Reduced-mobility layers with high internal mobility in poly(ethylene oxide)-silica nanocomposites

© 2017 Author(s). A series of poly(ethylene oxide) nanocomposites with spherical silica was studied by proton NMR spectroscopy, identifying and characterizing reduced-mobility components arising from either room-temperature lateral adsorption or possibly end-group mediated high-temperature bonding to the silica surface. The study complements earlier neutron-scattering results for some of the samples. The estimated thickness of a layer characterized by significant internal mobility resembling backbone rotation ranges from 2 nm for longer (20 k) chains adsorbed on 42 nm diameter particles to 0.5 nm and below for shorter (2 k) chains on 13 nm particles. In the latter case, even lower adsorbed amounts are found when hydroxy endgroups are replaced by methyl endgroups. Both heating and water addition do not lead to significant changes of the observables, in contrast to other systems such as acrylate polymers adsorbed to silica, where temperature- and solvent-induced softening associated with a glass transition temperature gradient was evidenced. We highlight the actual agreement and complementarity of NMR and neutron scattering results, with the earlier ambiguities mainly arising from different sensitivities to the component fractions and the details of their mobility

Depercolation of aggregates upon polymer grafting in simplified industrial nanocomposites studied with dielectric spectroscopy

The dynamics of polymer and filler in simplified industrial silica-styrene-butadiene nanocomposites (silica Zeosil 1165 MP, volume fraction 0-21%v) have been studied with broadband dielectric spectroscopy (BDS) and nuclear magnetic resonance (NMR). The fraction of graftable matrix chains was varied from 0 to 100%D3. The introduction of silica nanoparticles is shown to leave the segmental relaxation unaffected, an observation confirmed by the measurement of only a thin (some Angstroms thick) immobilized layer by NMR. The low-frequency measurements are resolved in two distinct dielectric Maxwell-Wagner-Sillars (MWS) processes of different behavior with respect to changes of large-scale silica structures induced by variations of filler fraction and grafting. It is found that increasing grafting leaves the first MWS-process unaffected, while it decreases the strength of the (slower) second MWS by about a decade. At constant silica volume fraction, this indicates depercolation of the filler, thereby providing a microscopic explanation of the evolution of rheological reinforcement. The sensitivity to large-scale reorganizations together with a characterization of local polymer dynamics provides insight over many length- and time-scales into structure and dynamics of nanocomposites, and thus the physical origin of the reinforcement effect.We are thankful for a “Chercheur d'Avenir” grant by the Languedoc-Roussillon region (J.O.) and Ph.D. funding “CIFRE” by Michelin (G.P.B.). The authors acknowledge financial support from the European Commission under the Seventh Framework Program by means of the grant agreement for the Integrated Infrastructure Initiative N. 262348 European Soft Matter Infrastructure (ESMI).Peer Reviewe

The Influence of Chemical Modification on Linker Rotational Dynamics in Metal–Organic Frameworks

The robust synthetic flexibility of metal–organic frameworks (MOFs) offers a promising class of tailorable materials, for which the ability to tune specific physicochemical properties is highly desired. This is achievable only through a thorough description of the consequences for chemical manipulations both in structure and dynamics. Magic angle spinning solid‐state NMR spectroscopy offers many modalities in this pursuit, particularly for dynamic studies. Herein, we employ a separated‐local‐field NMR approach to show how specific intraframework chemical modifications to MOF UiO‐66 heavily modulate the dynamic evolution of the organic ring moiety over several orders of magnitude.Intraframework ring rotations in metal–organic frameworks have been sensitively detected by dipolar dephasing over the rotor period in magic angle spinning solid‐state NMR experiments. Information on the dynamics within MOFs is important, because the rate of rotational motions of linkers affects sorption and separation properties of MOFs.Peer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/144616/1/anie201805004.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/144616/2/anie201805004-sup-0001-misc_information.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/144616/3/anie201805004_am.pd

Tuning the Properties and Self-Healing Behavior of Ionically Modified Poly(isobutylene-co-isoprene) Rubber

The focus of this work is on the nature of self-healing of ionically modified rubbers obtained by reaction of brominated poly(isobutylene-co-isoprene) rubber (BIIR) with various alkylimidazoles such as 1-methylimidazole, 1-butylimidazole, 1-hexylimidazole, 1-nonylimidazole, and 1-(6-chlorohexyl)-1H-imidazole. Based on stress-strain and temperature dependent DMA measurements, a structural influence of the introduced ionic imidazolium moieties on the formation of ionic clusters and, as a consequence, on the mechanical strength and self-healing behavior of the samples could be evidenced. These results are fully supported by a molecular-level assessment of the network structure (cross-link and constraint density) and the dynamics of the ionic clusters using an advanced proton low-field NMR technique. The results show distinct correlations between the macroscopic behavior and molecular chain dynamics of the modified rubbers. In particular, it is shown that the optimization of material properties with regard to mechanical and self-healing behavior is limited by opposing tendencies. Samples with reduced chain dynamics exhibit superior mechanical behavior but lack on self-healing behavior. In spite of these limitations, the overall performance of some of our samples including self-healing behavior exceeds distinctly that of other self-healing rubbers described in the literature so far

Microscopic State of Polymer Network Chains upon Swelling and Deformation

We use low-resolution proton NMR to probe the chain deformation in swollen and nonlinearly deformed vulcanized rubber and end-linked PDMS networks on a microscopic level, extending earlier work focusing on uniaxial stretching and isotropic dilation upon swelling toward biaxial deformation and deformation of swollen samples. Previous studies have revealed that chain deformation in bulk samples is best described by tube models, and that chains in swollen samples deform affinely after an initial desinterspersion stage, upon which entanglement-related packing effects are relieved. We test whether a subsequent deformation may also be closer to affine, and find that this is not the case. Unexpectedly, nonisotropic deformation of swollen samples also follows tube-model predictions, which is explained by a dominance of structural inhomogeneities and significant reorganization of the topological constraints active in the swollen and possibly even the bulk state.Fil: Naumova, Anna. Martin Luther Universität Halle Wittenberg; AlemaniaFil: Agudelo Mora, Diana Carolina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; ArgentinaFil: Villar, Marcelo Armando. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; Argentina. Universidad Nacional del Sur. Departamento de Ingeniería Química; ArgentinaFil: Vega, Daniel Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Física del Sur. Universidad Nacional del Sur. Departamento de Física. Instituto de Física del Sur; ArgentinaFil: Valentin, Juan Lopez. Instituto en Ciencia y Tecnología de Polímeros; España. Consejo Superior de Investigaciones Científicas; EspañaFil: Saalwächter, Kay. Martin Luther Universität Halle Wittenberg; Alemani

The Influence of Chemical Modification on Linker Rotational Dynamics in Metal–Organic Frameworks

The robust synthetic flexibility of metal–organic frameworks (MOFs) offers a promising class of tailorable materials, for which the ability to tune specific physicochemical properties is highly desired. This is achievable only through a thorough description of the consequences for chemical manipulations both in structure and dynamics. Magic angle spinning solid‐state NMR spectroscopy offers many modalities in this pursuit, particularly for dynamic studies. Herein, we employ a separated‐local‐field NMR approach to show how specific intraframework chemical modifications to MOF UiO‐66 heavily modulate the dynamic evolution of the organic ring moiety over several orders of magnitude.Ringrotationen in MOFs wurden in Festkörper‐NMR‐Experimenten unter Probenrotation um den magischen Winkel durch dipolare Dephasierung über die Rotorperiode detektiert. Informationen zur Dynamik in Metall‐organischen Gerüsten sind wichtig, weil die Geschwindigkeit der Rotationsbewegung des Linkers die Sorptions‐ und Trenneigenschaften von MOFs beeinflusst.Peer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/144665/1/ange201805004_am.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/144665/2/ange201805004-sup-0001-misc_information.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/144665/3/ange201805004.pd

Heteronuclear recoupling methods in solid-state NMR

This thesis is focused on the development of heteronuclear correlation methods in solid-state NMR spectroscopy, where the spatial dependence of the dipolar coupling is exploited to obtain structural and dynamical information in solids. Quantitative results on dipolar coupling constants are extracted by means of spinning sideband analysis in the indirect dimension of the two-dimensional experiments. The principles of sideband analysis were established and are currently widely used in the group of Prof. Spiess for the special case of homonuclear 1H double-quantum spectroscopy. The generalization of these principles to the heteronuclear case is presented, with special emphasis on naturally abundant 13C-1H systems. For proton spectroscopy in the solid state, line-narrowing is of particular importance, and is here achieved by very-fast sample rotation at the magic angle (MAS), with frequencies up to 35 kHz. Therefore, the heteronuclear dipolar couplings are suppressed and have to be recoupled in order to achieve an efficient excitation of the observed multiple-quantum modes. Heteronuclear recoupling is most straightforwardly accomplished by performing the known REDOR experiment, where pi-pulses are applied every half rotor period. This experiment was modified by the insertion of an additional spectroscopic dimension, such that heteronuclear multiple-quantum experiments can be carried out, which, as shown experimentally and theoretically, closely resemble homonuclear double-quantum experiments. Variants are presented which are well-suited for the recording of high-resolution 13C-1H shift correlation and spinning-sideband spectra, by means of which spatial proximities and quantitative dipolar coupling constants, respectively, of heteronuclear spin pairs can be determined. Spectral editing of 13C spectra is shown to be feasible with these techniques. Moreover, order phenomena and dynamics in columnar mesophases with 13C in natural abundance were investigated. Two further modifications of the REDOR concept allow the correlation of 13C with quadrupolar nuclei, such as 2H. The spectroscopic handling of these nuclei is challenging in that they cover large frequency ranges, and with the new experiments it is shown how the excitation problem can be tackled or circumvented altogether, respectively. As an example, one of the techniques is used for the identification of a yet unknown motional process of the H-bonded protons in the crystalline parts of poly(vinyl alcohol)