Dynamic mechanical properties of polymers filled with agglomerated particles

The filler particles in most filled polymers are not perfectly dispersed but are more or less agglomerated. The degree of agglomeration and the strength of the agglomerates, which can be modified by surface treatments, have a very great effect on the dynamic mechanical properties. Filler agglomerates which are wetted by the polymer matrix produce higher elastic moduli than similar agglomerates which are not wetted. The relative damping in most filled polymers is very temperature-dependent. A qualitative explanation is given for this temperature dependence. The degree of agglomeration and the strength of the agglomerates are important factors in determining the damping.     

Rheological properties of filled polymers

The rheological properties of two model suspensions using a Newtonian polymeric matrix are presented and discussed in light of results presented in the literature. It is shown that particle-particle interactions in concentrated suspensions are responsible for a gel-type behavior at very small strain and strain hardening at a critical strain. Suspensions of concentrated colloidal particles in a Newtonian matrix behave like typical viscoelastic molten polymers, but the properties are strongly dependent on the solids dispersion, and strain at small strain. A simple rheological model is proposed to describe the shear viscosity of these suspensions.     

Soft-to-hard transformation of the mechanical properties of dynamic covalent polymers through component incorporation

The mechanical properties of acylhydrazone dynamic polymers may be converted from soft to hard by the incorporation of rigid monomeric components into the original soft polymer backbone, taking advantage of acylhydrazone bond exchange.     

Temperature dependence of radiation effects on polymers

Temperature dependence of radiation effect on various polymers including hydrocarbon and fluorocarbon polymers was investigated. Gas evolution and mechanical properties were measured in a wide range of temperatures. G-values of chain scission and crosslinking were estimated. It has been made clear from those experimental results that radiation effect be profoundly affected by temperature. Particularly, significant changes of radiation effect in the melting region were found out.     

Temperature dependence of the bulk crystallization rate of polymers

Data already existing in the literature for the overall crystallization kinetics of a variety of polymers have been analyzed according to different possible nucleation mechanisms. The conclusions reached are similar to those previously deduced from an examination of ata for spherulite growth rates. It is demonstrated that, if allowed a reasonable choice for the equilibrium melting temperature, no unbiased selection of a unique nucleation process can be made. Moreover, a set of universal parameters exists for each of the nucleation and growth processes considered which allows the data for all polymers to be represented by a single straight line. The only quantities that are unique to a given polymer are the equilibriun melting temperature and the activation energy for transport.     

Frequency and temperature dependence of the dynamic mechanical properties of poly-4-methylpentene-1

The dynamic mechanical properties of poly-4-methylpentene-1 have been measured in torsion in the temperature range from 25 to 160°C. at frequencies from 10^?3 to 10 cps. Two transitions are found. The first, with a peak at 40°C. at 1 cps, appears as a normal glass transition. A broad high temperature peak appears at 130°C. The dynamic compliance-frequency data can be superposed by the conventional method of reduced variables for temperatures up to 100°C. The temperature dependence of the shift factors follows the WLF equation. Above this temperature, superposition can be achieved by applying horizontal and vertical shifts to both components of the dynamic compliance. When the vertical shift is permitted, the range of applicability of the WLF equation is extended to 160°C.     

Temperature dependence of relative modulus in filled polymer systems

The temperature dependence of relative modulus observed in filled thermoset, thermoplastic, and polyelectrolyte salt matrices is explained on the basis of induced stresses produced by the differences in the thermal expansion coefficients of the constituent materials. The analysis is based on the assumption that the modulus of the matrix in a filled polymer is less than that of the unfilled polymer. The temperature dependence of relative modulus is expressed as a function of the difference in thermal expansion coefficients, the volume fraction, the relative modulus in the unstressed state, and mechanical properties of the phases. Agreement is good between the analysis and experimental results for three systems: epoxy and glass, polyethylene and wollastonite, and a polyelectrolyte salt with mica and asbestos.     

Temperature dependence of exciton diffusion in conjugated polymers

The temperature dependence of the exciton dynamics in a conjugated polymer is studied using time-resolved spectroscopy. Photoluminescence decays were measured in heterostructured samples containing a sharp polymer-fullerene interface, which acts as an exciton quenching wall. Using a 1D diffusion model, the exciton diffusion length and diffusion coefficient were extracted in the temperature range of 4-293 K. The exciton dynamics reveal two temperature regimes: in the range of 4-150 K, the exciton diffusion length (coefficient) of approximately 3 nm (approximately 1.5 x 10 (-4) cm2/s) is nearly temperature independent. Increasing the temperature up to 293 K leads to a gradual growth up to 4.5 nm (approximately 3.2 x 10 (-4) cm2/ s). This demonstrates that exciton diffusion in conjugated polymers is governed by two processes: an initial downhill migration toward lower energy states in the inhomogenously broadened density of states, followed by temperature activated hopping. The latter process is switched off below 150 K.     

Temperature modulated dynamic mechanical analysis

Temperature modulated dynamic mechanical analysis (TMDMA) was performed in the same way as temperature modulated DSC (TMDSC) measurements. Temperature modulation with amplitude 0.5 K and period 20 min was realised by a series of linear heating and cooling cycles (saw-tooth modulation). As in TMDSC TMDMA allows for the investigation of reversible and non-reversible phenomena in the melting and crystallisation region of polymers. The advantage of TMDMA compared to TMDSC is the high sensitivity for small and slow changes in crystallinity, e.g. during re-crystallisation. The combination of TMDMA and TMDSC yields new information about local processes at the surface of polymer crystallites. It is shown that during and after isothermal crystallisation the surface of the individual crystallites is in equilibrium with the surrounding melt.     

Temperature dependence of the dynamic viscosity of liquid mercury

The dependence of the dynamic viscosity of mercury on temperature is calculated and expressed in terms of the cluster associate model, based on the Boltzmann distribution and with normalization at the melting point. The resulting refined equation for mercury viscosity adequately reflects this dependence over the range of the liquid state, including the critical point.     

Temperature dependence of nanoholes free volumes in amorphous polymers

Estimation of the free volume fraction in polymers from positron annihilation lifetime data is usually obtained by assuming spherical nanoholes. Although this guess is sometimes well verified, in other cases non-spherical geometries give better agreement with theoretical predictions. Furthermore, the assumption of isotropic expansion of nanoholes (implicit in these models) could be unrealistic owing to constrained movements of the molecules. Comparison of hole-lattice theory with experimental data for some oligomeric structures gives evidence of anisotropic nanoholes expansion versus temperature.     

Strain-dependent dynamic properties of filled rubber network systems

A model for strain-dependent dynamic properties of filler loaded rubber systems has been derived based on the Links-Nodes-Blobs (L-N-B) model of percolation theory. It is the first time that a L-N-B model is applied in the study of dynamic properties of filled rubbers. The density distribution function of the number of singly connected bonds f_1a(ϵ) and the apparent yield strain amplitude ϵ_app that corresponds to the on-set point of corruption of the filler network are introduced in the model. Simulation results indicate that both f_1a(ϵ) and ϵ_app control the break-down and recombination of the filler network. Two recombination mechanism are adopted in this study. Results of simulations from the extreme ends recombination mechanism match the experimental data better than those from the zero strain recombination mechanism. Also, via the proposed model, the strain-dependent storage modulus correlates well with the peak loss modulus at a low strain range of around 0.1% to 100%. Moreover, a universal plot of the normalized storage modulus (Z_L-N-B) as a function of the normalized Log strain amplitude (ϵ₀/ϵ_app) for different rubber systems is obtained. The loss moduli of systems are also simulated by the L-N-B model.     

Temperature dependence of the fluorescence properties of curcumin

Steady-state and time-resolved techniques were employed to study the nonradiative process of curcumin dissolved in ethanol and 1-propanol in a wide range of temperatures. We found that the nonradiative rate constants at temperatures between 175-250 K qualitatively follow the same trend as the dielectric relaxation times of both neat solvents. We attribute the nonradiative process to solvent-controlled proton transfer. We also found a kinetic isotope effect on the nonradiative process rate constant of ~2. We propose a model in which the excited-state proton transfer breaks the planar hexagonal structure of the keto-enol center of the molecule. This, in turn, enhances the nonradiative process driven by the twist angle between the two phenol moieties.     

Kinetics and dynamic properties of equilibrium polymers

The statistical mechanics and scission-recombination mechanism of self-assembling linear micelles are investigated by Brownian dynamics using a newly proposed mesoscopic model representing the micelles as equilibrium polymer chains. A semidilute concentration regime, yet dynamically unentangled, is considered over a wide range of scission/recombination rates. We focus on the analysis of short and long time behaviors of the scission and recombination mechanisms. Our results show that at time scales larger than the life time of the average chain length, the kinetics is in agreement with the mean-field kinetic model proposed by Cates and Candau [J. Phys.: Condens. Matter 2, 6869 (1990)] provided the kinetic constants are estimated as effective ones. These values do take into account through a transmission coefficient that a fraction of scission/recombination events is correlated over a short time (diffusion controlled mechanism) and thus turn out to be ineffective reactive events by annihilation effects. By studying macroscopic relaxation phenomena such as the average micelle length evolution after a T jump, the monomer diffusion, and the zero shear stress relaxation function, we confirm that the effective kinetic constants found are indeed the relevant parameters when macroscopic relaxation is coupled to the kinetics of micelles.     

Ageing of filled polymers

It is tried to examine briefly all the aspects of filler interactions with polymer ageing, including direct chemical (catalysis of degradation, stabilising effects) and physical (screen and thermooptical effects, modification of transport properties) interactions as well as indirect ones such as stabiliser trapping, influence on the rate of mechanical properties change or interfacial phenomena.     

Electrical properties of filled polymers and some examples of their applications

Polymers containing electrically conductive fillers show interesting electrical properties like semiconductors and metals without losing the processability of polymers. Typical applications are as antistatic (electrostatic dissipation) materials, electro-magnetic interference shielding materials, heaters and sensors. The selection of filler and polymer governs the properties obtained in such composites.