactured compression molded composite panels

Composite joining typically involves multiple steps, such as drilling and surface treatment, as part of the manufacturing process, which leads to low throughput and long cycle times. In the present study, we demonstrated a macro-level mechanical interlocking (MI) based, rapid joining technique to assemble additively manufactured compression molded (AMCM) panels, enabling the production of parts larger than the mold dimensions. Composite panels made of 20 wt% short carbon fiber reinforced acrylonitrile butadiene styrene (CF/ABS) were joined using MI features of various geometries, namely tree (TR), dovetail (Dov), rectangle 2 (Rect2), and rectangle 1 (Rect1), and their in-plane strength was evaluated. The resultant strength of the tested MI joints reached up to 74 % of the baseline tensile strength (i.e., the ‘no joint’ case). Observations from optical and scanning electron microscopy revealed inadequate polymer diffusion between the adherends, indicating that the joint strength was primarily derived from mechanical interlocking. Additionally, the fracture surfaces exhibited stress-whitening marks, which were characterized using differential scanning calorimetry (DSC). The increase in melting enthalpy suggested local stretching of polymer chains due to MI. Finite element analysis (FEA) indicated that the Rect1 MI feature, which generated the lowest stress concentration, outperformed the others in terms of joint strength, achieving 42 MPa. As a demonstration of the MI joining method, a battery box tray measuring 108 cm × 34 cm using a mold with an effective dimension of 36 cm × 34 cm successfully manufactured, resulting in a part with an area three times larger than the mold. In conclusion, this study presents a promising approach to improving composite joining techniques while minimizing production complexities.

In-plane joining↗

Development of polysilsesquioxane composites

Polymer composites are increasingly being required to operate for prolonged durations at higher temperatures than in the past. Hence there have been increased efforts devoted to synthesizing and characterizing polymers capable of withstanding temperatures greater than 300 C for long periods. Several such organic polymers have been investigated in recent times. This research effort seeks to enquire if inorganic polymers can be utilized to provide the same result. Ceramics have long been recognized as providing superior thermal properties for demanding applications. However, the extremely high softening temperatures preclude their being shaped into complex shapes through melt processing techniques common to organic polymers. One approach towards solving this problem has been through the development of preceramic polymers. These are capable of being processed in the polymeric state with ease, and subsequently being pyrolyzed to ceramic structures. This experimental study is aimed at studying the feasibility of using preceramic polymers (that have not been subject to the pyrolysis step) as high performance composite matrices for high temperature applications. A preliminary study of this nature is not geared towards optimizing mechanical properties suitable for such composites. Rather, this study attempts to process such resins in composite form and suitably characterize their properties.

Srinivasan, K.↗

Improved melt flow and physical properties of Mitsui Toatsu's LARC-TPI 1500 series polyimide

The basic thermal properties and melt behavior of an improved form of LARC-TPI polyimide, LARC-TPI 1500, are investigated and compared with those of LARC-TPI 1000 and 2000. The LARC-TPI 1500 powders are thermally stable and melt processable. The absolute molecular weight of the polymer varies from 20,000 to 30,000, indicating recurring unit numbers of about 40-60. The melt flow properties of LARC-TPI 1500 are comparable to those of other engineering plastics, such as PEEK, PSU, and PES. The flexural modulus of injection molded parts of LARC-TPI 1500 is the highest among commercial thermoplastic polymers.

Ohta, Masahiro↗

Using Crystallization to Control Filler Dispersion and Vice Versa in Polymer Nanocomposites

Our overall goal was to exploit our ability to control the spatial dispersion of spherical nanoparticles in a semicrystalline polymer matrix to tune the properties of the resulting nanocomposite. In particular, our two tasks were: Hierarchically organize spherical nanoparticles into unique morphologies by varying the ratio of the polymer crystallization rate to the filler diffusion rate during matrix solidification. Organize nanoparticles in the matrix melt into superstructrues as a means to tailor polymer crystallization rates, and potentially the crystal structure and/or morphology of the semicrystalline matrix.

36 MATERIALS SCIENCE↗