Paul Zoller

Bio: Paul Zoller is an academic researcher from DuPont. The author has contributed to research in topics: Enthalpy of fusion & Glass transition. The author has an hindex of 15, co-authored 18 publications receiving 1132 citations.

Standard Pressure Volume Temperature Data for Polymers

Abstract: 1. INTRODUCTION Pressure-Volume-Temperature (PVT) Data: Equilibrium and Nonequilibrium States of Polymers Scope of This Data Collection Equipment for PVT Measurements: Piston-Die Technique Confining Fluid Technique Equipment Used for Data in This Book Experimental Procedures: Stan- dard PVT Runs Sample Preparation Determination of the Specific Volume at Ambient Conditions Data Interpretation: Tables and Graphs in This Collection Liquids Materials Undergoing a Glass Transition Materials Having a Melt Transition Filled Materials and Blends Application of PVT Data Empirical and Theoretical Fits to PVT Data References 2. HYDROCARBONS n-Undecane (C11H24) n-Tetradecane (C14H30) n-Hexadecane (C16H34) n-Tetracosane (C24H50) n-Hexatriacotane (C36H74) n-Tetratetracotane (C44H90) 3. HYDROCARBON POLYMERS Polyethylene (linear) Polyethylene (branched) Polyethylene wax (M ~2100) Polyethylene wax (M ~1000) Poly(propylene) (atactic) Polypropylene (atactic) Polypropylene (isotactic) Poly(1-butene) (atactic) Poly(1-butene) (isotactic) Poly(1-octene) Polyisobutylene (M ~ 4.2 x 105) Polyisobutylene (M ~ 300) Polyisoprene (hydrogenated) Poly(4-methyl pentene-1) Polynorbornene Hydrocarbon resin Poly(ethylene-co-propylene) (23% polypropylene) Poly(ethylene-co-propylene) (57% propylene) Poly(ethylene-co-propylene) (76% propylene) Poly(ethylene-co-propylene) (84% propylene) Polybutadiene (M ~ 2.33 x 105) Polybutadiene (cis & trans) Polybutadiene (cis) Polybutadiene (M ~ 3000) Polybutadiene (M ~ 1000) Natural rubber 4. ETHYLENE POLYMERS crylic acid) Poly(ethylene-co-methacrylic acid) (9% methacrylic acid) Poly(ethylene-co-methacrylic acid) (11.5% methacrylic acid) Poly(ethylene-co-methacrylic acid) (12% methacrylic acid) Poly(ethylene-co-methacrylic acid) (15% methacrylic acid) Poly(ethylene-co-methacrylic acid) (20% methacrylic acid) Ionomer (~ 1.5% Na) Ionomer (~ 2.2% Na) Poly(ethylene-co-acrylic acid) (9% acrylic acid) Poly(ethylene-co-acrylic acid) (10% acrylic acid) Poly(ethylene-co-acrylic acid) (20% acrylic acid) Poly(ethylene-co-vinyl alcohol) (56% vinyl alcohol) Poly(ethylene-co-vinyl alcohol) (62% vinyl alcohol) Poly(ethylene-co-vinyl alcohol) (70% vinyl alcohol) 5. STYRENICS Polystyrene (M ~ 1.1 x 105) Polystyrene (M ~ 34500) Polystyrene (M ~ 9000) Polystyrene (M ~ 910) Poly(4-chloro styrene) Poly(styrene-block-hydrogenated butadiene) 6. ACRYLICS Poly(methyl methacrylate) (M ~ 1 x 105) Poly(methyl methacrylate) (M ~ 40000) Poly(methyl methacrylate) (M ~ 25000) Poly(methyl methacrylate) (M ~ 10000) Poly(ethyl methacrylate) Poly(propyl methacrylate) Poly(n-propyl methacrylate) Poly(n-butyl methacrylate) Poly(n-hexyl methacrylate) Poly(lauryl methacrylate) Poly(isobutyl methacrylate) Poly(methyl acrylate) Poly(ethyl acrylate) Poly(n-propyl acrylate) Poly(n-butyl acrylate) Poly(acrylic acid) Poly(methacrylic acid) 7. POLYACRYLONITRILE AND COPOLYMERS Polyacrylonitrile Poly(styrene-co-acrylonitrile) (25% acrylonitrile) Poly(acrylonitrile-co-butadiene) (67% butadiene) Nitrile rubber compound 8. OTHER C-C MAIN CHAIN POLYMERS Poly(vinyl acetate) Poly(vinyl alcohol) Poly(vinyl butyral) Poly(vinyl carbazole) Poly(vinyl chloride) Poly(vinyl fluoride) Poly(vinyl formal) Poly(vinylidene fluoride) Poly(tetrafluoro ethylene) Fluoropolymer glass Fluoroelastomer compound Perfluoroelastomer compound 9. POLYETHERS Poly(methylene oxide) (homopolymer) Poly(methylene oxide) (copolymer) Poly(ethylene oxide) (M x105) Poly(ethylene oxide) (M ~ 18500) Poly(ethylene oxide) (M ~ 1540) Poly(ethylene oxide) (M ~ 600) Poly(ethylene oxide) (M ~ 300) Poly(ethylene oxide) mono methyl ether (M ~ 750) Poly(ethylene oxide) mono methyl ether (M ~ 350) Poly(ethylene oxide) dimethyl ether (M ~ 1000) Poly(ethylene oxide) dimethyl ether (M ~ 600) Poly(propylene oxide) (M ~ 4000) Poly(propylene oxide) (M ~ 2000) Poly(propylene oxide) (M ~ 1025) Poly(propylene oxide) (M ~ 400) Poly(propylene oxide) dimethyl ether (M ~ 2000) Poly(propylene oxide) dimethyl ether (M ~ 1025) Poly(propylene oxide) dimethyl ether (M ~ 400) Poly(hexafluoropropylene oxide) (M ~ 7000) Poly(hexafluoropropylene oxide) (M ~ 2000) Silicone fluid (commercial) Poly(dimethyl siloxane) (M ~ 1.5 x 106) Poly(dimethyl siloxane) (M ~ 2.24 x 105) Poly(dimethyl siloxane) (M ~ 17200) Poly(dimethyl siloxane) (M ~ 9670) Poly(dimethyl siloxane) (M ~ 3900) Poly(dimethyl siloxane) (M ~ 870) Poly(dimethyl siloxane) (M ~ 340) 10. POLYAMIDES Nylon 6 Nylon 7 Nylon 9 Nylon 11 Nylon 12 Nylon 4/6 Nylon 6/6 Nylon 6/6 (rubber toughened) Nylon 6/7 Nylon 6/8 Nylon 6/9 Nylon 6/10 Nylon 6/10 (pure) Nylon 6/12 Nylon 13/13 Nylon 6I/6T Aramid fiber 11. POLYESTERS Poly(ethylene adipate) Poly(ethylene succinate) Polycaprolactone Poly-L-lactide Poly(ethylene isophthalate) Poly(ethylene terephthalate) Poly(ethylene naphthenoate) Poly(butylene terephthalate) Bisphenol A isophthalate Polyarylate 12. VARIOUS MAIN CHAIN AROMATICS Polycarbonate Chloral polycarbonate Poly(2-6-dimethyl phenylene oxide) Phenoxy resin Polyetherimide Polyimide (film) Poly(ether ether ketone) Poly(ether sulphone) Polysulfone Poly(azomethine ether) (n = 4) Poly(azomethine ether) (n= 7) Poly(azomethine ether) (n= 8) Poly(azomethine ether) (n= 9) Poly(azomethine ether) (n= 10)Poly(azomethine ether) (n= 11) 13. BLENDS Polystyrenepoly(vinyl methyl ether) blend (90/10) Polystyrenepoly(vinyl methyl ether) blend (80/20) Polystyrenepoly(vinyl methyl ether) blend (70/30) Polystyrenepoly(vinyl methyl ether) blend (60/40) Poly- styrenepoly(vinyl methyl ether) blend (50/50) Polystyrenepoly(vinyl methyl ether) blend (40/60) Polystyrenepoly(vinyl methyl ether) blend (30/70) Polystyrenepoly(vinyl methyl ether) blend (20/80) Poly- styrenepoly(vinyl methyl ether) blend (10/90) Poly(2,6-dimethyl phenylene oxide)polystyrene blend (90/10) Poly(2,6-dimethyl phenylene oxide)polystyrene blend (80/20) Poly(2,6-dimethyl phenylene oxide)poly- styrene blend (70/30) Poly(2,6-dimethyl phenylene oxide)polystyrene blend (60/40) Poly(2,6-dimethyl phenylene oxide)polystyrene blend (50/50) Poly(2,6-dimethyl phenylene oxide)polystyrene blend (40/60) Poly(2,6-dimethyl phenylene oxide)polystyrene blend (30/70) Poly(2,6-dimethyl phenylene oxide)polystyrene blend (20/80) Poly(2,6-dimethyl phenylene oxide)polystyrene blend (10/90) Polyethersulphonepoly- (ethylene oxide) blend (40/60) Polyethersulphonepoly(ethylene oxide) blend (20/80) 14. MISCELLANEOUS Starch triacetate >Poly(ethylene-co-vinyl acetate) (14% vinyl acetate) Poly(ethylene-co-vinyl acetate) (18% vinyl acetate) Poly(ethylene-co-vinyl acetate) (25% vinyl acetate) Poly(ethylene-co-vinyl acetate) (28% vinyl acetate) Poly(ethylene-co-vinyl acetate) (33% vinyl acetate) Poly(ethylene-co-vinyl acetate) (40% vinyl acetate) Poly(ethylene-co-vinyl acetate) (65% vinyl acetate) Poly(ethylene-co-methacrylic acid) (4% metha

Matrix solidification and the resulting residual thermal stresses in composites

Abstract: The disparate thermal expansion properties of the fibres and matrices in high-performance composites lead to an inevitable build up of residual thermal stresses during fabrication. We first discuss the thermal expansion behaviour of thermoplastic and thermoset polymers that may be used as high-performance composite matrices. The three classes of polymers considered are epoxies, amorphous thermoplastics, and semicrystalline thermoplastics. The relevant thermal expansion data for prediction of the magnitude of the residual stresses in composites is the zero (atmospheric)-pressure thermal expansion data; these data are plotted for a range of thermoplastics and a typical epoxy. Using the technique of photoelasticity, we have measured the magnitude of the residual stresses in unidirectional graphite composites with an amorphous thermoplastic matrix (polysulfone) and with an epoxy matrix (BP907). The temperature dependence of the residual stress build up and the resulting magnitude of the residual stresses correlate well with the thermal and physical properties of the matrix resin.

A study of the pressure‐volume‐temperature relationships of four related amorphous polymers: Polycarbonate, polyarylate, phenoxy, and polysulfone

Abstract: The pressure-volume-temperature (PVT) relationships of bisphenol-A polycarbonate, polyarylate, and phenoxy were studied at pressures to 1800 kg/cm2 and in both the glassy and melt states. Earlier data on polysulfone are included in the analysis and discussion of the results. All four polymers contain the bisphenol-A residue in their repeat unit, together with a moiety of varying complexity, and are therefore somewhat related. At the glass transition, equations of the Ehrenfest type hold, provided the pressure dependence of the glass transition temperature is defined from the line obtained by intersecting the quasiequilibrium PVT relationship of the glass with the equilibrium PVT surface of the melt. The Prigogine-Defay ratio r = ΔκΔCp/TgVg(Δα)2 at P = O is unity within experimental error for all four polymers. The melt data were fitted successfully to the Simha-Somcynsky theory. Molecular parameters deduced from the reducing parameters vary in a reasonable manner among these four related polymers, lending support to the foundations of the theory.

Pressure‐volume‐temperature properties of blends of poly(2,6‐dimethyl‐1,4‐phenylene ether) with polystyrene

Abstract: The pressure-volume-temperature (PVT) properties of blends of poly(2,6-dimethyl-1,4-phenylene ether) (PPO) with polystyrene (PS) have been studied experimentally in both the glassy and melt states at 0, 20, 40, 50, 60, 80, and 100% PPO content. In all compositions a strong glass transition was observed varying linearly with composition. For all but the 40% PPO composition this was the only transition, indicating molecular compatibility of the components in these blends. The 40% PPO composition showed a very weak second transition near the glass transition of pure PS. A small amount of phase separation may have occurred in this blend. The data for the glassy and melt states were fitted to an empirical equation of state based on the Tait equation. The volume of the melts at constant pressure and temperature showed a virtually linear dependence on composition. Any negative excess volume of mixing compatible with the data would have to be very small, smaller than expected from previous measurements in the glassy state. Various properties relating to the glassy and melt states and to the glass transition were evaluated and are discussed as a function of composition. It was found that most properties of the glasses could not be modeled by simple functions of composition.

The heat of fusion of polytetrafluoroethylene

Abstract: The heat of fusion of virgin and melt-processed polytetrafluoroethylene (PTFE) was determined using the Clapeyron equation. Experimental data were obtained from PVT experiments and high-temperature x-ray diffraction measurements. For virgin, as-polymerized PTFE, the melting temperature is given by where, for Tm in degrees Celsius, A = 346.3±1.2, B = 0.095±0.003, and P is the pressure in kilograms per square centimeter. At the end of the atmospheric-pressure melting interval, the amorphous and crystalline specific volumes V1 and Vc are 0.6517 and 0.492 cm3/g, respectively. Thus the heat of fusion is 24.4 cal/g, or nearly twice the value reported previously. The increases in enthalpy and volume at the melting point both indicate a degree of crystallinity of about 75–80% although infrared, x-ray, and NMR data give much higher levels. Data from calorimetry, NMR, and dynamic mechanical measurements indicate that in virgin PTFE some of the crystals continue to experience torsional oscillations at temperatures below the room-temperature transitions. This indicates that there are at least two kinds of crystalline regions. For previously melted PTFE, Tm is determined by A = 328.5±0.7 and B = 0.095±0.002, the volumes are Vam = 0.6349 and Vcr = 0.4855 cm3/g, and the heat of fusion is 22.2 cal/g. The entropy of fusion for PTFE is much closer to that of polyethylene than was previously believed.

Effects of confinement on material behaviour at the nanometre size scale

Abstract: In this article, the effects of size and confinement at the nanometre size scale on both the melting temperature, Tm, and the glass transition temperature, Tg, are reviewed. Although there is an accepted thermodynamic model (the Gibbs–Thomson equation) for explaining the shift in the first-order transition, Tm, for confined materials, the depression of the melting point is still not fully understood and clearly requires further investigation. However, the main thrust of the work is a review of the field of confinement and size effects on the glass transition temperature. We present in detail the dynamic, thermodynamic and pseudo-thermodynamic measurements reported for the glass transition in confined geometries for both small molecules confined in nanopores and for ultrathin polymer films. We survey the observations that show that the glass transition temperature decreases, increases, remains the same or even disappears depending upon details of the experimental (or molecular simulation) conditions. Indeed, different behaviours have been observed for the same material depending on the experimental methods used. It seems that the existing theories of Tg are unable to explain the range of behaviours seen at the nanometre size scale, in part because the glass transition phenomenon itself is not fully understood. Importantly, here we conclude that the vast majority of the experiments have been carried out carefully and the results are reproducible. What is currently lacking appears to be an overall view, which accounts for the range of observations. The field seems to be experimentally and empirically driven rather than responding to major theoretical developments.

Supercooled dynamics of glass-forming liquids and polymers under hydrostatic pressure

Abstract: An intriguing problem in condensed matter physics is understanding the glass transition, in particular the dynamics in the equilibrium liquid close to vitrification Recent advances have been made by using hydrostatic pressure as an experimental variable These results are reviewed, with an emphasis in the insight provided into the mechanisms underlying the relaxation properties of glass-forming liquids and polymers