Dielectric properties and molecular mobility of organic/inorganic polymer composites

Microstructure-dielectric properties relationship and molecular mobility of organic/inorganic polymer composites (OIPCs), consisting of polyurethane (PU) and sodium silicate (NaSi), were investigated in this work. Broadband dielectric relaxation spectroscopy (DRS) and thermally stimulated depolarization current (TSDC) techniques were employed. Our interest was focused on the study of the glass transition mechanism and conductivity relaxation. The influence of the molecular weight of PU and inorganic phase content on the dielectric properties of the composites was of particular interest. Glass transition temperature shifts to higher temperatures with the addition of NaSi. The overall molecular mobility was found to increase in the composites, compared to the pure PU matrix. The results are more intense for the composites based on the PU with low molecular weight.     

Dielectric studies of polymer-water interactions and water organization in PEO/water systems

We report the results of detailed investigations of polymer-water interactions and of the organization of water in the poly(ethylene oxide) (PEO)/water system by dielectric techniques. They include thermally stimulated depolarization currents (TSDC) techniques in the temperature range of 77-300 K and broadband dielectric relaxation spectroscopy (DRS) techniques of frequencies, 5 Hz-10 GHz, and temperatures, 173-300 K. The water content h was varied between 0 and 1.21 (grams of water per gram of dry PEO). The secondary γ mechanism of PEO and the reorientation of absorbed water molecules were extensively studied. The γ mechanism was found to be plasticized up to water contents of about 0.20. The reorientation of water molecules was studied in three different experiments and frequency/temperature regions. The results suggest strong interactions in the PEO/water system and indicate the presence of a separate water phase at high water contents. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 1545–1560, 1997     

Water sorption and electrical/dielectric properties of organic-inorganic polymer blends

Organic-inorganic polymer blends (OIPB) were obtained by reaction of organic and inorganic oligomers. The organic oligomer was synthesized with 2,4-toluene diisocyanate (TDI) and oligooxypropylene glycols (OPG) with various molecular weights (MW). The inorganic component was a water solution of sodium silicate. The OIPB obtained are hydrophilic and have great water sorption ability (the relative weight of sorbed water reaches 2000 %). The kinetics of water sorption and the changes of electrical conductivity during sorption were studied. Sorption ability, and mechanical, electrical and dielectric properties of OIPB depend on molecular weight of OPG: conductivity increases with increasing MW, whereas the sorption ability correlates with the mechanical properties. The influence of the inorganic phase content on the electrical and dielectric properties was studied as well.     

Structure‐dependent conductivity and microhardness of metal‐filled PVC composites

Metal‐filled composites of a commercial PVC (polyvinyl chloride) powder (mean particle size d_p ≈ 100 microns) and a metal powder (mean particle size d_f about 100 microns for copper, Cu, and about 10 microns for nickel, Ni) prepared by mechanical mixing in a ball mill, subsequent hot‐pressing at 443 K and rapid cooling to 300 K, were characterized by the room‐temperature measurements of electrical conductivity σ, density ρ and microhardness H. The sudden jumps of about 17 orders of magnitude followed by a much slower growth up to the limiting filler fraction ϕ* on the log σ vs. ϕ plots are the evidence for the onset of percolation transitions, at filler volume contents ϕ_c1 = 0.05 and 0.04 for PVC/Cu and PVC/Ni, respectively. For both systems, the values of H exhibited an initial steep increase up to ϕ_c2 = 0.07, followed by an apparent plateau extending up to ϕ = 0.18. However, drastic differences in the patterns of composition dependence of H were observed at higher metal loadings, i.e., a continuous increase of H up to the leveling‐off at ϕ* for PVC/Cu, in contrast to a sudden drop of H at ϕ = 0.20 and subsequent slow increase for PVC/Ni. For both composites the apparent density ρ′ of a polymer matrix remained the same as that of the neat PVC in the composition interval ϕ < 0.20, while at ϕ* > 0.20 a precipitous drop of ρ₁ was observed due to the formation of polymer‐free voids between filler particles (crowding effect) as ϕ approaches ϕ*. The observed effects were analyzed in terms of a tentative model envisaging cross‐overs from “dilute suspension regime” to “semi‐dilute suspension regime” in the concentration range ϕ_c1 to ϕ_c2, and from “semi‐dilute suspension regime” to “concentrated suspension regime” above ϕ = 0.20. Different behavior in this latter regime was explained by intrinsic differences in the structure of conductive infinite clusters between mixtures of particles of about the same size (PVC/Cu) and of widely different sizes (PVC/Ni).