Local and global expansivity in water.

The supra-molecular structure of a liquid is strongly connected to its dynamics, which in turn control macroscopic properties such as viscosity. Consequently, detailed knowledge about how this structure changes with temperature is essential to understand the thermal evolution of the dynamics ranging from the liquid to the glass. Here, we combine infrared spectroscopy (IR) measurements of the hydrogen (H) bond stretching vibration of water with molecular dynamics simulations and employ a quantitative analysis to extract the inter-molecular H-bond length in a wide temperature range of the liquid. The extracted expansivity of this H-bond differs strongly from that of the average nearest neighbor distance of oxygen atoms obtained through a common conversion of mass density. However, both properties can be connected through a simple model based on a random loose packing of spheres with a variable coordination number, which demonstrates the relevance of supra-molecular arrangement. Furthermore, the exclusion of the expansivity of the inter-molecular H-bonds reveals that the most compact molecular arrangement is formed in the range of ∼316-331K (i.e., above the density maximum) close to the temperature of several pressure-related anomalies, which indicates a characteristic point in the supra-molecular arrangement. These results confirm our earlier approach to deduce inter-molecular H-bond lengths via IR in polyalcohols [Gabriel et al. J. Chem. Phys. 154, 024503 (2021)] quantitatively and open a new alley to investigate the role of inter-molecular expansion as a precursor of molecular fluctuations on a bond-specific level.

Synthesis of polar polynorbornenes with high dielectric relaxation strength as candidate materials for dielectric applications.

Materials with high dielectric permittivity and dielectric relaxation strength are sought for thermal and pressure sensors and electrical energy generators. However, most polymers have either too low dielectric permittivity or are so polar that their glass transition temperature (T g) is too high and thus decomposition and side reactions occur before an electric field can polarize the polar groups. Here, we use the power and versatility of ring-opening metathesis polymerization (ROMP) to synthesize polar polymers with high dielectric relaxation strength and T g significantly below the decomposition temperature. We first synthesized six polar norbornene monomers by conventional esterification, which were then polymerized by ROMP using Grubbs first- and third-generation catalysts. The structure of the polynorbornenes obtained were verified by multinuclear NMR spectroscopy, molecular weights determined by gel permeation chromatography (GPC), and thermal properties evaluated by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). Additionally, their dielectric permittivity, conductivity, and dielectric losses were measured at different temperatures and frequencies ranging between 0.1 and 106 Hz.

Ionic Liquids [M3+ ][A- ]3 with Three-Valent Cations and Their Possible Use to Easily Separate Rare Earth Metals.

We introduce a simple way to liquify rare earth metals (REM) by incorporating the corresponding cations, in particular Eu3+ , La3+ , and Y3+ , into polyvalent ionic liquids (ILs). In contrast to conventional methods, this is achieved not by transforming them into anionic complexes, but by keeping them as bare cations and combining them with convenient, cheap and commercially available anions (A) in the form [REM3+ ][A- ]3 . To do so, we follow the COncept of Melting Point Lowering due to EThoxylation (COMPLET) with alkyl polyethylene oxide carboxylates as anions. We provide basic properties, such as glass transition temperatures, viscosities, electrical conductivities, as well as water-octanol partition constants P and show that these ILs have remarkably different properties, despite the similarity of their cations. In addition, we show that the ionic liquids possess interesting luminescent properties as non-conventional fluorophores.

Molecular heterogeneities in the thermal expansivity of polyalcohols.

Density is the key quantity for nearly all the numerous theories of the (dynamic) glass transition of supercooled liquids and melts. As mean field quantity, it is used to describe correlations and heterogeneities between regions consisting of several molecules. In contrast, the question how density is created by the interactions (i.e., bonds) within a molecule and to its nearest neighbors is almost unexplored. To investigate this for the example of a homologous series of polyalcohols (glycerol, threitol, xylitol, and sorbitol), Fourier-Transform InfraRed (FTIR) spectroscopy is carried out in a wide range of temperatures from far above to far below the calorimetric glass transition Tg. This enables us to determine the potentials and hence the bond lengths of specific intramolecular and intermolecular interactions. While the former has an expansion coefficient of (∼0.1 pm/100 K) with only smooth changes, the latter shows a 30-40 times stronger response with pronounced kinks at Tg. A comparison with the overall expansion based on mass density reveals that one has to separate between strong (OH⋅⋅⋅O) and weak (CH⋅⋅⋅O) intermolecular hydrogen (H)-bridges. Despite the fact that the latter dominates glassy dynamics, their expansivity is 5 times smaller than that of the weak H-bridges. It is to be expected that such heterogeneities on intramolecular and intermolecular scales are a general phenomenon in liquids and glassy systems demonstrating especially the necessity of atomistic simulations.

Turning Rubber into a Glass: Mechanical Reinforcement by Microphase Separation.

Supramolecular associations provide a promising route to functional materials with properties such as self-healing, easy recyclability or extraordinary mechanical strength and toughness. The latter benefit especially from the transient character of the formed network, which enables dissipation of energy as well as regeneration of the internal structures. However, recent investigations revealed intrinsic limitations in the achievable mechanical enhancement. This manuscript presents studies of a set of telechelic polymers with hydrogen-bonding chain ends exhibiting an extraordinarily high, almost glass-like, rubbery plateau. This is ascribed to the segregation of the associative ends into clusters and formation of an interfacial layer surrounding these clusters. An approach adopted from the field of polymer nanocomposites provides a quantitative description of the data and reveals the strongly altered mechanical properties of the polymer in the interfacial layer. These results demonstrate how employing phase separating dynamic bonds can lead to the creation of high-performance materials.

Hydrogen bonding and charge transport in a protic polymerized ionic liquid.

Hydrogen bonding and charge transport in the protic polymerized ionic liquid poly[tris(2-(2-methoxyethoxy)ethyl)ammoniumacryloxypropyl sulfonate] (PAAPS) are studied by combining Fourier transform infrared (FTIR) and broadband dielectric spectroscopy (BDS) in a wide temperature range from 170 to 300 K. While the former enables to determine precisely the formation of hydrogen bonds and other moiety-specific quantized vibrational states, the latter allows for recording the complex conductivity in a spectral range from 10-2 to 10+9 Hz. A pronounced thermal hysteresis is observed for the H-bond network formation in distinct contrast to the reversibility of the effective conductivity measured by BDS. On the basis of this finding and the fact that the conductivity changes with temperature by orders of magnitude, whereas the integrated absorbance of the N-H stretching vibration (being proportional to the number density of protons in the hydrogen bond network) changes only by a factor of 4, it is concluded that charge transport takes place predominantly due to hopping conduction assisted by glassy dynamics (dynamic glass transition assisted hopping) and is not significantly affected by the establishment of H-bonds.

Viscoelasticity in associating oligomers and polymers: experimental test of the bond lifetime renormalization model.

Recent findings that the association bond lifetimes τα* in associating polymers diverge from their supramolecular network relaxation times τc challenge past theories. The bond lifetime renormalization proposed by Rubinstein and coworkers [Stukalin et al., Macromolecules, 2013, 46, 7525] provides a promising explanation. To examine systematically its applicability, we employ shear rheology and dielectric spectroscopy to study telechelic associating polymers with different main chain (polypropylene glycol and polydimethylsiloxane), molecular weight (below entanglement molecular weight) and end groups (amide, and carboxylic acid) which form dimeric associations by hydrogen bonding. The separation between τc (probed by rheology) and τα* (probed by dielectric spectroscopy) strongly increases with chain length as qualitatively predicted by the model. However, to describe the increase quantitatively, a transition from Rouse to reptation dynamics must be assumed. This suggests that dynamics of super-chains must be considered to properly describe the transient network.

What dielectric spectroscopy can tell us about supramolecular networks⋆.

Polymers which can form supramolecular networks are a promising class of materials to provide highly sought-after properties such as self-healing, enhanced mechanical strength, super-stretchability as well as easy recyclability. However, due to the vast range of possible chemical structures it is very demanding to optimize these materials for the desired performance. Consequently, a detailed understanding of the molecular processes that govern the macroscopic properties is paramount to their technological application. Here we discuss some telechelic model systems with hydrogen-bonding end groups and how dielectric spectroscopy in combination with linear oscillatory shear rheology helped to understand the association mechanism on a molecular scale, and verify the model of bond-lifetime renormalization. Furthermore, we analyze a limitation of these H-bonding polymers, namely that there is a trade-off between high plateau modulus and long terminal relaxation time --both cannot be maximized at the same time. Finally, we show how more complex end groups phase separate from the main chain melt and thus lead to a more sophisticated rheological behavior which can overcome that limitation.

Wetting of soft superhydrophobic micropillar arrays.

Superhydrophobic surfaces are usually assumed to be rigid so that liquids do not deform them. Here we analyze how the relation between microstructure and wetting changes when the surface is flexible. Therefore we deposited liquid drops on arrays of flexible micropillars. We imaged the drop's surface and the bending of micropillars with confocal microscopy and analyzed the deflection of micropillars while the contact line advanced and receded. The deflection is directly proportional to the horizontal component of the capillary force acting on that particular micropillar. In the Cassie or "fakir" state, drops advance by touching down on the next top faces of micropillars, much like on rigid arrays. In contrast, on the receding side the micropillars deform. The main force hindering the slide of a drop is due to pinning at the receding side, while the force on the advancing side is negligible. In the Wenzel state, micropillars were deflected in both receding and advancing states.

Hydrogen-bond strength changes network dynamics in associating telechelic PDMS.

Associating polymers are a class of materials with widely tunable macroscopic properties. Here, we investigate telechelic poly(dimethylsiloxanes) of several molecular weights (MW) with different hydrogen bonding end groups. Besides the well-established increase of the glass transition temperature Tg with decreasing MW, Tg remains unchanged as the end group varies from NH2 over OH to COOH. For the latter system, a 2nd Tg is found which indicates a segregated phase. In contrast, rheological measurements reveal a qualitative difference in the viscoelastic response of NH2-terminated and COOH-terminated chains. Both systems show clear signs of end group association, but only the latter exhibits an extended rubbery plateau. All features observed in the rheology experiments have corresponding processes in the dielectric measurements. This provides insight into the underlying molecular mechanisms, and especially reveals that many end groups of the COOH-terminated chains phase segregate while a certain fraction forms binary associates and remains non-segregated. In contrast, the NH2-terminated systems form only binary associates increasing the effective chain length, whereas the COOH-terminated system consists of two types of associates forming a crosslinked network. Remarkably, a single species of end group forms two qualitatively different types of associates: transient bonds which allow stress release by a bond-partner exchange mechanism, and effectively permanent bonds formed by a phase segregated fraction of end groups which are stable on the timescale of the transient mechanism.

Shape of a sessile drop on a flat surface covered with a liquid film.

Motivated by the development of lubricant-infused slippery surfaces, we study a sessile drop of a nonvolatile (ionic) liquid which is embedded in a slowly evaporating lubricant film (n-decane) on a horizontal, planar solid substrate. Using laser scanning confocal microscopy we imaged the evolution of the shape of the liquid/liquid and liquid/air interfaces, including the angles between them. Results are compared to solutions of the generalized Laplace equations describing the drop profile and the annular wetting ridge. For all film thicknesses, experimental results agree quantitatively with the calculated drop and film shapes. With the verified theory we can predict height and volume of the wetting ridge. Two regimes can be distinguished: for macroscopically thick films (excess lubrication) the meniscus size is insensitive to changes in film thickness. Once the film is thin enough that surface forces between the lubricant/air and solid/lubricant interfaces become significant the meniscus changes significantly with varying film thickness (starved lubrication). The size of the meniscus is particularly relevant because it affects sliding angles of drops on lubricant-infused surfaces.

Glassy dynamics of poly(2-vinyl-pyridine) brushes with varying grafting density.

The molecular dynamics of poly(2-vinyl-pyridine) (P2VP) brushes is measured by Broadband Dielectric Spectroscopy (BDS) in a wide temperature (250 K to 440 K) and broad spectral (0.1 Hz to 1 MHz) range. This is realized using nanostructured, highly conductive silicon electrodes being separated by silica spacers as small as 35 nm. A "grafting-to"-method is applied to prepare the P2VP-brushes with five different grafting densities (0.030 nm(-2) to 0.117 nm(-2)), covering the "true-brush" regime with highly stretched coils and the "mushroom-to-brush" transition regime. The film thickness ranges between 1.8 to 7.1 (±0.2) nm. Two relaxations are observed, an Arrhenius-like process being attributed to fluctuations in the poly(glycidyl-methacrylate) (PGMA) linker used for the grafting reaction and the segmental dynamics (dynamic glass transition) of the P2VP brushes. The latter is characterized by a Vogel-Fulcher-Tammann dependence similar to bulk P2VP. The results can be comprehended considering the length scale on which the dynamic glass transition (≤1 nm) takes place.

Confinement for More Space: A Larger Free Volume and Enhanced Glassy Dynamics of 2-Ethyl-1-hexanol in Nanopores.

Broadband dielectric spectroscopy and positron annihilation lifetime spectroscopy are employed to study the molecular dynamics and effective free volume of 2-ethyl-1-hexanol (2E1H) in the bulk state and when confined in unidirectional nanopores with average diameters of 4, 6, and 8 nm. Enhanced α-relaxations with decreasing pore diameters closer to the calorimetric glass-transition temperature (T(g)) correlate with the increase in the effective free volume. This indicates that the glassy dynamics of 2D constrained 2E1H is mainly controlled by density variation.

The kinetics of mutarotation in L-fucose as monitored by dielectric and infrared spectroscopy.

Fourier Transform Infrared Spectroscopy and Broadband Dielectric Spectroscopy are combined to trace kinetics of mutarotation in L-fucose. After quenching molten samples down to temperatures between T = 313 K and 328 K, the concentrations of two anomeric species change according to a simple exponential time dependence, as seen by an increase in absorbance of specific IR-vibrations. In contrast, the dielectric spectra reveal a slowing down of the structural (α-) relaxation process according to a stretched exponential time dependence (stretching exponent of 1.5 ± 0.2). The rates of change in the IR absorption for α- and ß-fucopyranose are (at T = 313 K) nearly one decade faster than that of the intermolecular interactions as measured by the shift of the α-relaxation. This reflects the fact that the α-relaxation monitors the equilibration at a mesoscopic length scale, resulting from fluctuations in the anomeric composition.

Glassy dynamics in condensed isolated polymer chains.

In the course of miniaturization down to the nanometer scale, much remains unknown concerning how and to what extent the properties of materials are changed. To learn more about the dynamics of condensed isolated polymer chains, we used broadband dielectric spectroscopy and a capacitor with nanostructured electrodes separated by 35 nanometers. We measured the dynamic glass transition of poly(2-vinylpyridine) and found it to be bulk-like; only segments closer than 0.5 nanometer to the substrate were weakly slowed. Our approach paves the way for numerous experiments on the dynamics of isolated molecules.