Increase of long-chain branching by thermo-oxidative treatment of LDPE: Chromatographic, spectroscopic, and rheological evidence

Low-density polyethylene was thermo-oxidatively degraded at 170°C, i.e., degraded in the presence of air, by a one thermal cycle (1C) treatment during times between 30 and 90min, and by a two thermal cycles (2C) treatment, i.e., after storage at room temperature, an already previously degraded sample was further degraded during times between 15 and 45min. Characterization methods include gel permeation chromatography (GPC), Fourier transform infrared (FTIR) spectroscopy, as well as linear and nonlinear rheology. A reduction of molar mass was detected for all degraded samples by GPC, as well as an increase of the high molar mass fraction of the 1C sample degraded for the longest time. Intrinsic viscosity measurements indicate also a reduction of molar mass with increasing degradation times for both 1C and 2C samples. Thermo-oxidation is confirmed for 1C and 2C samples by analyzing specific indices in FTIR. Linear viscoelasticity seems to be in general only marginally affected by thermo-oxidative exposure, while the enhanced strain-hardening effect observed in uniaxial extension experiments presents a clear evidence for an increased long-chain branching (LCB) content in both 1C and 2C samples. Elongational viscosity data were analyzed by the molecular stress function (MSF) model as well as the Wagner-I model, and for both models, quantitative description of the experimental data for all samples was achieved by fit of only one nonlinear model parameter. Time-deformation separability was confirmed for all samples degraded, 1C as well as 2C, for cumulative degradation times of up to 90min. The characterization by GPC was confronted with the characterization obtained from nonlinear rheology. It can be stated that elongational rheology is a powerful method to detect structural changes due to thermo-oxidative degradation, especially the formation of enhanced LCB. It has the further advantage that experimental data can be quantified by a single nonlinear model parameter of constitutive equations like the MSF or the Wagner-I model. © 2013 The Society of Rheology

Rheological characterization and constitutive modeling of two LDPE melts

V této praci byly analyzovány experimentální reologické data dvou tavenin LDPE pomocí MSF modelu. Bylo zjištěno, že pro kvantitativní modelování obou toků bylo nutné použít pouze tři nelineární viskoelastické materiálové parametry.Experimental data of two low-density polyethylene (LDPE) melts at 200 degrees C for both shear flow (transient and steady shear viscosity as well as steady first normal stress coefficient) and elongational flow (transient and steady-state elongational viscosity) as published by Pivokonsky et al. [1] were analyzed by use of the Molecular Stress Function (MSF) model for broadly distributed, randomly branched molecular structures. For quantitative modeling of melt rheology in both types of flow and in a very wide range of deformation rates, only three nonlinear viscoelastic material parameters are needed: While the rotational parameter, a(2), and the structural parameter, beta, are found to be equal for the two melts considered, the melts differ in the parameter f(max)(2), describing maximum stretch of the polymer chains.SIP-IPN [20082971]; Mexico, by Grant Agency of the Czech Republic [A200600703]; Ministry of Education of the Czech Republic [MSM 7088352101]; German Science Foundation (DFG

Modelling elongational and shear rheology of two LDPE melts

V této praci byly analyzovány experimentální reologické data dvou tavenin LDPE pomocí MSF modelu. Bylo zjištěno, že pro kvantitativní modelování obou toků bylo nutné použít pouze tři nelineární viskoelastické materiálové parametry.Experimental data of two low-density polyethylene (LDPE) melts at 200 degrees C for both shear flow (transient and steady shear viscosity as well as transient and steady first normal stress coefficient) and elongational flow (transient and steady-state elongational viscosity) as published by Pivokonsky et al. (J Non-Newtonian Fluid Mech 135: 58-67, 2006) were analysed using the molecular stress function model for broadly distributed, randomly branched molecular structures. For quantitative modelling of melt rheology in both types of flow and in a very wide range of deformation rates, only three nonlinear viscoelastic material parameters are needed: Whilst the rotational parameter, a(2), and the structural parameter, beta, are found to be equal for the two melts considered, the melts differ in the parameter f(max)(2) describing maximum stretch of the polymer chains