Solution processable metal-organic frameworks for mixed matrix membranes using porous liquids.

The combination of well-defined molecular cavities and chemical functionality makes crystalline porous solids attractive for a great number of technological applications, from catalysis to gas separation. However, in contrast to other widely applied synthetic solids such as polymers, the lack of processability of crystalline extended solids hampers their application. In this work, we demonstrate that metal-organic frameworks, a type of highly crystalline porous solid, can be made solution processable via outer surface functionalization using N-heterocyclic carbene ligands. Selective outer surface functionalization of relatively large nanoparticles (250 nm) of the well-known zeolitic imidazolate framework ZIF-67 allows for the stabilization of processable dispersions exhibiting permanent porosity. The resulting type III porous liquids can either be directly deployed as liquid adsorbents or be co-processed with state-of-the-art polymers to yield highly loaded mixed matrix membranes with excellent mechanical properties and an outstanding performance in the challenging separation of propylene from propane. We anticipate that this approach can be extended to other metal-organic frameworks and other applications.

Micromechanics of Stress-Softening and Hysteresis of Filler Reinforced Elastomers with Applications to Thermo-Oxidative Aging.

A micromechanical concept of filler-induced stress-softening and hysteresis is established that describes the complex quasi-static deformation behavior of filler reinforced rubbers upon repeated stretching with increasing amplitude. It is based on a non-affine tube model of rubber elasticity and a distinct deformation and fracture mechanics of filler clusters in the stress field of the rubber matrix. For the description of the clusters we refer to a three-dimensional generalization of the Kantor-Webman model of flexible chain aggregates with distinct bending-twisting and tension deformation of bonds. The bending-twisting deformation dominates the elasticity of filler clusters in elastomers while the tension deformation is assumed to be mainly responsible for fracture. The cluster mechanics is described in detail in the theoretical section, whereby two different fracture criteria of filler-filler bonds are considered, denoted "monodisperse" and "hierarchical" bond fracture mechanism. Both concepts are compared in the experimental section, where stress-strain cycles of a series of ethylene-propylene-diene rubber (EPDM) composites with various thermo-oxidative aging histories are evaluated. It is found that the "hierarchical" bond fracture mechanism delivers better fits and more stable fitting parameters, though the evolution of fitting parameters with aging time is similar for both models. From the adaptations it is concluded that the crosslinking density remains almost constant, indicating that the sulfur bridges in EPDM networks are mono-sulfidic, and hence, quite stable-even at 130 °C aging temperature. The hardening of the composites with increasing aging time is mainly attributed to the relaxation of filler-filler bonds, which results in an increased stiffness and strength of the bonds. Finally, a frame-independent simplified version of the stress-softening model is proposed that allows for an easy implementation into numerical codes for fast FEM simulations.

Modeling the Full Time-Dependent Phenomenology of Filled Rubber for Use in Anti-Vibration Design.

Component design of rubber-based anti-vibration devices remains a challenge, since there is a lack of predictive models in the typical regimes encountered by anti-vibration devices that are deformed to medium dynamic strains (0.5 to 3.5) at medium strain rates (0.5/s to 10/s). An approach is proposed that demonstrates all non-linear viscoelastic effects such as hysteresis and cyclic stress softening. As it is based on a free-energy, it is fast and easily implementable. The fitting parameters behave meaningfully when changing the filler volume fraction. The model was implemented for use in the commercial finite element software ABAQUS. Examples of how to fit experimental data and simulations for a variety of carbon black filled natural rubber compounds are presented.

Carbon black networking in elastomers monitored by simultaneous rheological and dielectric investigations.

The rheo-dielectric response of carbon black filled elastomer melts is investigated by dielectric relaxation spectroscopy in the frequency range from 0.1 Hz up to 10 MHz during oszillatory shearing in a plate-plate rheometer. Various concentrations and types of carbon blacks dispersed in a non-crosslinked EPDM melt are considered. It is demonstrated that during heat treatment at low strain amplitude a pronounced flocculation of filler particles takes place leading to a successive increase of the shear modulus and conductivity. Followed up by a strain sweep, the filler network breaks up and both quantities decrease simultaneously with increasing strain amplitude. Two relaxation times, obtained from a Cole-Cole fit of the dielectric spectra, are identified, which both decrease strongly with increasing flocculation time. This behaviour is analyzed in the frame of fractal network models, describing the effect of structural disorder of the conducting carbon black network on the diffusive charge transport. Significant deviations from the predictions of percolation theory are observed, which are traced back to a superimposed cluster-cluster aggregation process (CCA). During flocculation, a universal scaling behaviour holds between the conductivity and the corresponding high frequency relaxation time, which fits all the measured data. The scaling exponent agrees fairly well with the prediction obtained from CCA. It is demonstrated that the underlying basic mechanism is a change of the correlation length of the filler network, i.e. the size of the fractal heterogeneities. This decreases during flocculation due to the formation of additional conductive paths, making the system more homogeneous. An addition less pronounced effect is found from nanoscopic gaps between adjacent filler particles, which decrease during flocculation. The same universal scaling behaviour, as obtained for flocculation, is found for temperature-dependent dielectric measurements of the cured crosslinked systems, which are heated from room temperature up to 200 °C. Thereby, the conductivity decreases significantly and the relaxation time increases, indicating that the filler network breaks up randomly due to the thermal expansion of the rubber matrix.

Molecular dynamics simulation of rupture in glassy polymer bridges within filler aggregates.

We present a series of nonequilibrium molecular dynamics simulations, investigating the rupture mechanisms in glassy polymer films confined between two solid surfaces. Such systems provide a useful model for the strong nonlinear reinforcement of rubber by colloidal filler particles. Depending on the degree of confinement three qualitatively different rupture modes have been found, which originate from the interplay of internal (polymer-polymer) and external (polymer-wall) interactions. In very thin films we observe the formation and stretching of many single-chain bridges between the confining surfaces. Progressing to thicker samples we observe fewer bridges, consisting of bundled polymer chains, and eventually just one large bridge in thick specimens. The yield stress and the elongational modulus of the polymer films have been calculated from the stress-strain curves at various temperatures and confinements and their behavior has been analyzed in terms of polymer-polymer and polymer-surface interaction energies. The thinnest films (5 monomer diameters) are always glassy in our simulations, while the others display a glass transition temperature around 0.50-0.55 (in units ε(0)/k(B) of the Lennard-Jones interaction energy), depending on their thickness. This range of values, which has been determined using both the nonequilibrium tensile simulations and equilibrium diffusion data, agrees with the transition temperature previously found by shear simulations [Baljon and Robbins, Science 271, 482 (1996)].

Evaluation of sliding friction and contact mechanics of elastomers based on dynamic-mechanical analysis.

The paper presents a combined experimental and theoretical approach to the understanding of hysteresis and adhesion contributions to rubber friction on dry and lubricated rough surfaces. Based on a proper analysis of the temperature- and frequency-dependent behaviors of nonlinear viscoelastic materials such as filler reinforced elastomer materials, master curves for the viscoelastic moduli are constructed. It is shown that the classical williams-Landel-Ferry equation cannot be applied in its simple form, but needs the introduction of an energy term describing the temperature dependency of glassy polymer bridges, which transmit the forces within flocculated filler clusters. The activation energy for carbon black and silica-filled elastomers is compared based on two different evaluation methods. The obtained dynamic data are shown to be related to a different friction behavior of elastomers regarding the two filler systems. Theoretical predictions of the stationary frictional behavior of the systems are in fair agreement with the experimental friction data at low sliding velocities. It is found that the formulated adhesion plays a dominant role on rough dry surfaces within this range of velocities.