Richard J. Spontak

Correlated electrical conductivity and mechanical property analysis of high-density polyethylene filled with graphite and carbon fiber

Abstract The development of conductive polymer composites remains an important endeavor in light of growing energy concerns. In the present work, graphite (G), carbon fiber (CF) and G/CF mixtures are added to high-density polyethylene (HDPE) to discern if mixed fillers afford appreciable advantages over single fillers. The effects of filler type and composition on electrical conductivity, composite morphology and mechanical properties have been examined and correlated to establish structure–property relationships. The threshold loading levels required for G and CF to achieve measurable conductivity in HDPE have been identified. Addition of CF to HDPE/G composites is found to increase the conductivity relative to that of HDPE/G composites at the same filler concentration. This observed increase depends on CF length and becomes more pronounced at and beyond the threshold loading of the HDPE/G composite. Scanning electron microscopy is employed to elucidate the morphology of these multicomponent composites, whereas dynamic mechanical analysis reveals that filler concentration, composition and CF length impact both the magnitude and temperature dependence of the dynamic storage modulus.

Bridged double percolation in conductive polymer composites: an electrical conductivity, morphology and mechanical property study

Conductive polymer composites are ubiquitous in technological applications and constitute an ongoing topic of tremendous commercial interest. Strategies developed to improve the level of electrical conductivity achieved at a given filler concentration have relied on double-percolated networks induced by immiscible polymer blends, as well as mixtures of fillers in a single polymer matrix, to enhance interparticle connectivity. In this work, we combine these two strategies by examining quaternary composites consisting of high-density polyethylene (HDPE), ultrahigh molecular weight polyethylene (UHMWPE), graphite (G) and carbon fiber (CF). On the basis of our previous findings, we examine the electrical conductivity, morphology, thermal signature and mechanical properties of HDPE/UHMWPE/G systems that show evidence of double percolation. Upon addition of CF, tremendous increases in conductivity are realized. The mechanism by which this increase occurs is termed bridged double percolation to reflect the role of CF in spanning non-conductive regions and enhancing the continuity of conductive pathways. At CF concentrations above the percolation threshold concentration, addition of G promotes increases in conductivity and dynamic storage modulus in which the conductivity increases exponentially with increasing modulus.

Thermoplastic elastomers: fundamentals and applications

Abstract Thermoplastic elastomers are multi-functional polymeric materials that generally possess the processability of thermoplastics and the elasticity of vulcanized rubber. Intrinsic thermoplastic elastomers include microphase-separated block and segmented copolymers containing a soft (low- T g ) species. Recent achievements regarding thermoplastic elastomer block and segmented copolymers in the past year have improved the current understanding of (i) complex nanostructures in unary and multicomponent systems and (ii) the thermally-activated sphere→cylinder and cylinder→gyroid order–order transitions. The use of these materials in organogel, electro-responsive and nanocomposite applications illustrates the diversity and future potential of these technologically important materials.

Self‐organization and polyolefin nucleation efficacy of 1,3:2,4‐di‐p‐methylbenzylidene sorbitol

Recent studies have demonstrated that addition of a small quantity of dibenzylidene sorbitol (DBS) to a molten polymer may result in a physical gel if conditions permit the DBS molecules to self-organize into a three-dimensional network composed of highly connected nanofibrils. If the polymer crystallizes, DBS may also serve as a nucleating agent, promoting the formation of spherulites, especially in commercially important polyolefins such as polypropylene. We examine the thermal and mechanical properties, as well as the morphological characteristics, of an isotactic polypropylene copolymer with 3 wt % ethylene upon addition of less than 1 wt % of 1,3:2,4-di-p-methylbenzylidene sorbitol (MDBS). From dynamic rheological measurements, pronounced complex viscosity increases, attributed to MDBS nanofibril network formation, are observed at concentration-dependent temperatures above the melting point of the nucleated copolymer. Transmission electron micrographs of RuO4-stained sections confirm the existence of MDBS nanofibrils measuring on the order of 10 nm in diameter and, at higher concentrations, fibrillar bundles measuring up to about 200 nm across and several microns in length. The addition of MDBS at different concentrations is also found to promote increases in optical clarity, yield strength, tensile strength, and ultimate elongation of modified copolymer formulations.

Generation of microcellular foams of PVDF and its blends using supercritical carbon dioxide in a continuous process

Abstract Use of supercritical carbon dioxide (scCO 2 ) as a blowing agent to generate microcellular polymer foams (MPFs) has recently received considerable attention due to environmental concerns associated with conventional organic blowing agents. While such foams derived from amorphous thermoplastics have been previously realized, semicrystalline MPFs have not yet been produced in a continuous scCO 2 process. This work describes the foaming of highly crystalline poly(vinylidene fluoride) (PVDF) and its blends with amorphous polymers during extrusion. Foams composed of neat PVDF and immiscible blends of PVDF with polystyrene exhibit poor cell characteristics, whereas miscible blends of PVDF with poly(methyl methacrylate) (PMMA) yield foams possessing vastly improved morphologies. The results reported herein illustrate the effects of blend composition and scCO 2 solubility on PVDF/PMMA melt viscosity, which decreases markedly with increasing PMMA content and scCO 2 concentration. Morphological characterization of microcellular PVDF/PMMA foams reveals that the cell density increases as the PMMA fraction is increased and the foaming temperature is decreased. This study confirms that novel MPFs derived continuously from semicrystalline polymers in the presence of scCO 2 can be achieved through judicious polymer blending.

Thermoplastic elastomer gels. I. Effects of composition and processing on morphology and gel behavior

Thermoplastic elastomer gels (TPEGs) composed of a poly[styrene-b-(ethylene-co-butylene)-b-styrene] triblock copolymer and a low-volatility, midblock-compatible mineral oil have been investigated at different oil concentrations to ascertain the effect of composition on TPEG morphology and mechanical properties. The impact of thermal processing is also examined by comparing gels thermally quenched to 0°C or slowly cooled to ambient temperature. Transmission electron micrographs reveal that gels with 70 to 90 wt % oil exhibit styrenic micelles measuring ca. 24 nm in diameter. Variation in composition or cooling rate does not have any perceivable effect on micelle size or shape, whereas the rate at which the gels are cooled influences the extent of microstructural order and the time to rupture (tR) at constant strain. Dynamic rheological testing confirms the presence of a physically crosslinked network at TPEG compositions ranging from 70 to 90 wt % oil, independent of cooling rate. Results presented here suggest that the dynamic elastic shear modulus (G′) scales as tαR where α varies from 0.41 to 0.59, depending on cooling rate.

Morphology and gas barrier properties of thin SiO x coatings on polycarbonate: Correlations with plasma-enhanced chemical vapor deposition conditions

Plasma-enhanced chemical vapor deposition of SiO x coatings on thermoplastics provides a viable route for production of transparent composite materials with high fracture toughness and high gas barrier properties, which are important considerations in the food packaging and biomedical device industries. By examining several series of systematically varied SiO x /polycarbonate composites, we have identified design correlations between coating characteristics (thickness, density, surface roughness, and O 2 transmission) and deposition conditions (time, power, pressure, and flow rates). Of particular interest is the observation that the thermal activation energy for O 2 permeation through these composites increases (by up to 17 kJ/mol) as their barrier efficacy increases.

Long-Range Alignment of Gold Nanorods in Electrospun Polymer Nano/Microfibers

In this study, a scalable fabrication technique for controlling and maintaining the nanoscale orientation of gold nanorods (GNRs) with long-range macroscale order has been achieved through electrospinning. The volume fraction of GNRs with an average aspect ratio of 3.1 is varied from 0.006 to 0.045 in aqueous poly(ethylene oxide) solutions to generate electrospun fibers possessing different GNR concentrations and measuring 40-3000 nm in diameter. The GNRs within these fibers exhibit excellent alignment with their longitudinal axis parallel to the fiber axis n. According to microscopy analysis, the average deviant angle between the GNR axis and n increases modestly from 3.8 to 13.3° as the fiber diameter increases. Complementary electron diffraction measurements confirm preferred orientation of the {100} GNR planes. Optical absorbance spectroscopy measurements reveal that the longitudinal surface plasmon resonance bands of the aligned GNRs depend on the polarization angle and that maximum extinction occurs when the polarization is parallel to n.

Bi-directional Kirkendall Effect in Coaxial Microtube Nanolaminate Assemblies Fabricated by Atomic Layer Deposition

The solid-state reaction within a coaxial Al2O3/ZnO/Al2O3 multilayered microtubular structure can be used to prepare discrete microtube-in-microtube ZnAl2O4 spinel assemblies through a Kirkendall void production mechanism at 700 degrees C. In contrast with previous studies of the nanoscale Kirkendall effect, the reaction observed here proceeds through a bi-directional vacancy diffusion mechanism wherein ZnO species diffuse into inner- and outer-Al2O3 concentric layers, thereby resulting in vacancy supersaturation and void production between two isolated spinel microtubes. Low-temperature atomic layer deposition (ALD) of Al2O3 and ZnO enables the fabrication of complex coaxial multilayered microtubes with precise control of the starting film thicknesses and relative composition. When a molar excess of ZnO is present between two Al2O3 layers, electron microscopy images reveal incomplete ZnO consumption after annealing at 700 degrees C. At higher initial Al2O3 concentrations, however, complete reaction with ZnO is observed, and the size of the Kirkendall gap between isolated spinel microtubes appears to be directly influenced by the thickness of the intermediate ZnO layer.

High-energy mechanical milling of poly(methyl methacrylate), polyisoprene and poly(ethylene-alt-propylene)

High-energy mechanical milling has been performed on poly(methyl methacrylate) (PMMA) at ambient and cryogenic temperatures, as well as on polyisoprene (PI) and poly(ethylene-alt-propylene) (PEP) at cryogenic conditions only. Milling conducted at ambient temperature has a substantially greater impact on the molecular characteristics of PMMA than milling at cryogenic temperatures. An increase in the milling time is accompanied by substantial reductions in PMMA molecular weight and, hence, glass transition temperature and impact strength under both sets of experimental conditions. An unexpected trend identified here is that the PMMA molecular weight distribution initially broadens and subsequently narrows with increasing milling time. Solid-state mechanical milling promotes comparable decreases in molecular weight and glass transition temperature in PEP (at a slower rate relative to PMMA), but induces chemical crosslinking in PI, as confirmed by FTIR spectroscopy. Charlesby‐Pinner analysis yields not only the degree of PI crosslinking, but also the relative crosslinking and scission rates of PI, during cryogenic milling. q 2000 Elsevier Science Ltd. All rights reserved.