Ulrich A. Handge

Tailoring Shear-Stiff, Mica-like Nanoplatelets

This work introduces a novel facile method to produce shear-stiff, mica-like nanoplatelets by efficient exfoliation. The essence of this procedure is the nonreversible alteration of the interlamellar reactivity of a synthetic fluorohectorite by simple cation exchange. The possibility of switching from highly hydrated to collapsed interlayers permits a highly efficient exfoliation in the swollen state while providing shear-stiffness in the collapsed state. This method restricts cation exchange in the mica-like nanoplatelets to the outer surfaces, which represents a significant advantage for use in nanocomposites as compared to conventional organoclays which contain up to 40%/wt of organocations. It is expected that this new type of rigid, shear-stiff, clay-based nanoplatelets will be superior for reinforcement when used in composite materials like polymer layered silicate nanocomposites or artificial nacre.

Numerical Simulation of Mechanical Properties of Cellular Materials Using Computed Tomography Analysis

The IUPAC study ‘‘Structure and Properties of Linear and Cross-Linked Structural Polyvinylchloride Foams’’ (IUPAC no. 2003-038-4-400) of the IUPAC Subcommittee ‘‘Structure and Properties of Commercial Polymers’’ elucidates the mechanical properties of Polyvinylchloride foams. In order to predict the mechanical properties of polymer foams several simplified models were developed which take into account the density and stiffness of the bulk material, but do not apply any morphological information. Previous results on Polyvinylchloride foams indicate that the cubic model of Gibson and Ashby is not suitable to predict their compressive modulus. In this article, we discuss several alternatives for the prediction of the mechanical properties. In particular, a novel approach is presented in order to transfer cell morphological data obtained by computer tomography to realistic finite element meshes for numerical simulations. This approach allows to take into account the statistical character of the foam morphology and can be applied to predict the mechanical properties of foams. First, a computer tomography analysis was performed to determine the size distribution of the polymer foams using a nondestructive technique. The computer tomography information was applied to build finite element meshes using a tessellation of modified Kelvin cell units or truncated octahedra of various cell sizes. Then finite element simulations were performed using these meshes in order to predict the compressive behavior of polymer foams. The results of the numerical simulations were in a good agreement with those of experimental data. In conclusion, the mechanical properties of cellular polymers can be adequately predicted by taking into account the inhomogeneous foam structure, in particular the cell size distribution.

Viscoelastic properties of solutions of polystyrene melts and carbon dioxide: Analysis of a transient shear rheology approach

In this work, the viscoelastic, thermal, and diffusion properties of solutions of polystyrene melts and carbon dioxide (CO2) were analyzed using plate–plate rheometry in the transient mode. The objective of this study was to evaluate a transient shear rheology approach for high viscosity polymer melts, to verify superposition principles for polystyrene/CO2 solutions, and to measure the glass transition temperature as a function of pressure and CO2 concentration. Two different procedures of saturating polystyrene with carbon dioxide were applied, i.e., loading with the blowing agent below the glass transition temperature of polystyrene and at the measurement temperature. Stress-growth experiments in shear were performed in order to measure the transient viscosity of polystyrene/CO2 solutions in the linear regime. A shift of the transient viscosity data to a mastercurve was applied in order to determine the shift factor of the viscosity and the average relaxation time. Our data indicate that the steady-stat...

Extensional flow behavior of aqueous guar gum derivative solutions by capillary breakup elongational rheometry (CaBER)

The extensional rheological properties of aqueous ionic carboxymethyl hydroxypropyl guar gum (CMHPG) and non-ionic hydroxypropyl guar gum (HPG) solutions between the semi-dilute solution state and the concentrated network solution state were investigated by capillary breakup elongational rheometry (CaBER). Carboxymethylated guar gum derivatives show an instable filament formation in deionized water. The ratio of elongational relaxation time λE over the shear relaxation time λS follows a power law of λE/λS∼(c · [η])(-2). The difference of the relaxation times in shear and elongation can be related to the loss of entanglements and superstructures in elongational flows at higher strains.

Morphology and elasticity of polystyrene-block-polyisoprene diblock copolymers in the melt

The influence of morphology on the viscoelastic properties of melts of microphase-separated polystyrene-block-polyisoprene (PS-b-PI) diblock copolymers was investigated in oscillatory shear and creep recovery experiments. By means of anionic polymerization, three PS-b-PI diblock copolymers with a narrow molecular weight distribution and different types of morphology (spherical, cylindrical and lamellar microstructure) were prepared. Linear viscoelastic shear oscillations and creep recovery experiments in shear were performed in order to determine the elastic and viscous properties of the diblock copolymers in the melt at small and large time scales. Our analysis reveals that melts of diblock copolymers are characterized by a pronounced elastic behavior leading to a relatively large recoverable deformation in creep recovery experiments. The elasticity of the diblock copolymers is also revealed by the appearance of the creep-ringing effect. Morphological investigations were carried out to establish relations between microstructure and melt elasticity. Since ordering phenomena take place in melts of diblock copolymers until an equilibrium morphology is achieved, the storage modulus G′ of diblock copolymer melts increases with time up to a steady-state value.

Analysis of glass transition and relaxation processes of low molecular weight polystyrene-b-polyisoprene diblock copolymers

The objective of this study is to analyze the glass transition temperature and relaxation processes of low molecular weight polystyrene-block-polyisoprene diblock copolymers with different compositions, synthesized via anionic polymerization. Thermal properties were investigated by differential scanning calorimetry and dynamic-mechanical thermal analysis, while the morphologies at room temperature were investigated by transmission electron microscopy and small-angle X-ray scattering. The χN values indicate that the diblock copolymers lie near the weak segregation regime. Three different experimental techniques were applied to determine the dynamic properties, i.e., linear viscoelastic shear oscillations, creep recovery experiments, and dielectric spectroscopy. The rheological experiments were performed above the order–disorder transition temperature where the diblock copolymers behave like a Maxwell fluid. Our results indicate that the presence of the polyisoprene segments strongly influences the monomeric friction coefficient and the tendency to form entanglements above the order–disorder temperature. Consequently, the zero-shear rate viscosity of a diblock copolymer is much lower than the zero-shear rate viscosity of the neat polystyrene block (the polystyrene precursor of the polymerization procedure). Dielectric spectroscopy enables the analysis of relaxation processes below the glass transition of the polystyrene microphase. Frequency sweeps indicate the dynamic glass transition of the polyisoprene blocks, which are partly mixed with the polystyrene blocks, which are always the majority component in the block copolymers of this study.

Guidelines for checking performance and verifying accuracy of rotational rheometers: viscosity measurements in steady and oscillatory shear (IUPAC Technical Report)

Abstract The paper addresses techniques for checking the performance of rotational rheometers with cone–plate, plate–plate, or concentric cylinder geometry. We focus on the determination of the viscosity as a function of the shear rate and of the magnitude of the complex viscosity as a function of the angular frequency. After summarizing the relevant definitions and test modes, we show examples of measurements in the linear viscoelastic range, and applications of the Cox–Merz relationship. Sources of reference fluids with defined viscosities are presented, and their use in tests for verification of accuracy is demonstrated. Relevant issues, predominantly for Newtonian reference liquids, are the exploration of measurement limits, related either to the shear rate range or to reliably accessible viscosity levels. Viscoelastic reference samples are also discussed. Prerequisites for sample preparation and loading are addressed. In particular, we present recommendations based on experience from various laboratories. Finally, we discuss the problem of temperature calibration, presenting techniques that allow the determination of the true sample temperature for a given set temperature of the rheometer. This paper summarizes contributions from various industrial and academic laboratories.

Mechanical Failure of Thin Ta and Cu/Ta Layers on Polyimide Substrates: A Synchrotron‐Based Technique for In Situ Characterization

In situ synchrotron radiation diffraction and confocal light microscopy is used to study fragmentation and buckling of thin brittle Ta layers with thicknesses of 50 nm, 100 nm and 200 nm on polyimide substrates. Synchrotron‐based stress measurements confirm that cracking leads to relaxation of tensile stress. Simultaneously, compressive stress arises in transverse direction, which finally leads to buckling. This behavior can be explained quantitatively by a two‐dimensional shear lag model. It is well established that the properties of the coating‐substrate interface determine the processes of coating fragmentation and delamination. A possible approach for influencing and controlling these processes is given by the incorporation of a ductile interlayer. It can be observed that the presence of Cu interlayers with thicknesses of 5 nm, 20 nm and 50 nm reduces the fracture strength of brittle Ta coatings on polyimide substrates, whereas the resistance to buckling is increased significantly.

Exceptionally strong, stiff and hard hybrid material based on an elastomer and isotropically shaped ceramic nanoparticles

In this work the fabrication of hard, stiff and strong nanocomposites based on polybutadiene and iron oxide nanoparticles is presented. The nanocomposites are fabricated via a general concept for mechanically superior nanocomposites not based on the brick and mortar structure, thus on globular nanoparticles with nanosized organic shells. For the fabrication of the composites oleic acid functionalized iron oxide nanoparticles are decorated via ligand exchange with an α,ω-polybutadiene dicarboxylic acid. The functionalized particles were processed at 145 °C. Since polybutadiene contains double bonds the nanocomposites obtained a crosslinked structure which was enhanced by the presence of oxygen or sulfur. It was found that the crosslinking and filler percolation yields high elastic moduli of approximately 12–20 GPa and hardness of 15–18 GPa, although the polymer volume fraction is up to 40%. We attribute our results to a catalytically enhanced crosslinking reaction of the polymer chains induced by oxygen or sulfur and to the microstructure of the nanocomposite.

Analysis of stability and viscoelastic properties of melts of polystyrene-block-polyisoprene diblock copolymers in oscillatory shear and creep-recovery experiments

In this study, the rheological properties of polystyrene-block-polyisoprene (PS-b-PI) diblock copolymer melts with different types of morphology are analysed. Using the technique of anionic polymerization three different PS-b-PI diblock copolymers with a spherical, cylindrical and lamellar morphology, respectively, were synthesised. The objective of our study was to determine the viscous and elastic properties of these PS-b-PI diblock copolymers and to investigate the influence of morphology on the viscoelastic properties at short and long times. The analysis of our experiments reveals that morphological changes take place in the melt which lead to changes of the dynamic moduli. Furthermore, all three diblock copolymers of this study reveal a non-terminal behaviour in oscillatory shear flow in the microphase-separated state. Our creep recovery experiments indicate that microphase-separated diblock copolymers are characterised by a pronounced recoverable deformation.