Rheological and Mechanical Gradient Properties of Polyurethane Elastomers for 3D-Printing with Reactive Additives

Polyurethane (PU) elastomers with their broad range of strength and elasticity are ideal materials for additive manufacturing of shapes with gradients of mechanical properties. By adjusting the mixing ratio of different polyurethane reactants during 3D-printing it is possible to change the mechanical properties. However, to guarantee intra- and inter-layer adhesion, it is essential to know the reaction kinetics of the polyurethane reaction, and to be able to influence the reaction speed in a wide range. In this study, the effect of adding three different catalysts and two inhibitors to the reaction of polyurethane elastomers were studied by comparing the time of crossover points between storage and loss modulus G′ and G′′ from time sweep tests of small amplitude oscillatory shear at 30°C. The time of crossover points is reduced with the increasing amount of catalysts, but only the reaction time with one inhibitor is significantly delayed. The reaction time of 90% NCO group conversion calculated from the FTIR-spectrum also demonstrates the kinetics of samples with different catalysts. In addition, the relation between the conversion as determined from FTIR spectroscopy and the mechanical properties of the materials was established. Based on these results, it is possible to select optimized catalysts and inhibitors for polyurethane 3D-printing of materials with gradients of mechanical properties.DFG, 414044773, Open Access Publizieren 2019 - 2020 / Technische Universität Berli

Modeling elongational viscosity of polystyrene Pom-Pom/linear and Pom-Pom/star blends

The elongational rheology of blends of a polystyrene (PS) Pom-Pom with two linear polystyrenes was recently reported by Hirschberg et al. (J. Rheol. 2023, 67:403–415). The Pom-Pom PS280k-2x22-22k with a self-entangled backbone (M$_{w,bb}$ = 280 kg/mol) and 22 entangled sidearms (M$_{w,a}$ = 22 kg/mol) at each of the two branch points was blended at weight fractions from 75 to 2 wt% with two linear polystyrenes (PS) having M$_w$ of 43 kg/mol (PS43k) and 90 kg/mol (PS90k), respectively. While the pure Pom-Pom shows strong strain hardening in elongational flow (SHF > 100), strain hardening (SHF > 10) is still observed in Pom-Pom/linear blends containing only 2 wt% of Pom-Pom. The elongational start-up viscosities of the blends with Pom-Pom weight fractions above 10 wt% are well described by the Molecular Stress Function (MSF) model, however, requiring two nonlinear fit parameters. Here we show that quantitative and parameter-free modeling of the elongational viscosity data is possible by the Hierarchical Multi-mode Molecular Stress Function (HMMSF) model based on the concepts of hierarchical relaxation and dynamic dilution. In addition, we investigated the elongational viscosity of a blend consisting of 20 wt% Pom-Pom PS280k-2x22-22k and 80 wt% of a PS star with 11 arms of M$_{w,a}$ = 25 kg/mol having a similar span molecular weight as PS43k and similar M$_{w,a}$ as the Pom-Pom. This work might open up possibilities toward polymer upcycling of less-defined polymers by adding a polymer with optimized topology to gain the intended strain hardening, e.g., for film blowing applications

Modeling elongational viscosity and brittle fracture of 10 polystyrene Pom-Poms by the hierarchical molecular stress function model

A Pom-Pom polymer with qa side chains of molecular weight Mw,a at both ends of a backbone chain of molecular weight Mw,b is the simplest branched polymer topology. Ten nearly monodisperse polystyrene Pom-Pom systems synthesized via an optimized anionic polymerization and a grafting-onto method with Mw,b of 100 to 400 kg/mol, Mw,a of 9 to 50 kg/mol, and qa between 9 and 22 are considered. We analyze the elongational rheology of the Pom-Poms by use of the hierarchical multi-mode molecular stress function (HMMSF) model, which has been shown to predict the elongational viscosity of linear and long-chain branched (LCB) polymer melts based exclusively on the linear-viscoelastic characterization and a single material parameter, the so-called dilution modulus GD. For the Pom-Poms considered here, we show that GD can be identified with the plateau modulus G0N=GD, and the modeling of the elongational viscosity of the Pom-Poms does therefore not require any fitting parameter but is fully determined by the linear-viscoelastic characterization of the melts. Due to the high strain hardening of the Pom-Poms, brittle fracture is observed at higher strains and strain rates, which is well described by the entropic fracture criterion

Elongational viscosity and brittle fracture of bidisperse blends of a high and several low molar mass polystyrenes

Elongational viscosity data of four well-characterized blends consisting of 10% mass fraction of monodisperse polystyrene PS-820k (molar mass of 820 kg/mol) and 90% matrix polystyrenes with a molar mass of 8.8, 23, 34, and 73 kg/mol, respectively, as reported by Shahid et al. Macromolecules 52: 2521–2530, 2019 are analyzed by the extended interchain pressure (EIP) model including the effects of finite chain extensibility and filament rupture. Except for the linear-viscoelastic contribution of the matrix, the elongational viscosity of the blends is mainly determined by the high molar mass component PS-820k at elongation rates when no stretching of the lower molar mass matrix chains is expected. The stretching of the long chains is shown to be widely independent of the molar mass of the matrix reaching from non-entangled oligomeric styrene (8.8 kg/mol) to well-entangled polystyrene (73kg/mol). Quantitative agreement between data and model can be obtained when taking the interaction of the long chains of PS-820k with the shorter matrix chains of PS-23k, PS-34k, and PS-73k into account. The interaction of long and short chains leads to additional entanglements along the long chains of PS-820k, which slow down relaxation of the long chains, as clearly seen in the linear-viscoelastic behavior. According to the EIP model, an increased number of entanglements also lead to enhanced interchain pressure, which limits maximal stretch. The reduced maximal stretch of the long chains due to entanglements of long chains with shorter matrix chains is quantified by introducing an effective polymer fraction of the long chains, which increases with the increasing length of the matrix chains resulting in the excellent agreement of experimental data and model predictions.TU Berlin, Open-Access-Mittel – 202

The elastic stiffness tensor of cellulosic viscose fibers measured with Brillouin spectroscopy

Brillouin light scattering spectroscopy (BLS) is applied to study the micromechanics of cellulosic viscose fibers, one of the commercially most important, man-made biobased fibers. Using an equal angle scattering geometry, we provide a thorough description of the procedure to determine the complete transversely isotropic elastic stiffness tensor. From the stiffness tensor the engineering-relevant material parameters such as Young's moduli, shear moduli, and Poisson's ratios in radial and axial fiber direction are evaluated. The investigated fiber type shows that, at ideal conditions, the material exhibits optical waveguide properties resulting in spontaneous Brillouin backscattering which can be used to obtain additional information from the Brillouin spectra, enabling the measurement of two different scattering processes and directions with only one scattering geometry

A Compact Two-Frequency Notch Filter for Millimeter Wave Plasma Diagnostics

Sensitive millimeter wave diagnostics in magnetic confinement plasma fusion experiments need protection from gyrotron stray radiation in the plasma vessel. Modern electron cyclotron resonance heating (ECRH) systems take advantage of multifrequency gyrotrons. This means that the frequency band of some millimeter wave diagnostics contains more than one narrow-band gyrotron-frequency line, which needs to be effectively suppressed. A compact standard waveguide notch filter based on coupled waveguide resonators with rectangular cross-section is presented which can provide very high suppression of several gyrotron frequencies and has low insertion loss of the passband