Entering a New Dimension in Powder Processing for Advanced Ceramics Shaping.

Filigree structures can be manufactured via two-photon polymerization (2PP) operating in the regime of nonlinear light absorption. For the first time, it is possible to apply this technique to the powder processing of ceramic structures with a feature size in the range of the critical defect sizes responsible for brittle fracture and, thus, affecting fracture toughness of high-performance ceramics. In this way, tailoring of advanced properties can be achieved already in the shaping process. Traditionally, 2PP relies on transparent polymerizable resins, which are diametrically opposed to the usually completely opaque ceramic resins and slurries. Here a transparent and photocurable suspension of nanoparticles (resin) with very high mass fractions of yttria-stabilized zirconia particles (YSZ) is presented. Due to the extremely well-dispersed nanoparticles, scattering of light can be effectively suppressed at the process-relevant wavelength of 800 nm. Sintered ceramic structures with a resolution of down to 500 nm are obtained. Even at reduced densities of 1-4 g cm-3 , the resulting compressive strength with 4.5 GPa is equivalent or even exceeding bulk monolithic yttria-stabilized zirconia. A ceramic metamaterial is born, where the mechanical properties of yttria-stabilized zirconia are altered by changing geometrical parameters, and gives access to a new class of ceramic materials.

Predicting nonlinear physical aging of glasses from equilibrium relaxation via the material time.

The noncrystalline glassy state of matter plays a role in virtually all fields of materials science and offers complementary properties to those of the crystalline counterpart. The caveat of the glassy state is that it is out of equilibrium and therefore exhibits physical aging, i.e., material properties change over time. For half a century, the physical aging of glasses has been known to be described well by the material-time concept, although the existence of a material time has never been directly validated. We do this here by successfully predicting the aging of the molecular glass 4-vinyl-1,3-dioxolan-2-one from its linear relaxation behavior. This establishes the defining property of the material time. Via the fluctuation-dissipation theorem, our results imply that physical aging can be predicted from thermal-equilibrium fluctuation data, which is confirmed by computer simulations of a binary liquid mixture.

Time-scale ordering in hydrogen- and van der Waals-bonded liquids.

The time scales of structural relaxation are investigated on the basis of five different response functions for 1,2, 6-hexanetriol, a hydrogen-bonded liquid with a minor secondary contribution, and 2,6,10,15,19,23-hexamethyl-tetracosane (squalane), a van der Waals-bonded liquid with a prominent secondary relaxation process. Time scales of structural relaxation are derived as inverse peak frequencies for each investigated response function. For 1,2,6-hexanetriol, the ratios of the time scales are temperature-independent, while a decoupling of time scales is observed for squalane in accordance with the literature. An alternative evaluation approach is made on the squalane data, extracting time scales from the terminal relaxation mode instead of the peak position, and in this case, temperature-independent time-scale ratios are also found for squalane, despite its strong secondary relaxation contribution. Interestingly, the very same ordering of response-function-specific time scales is observed for these two liquids, which is also consistent with the observation made for simple van der Waals-bonded liquids reported previously [Jakobsen et al., J. Chem. Phys. 136, 081102 (2012)]. This time-scale ordering is based on the following response functions, from fast to slow dynamics: shear modulus, bulk modulus, dielectric permittivity, longitudinal thermal expansivity coefficient, and longitudinal specific heat. These findings indicate a general relation between the time scales of different response functions and, as inter-molecular interactions apparently play a subordinate role, suggest a rather generic nature of the process of structural relaxation.

Polyamorphism in vapor-deposited 2-methyltetrahydrofuran: A broadband dielectric relaxation study.

Depositing a simple organic molecular glass-former 2-methyltetrahydrofuran (MTHF) onto an interdigitated electrode device via physical vapor deposition gives rise to an unexpected variety of states, as revealed by dielectric spectroscopy. Different preparation parameters, such as deposition temperature, deposition rate, and annealing conditions, lead, on the one hand, to an ultrastable glass and, on the other hand, to a continuum of newfound further states. Deposition below the glass transition temperature of MTHF leads to loss profiles with shape parameters and peak frequencies that differ from those of the known bulk MTHF. These loss spectra also reveal an additional process with Arrhenius-like temperature dependence, which can be more than four decades slower than the main structural relaxation peak. At a given temperature, the time constants of MTHF deposited between 120 K and 127 K span a range of more than three decades and their temperature dependencies change from strong to fragile behavior. This polyamorphism involves at least three distinct states, each persisting for a duration many orders of magnitude above the dielectric relaxation time. These results represent a significant expansion of a previous dielectric study on vapor deposited MTHF [B. Riechers et al., J. Chem. Phys. 150, 214502 (2019)]. Plastic crystal states and the effects of weak hydrogen bonding are discussed as structural features that could explain these unusual states.

Mechanical and dielectric response within and beyond the linear regime.

In this work a comparison of dielectric and mechanical data is presented based on experiments within the linear response limit and beyond that limit. The linear dynamic and shear-mechanical response is discussed in terms of the molecular supercooled liquid tetramethyl-tetraphenyl-trisiloxane. As the dynamics measured by the two methods depict the same temperature-dependence, the underlying cause for the observed responses is assumed to be identical for both methods, namely structural relaxation. The comparison of dielectric and mechanical measurements under high excitation amplitudes reveals that this cannot be assumed for the nonlinear response: Mechanical experiments on metallic glasses suggest that involved energies are clearly beyond k B T, with observed nonlinear effects based on the activation of microstructural plastic rearrangements. In contrast, nonlinear dielectric measurements on another molecular glass-former involve energies clearly below k B T, so that nonlinear dielectric effects occur due to energy uptake from the electric field or entropy-based changes in the dynamics, but are very unlikely connected to the triggering of plastic rearrangements by the applied electric field.

Dielectric properties of vapor-deposited propylbenzenes.

Dielectric susceptibility data of vapor-deposited films of iso-propylbenzene (IPB) and n-propylbenzene (NPB) have been recorded across a wide range of deposition temperatures, Tdep, mostly below the glass transition temperature, Tg. The results for the real and imaginary components of dielectric susceptibility are compared with recently published results for 2-methyltetrahydrofuran (MTHF). Common to all three systems are the following: (i) increased kinetic stability seen as higher onset temperature for the transformation to the liquid state for Tdep ≈ 0.85Tg; (ii) the reduction of the dielectric loss (χ″) for as-deposited glasses, a signature of increased packing density that is maximal for Tdep ≈ 0.85Tg; and (iii) a reduced level of the storage component (χ') for as-deposited glasses, an effect that is almost deposition temperature invariant for Tdep < Tg. Material specific behavior is observed when heating the as-deposited films to 1.2Tg: IPB and NPB transform directly into the ordinary liquid state if judged on the basis of dielectric susceptibility, whereas MTHF has been reported to enter an unusual liquid state prior to a liquid-liquid transition at higher temperatures. These results are discussed in the context of the curious scattering results reported by Ishii et al. for some benzene derivatives, which hint at a liquid-liquid transformation.

Ultrastable and polyamorphic states of vapor-deposited 2-methyltetrahydrofuran.

This work reports results gained from dielectric spectroscopy on the organic molecular glass-former 2-methyltetrahydrofuran (MTHF), which was deposited onto an interdigitated electrode device by physical vapor deposition. By a suitable selection of preparation parameters (deposition temperature, deposition rate, and annealing conditions), various states of MTHF could be created: ultrastable glass, a liquid state with unusual dielectric properties, or the ordinary liquid state as obtained by supercooling. Observations on kinetic stability as well as on the suppression of dielectric loss in the ultrastable state resemble previous findings for other molecular glass-formers. Remarkably, after annealing just above Tg, all vapor-deposited films of MTHF display a static dielectric constant in the liquid state (εs) that is up to a factor of two below that of the ordinary bulk liquid. A structural transition to the ordinary liquid-cooled state of MTHF occurs at temperatures far above its conventional Tg, indicative of polyamorphism: the formation of an unusual structure that is achieved by physical vapor deposition and that differs from the ordinary liquid state obtained by supercooling. The present results also reveal that the dielectric constant of the as deposited glass (ε∞) is reduced to practically the value of the squared refractive index, n2.

Rate exchange rather than relaxation controls structural recovery.

We observe structural recovery after an electric field step by probing the dielectric loss profile near its maximum, which displays a field-induced shift towards lower frequencies. These dynamics display time aging-time superposition (TaTS) for the majority of relaxation modes, thus implying homogeneous recovery dynamics. Although assumed by generally accepted models, the same modes can not be responsible for structural relaxation and for structural recovery, as the former is heterogeneous and the latter is homogeneous regarding the nature of the dynamics. This conflict is resolved by proposing that structural recovery is governed by rate exchange, a process that refers to the homogeneous fluctuations of rate constants in equilibrium and restores ergodicity more slowly than the relaxation observed as a simple correlation decay. This recognition has wide-ranging consequences on how aging and nonlinear dynamics such as scanning calorimetry should be modeled.

Emergent interparticle interactions in thermal amorphous solids.

Amorphous media at finite temperatures, be them liquids, colloids, or glasses, are made of interacting particles that move chaotically due to thermal energy, continuously colliding and scattering off each other. When the average configuration in these systems relaxes only at long times, one can introduce effective interactions that keep the mean positions in mechanical equilibrium. We introduce a framework to determine the effective force laws that define an effective Hessian that can be employed to discuss stability properties and the density of states of the amorphous system. We exemplify the approach with a thermal glass of hard spheres; these experience zero forces when not in contact and infinite forces when they touch. Close to jamming we recapture the effective interactions that at temperature T depend on the gap h between spheres as T/h [C. Brito and M. Wyart, Europhys. Lett. 76, 149 (2006)EULEEJ0295-507510.1209/epl/i2006-10238-x]. For hard spheres at lower densities or for systems whose binary bare interactions are longer ranged (at any density), the emergent force laws include ternary, quaternary, and generally higher-order many-body terms, leading to a temperature-dependent effective Hessian.

Surfactant adsorption kinetics in microfluidics.

Emulsions are metastable dispersions. Their lifetimes are directly related to the dynamics of surfactants. We design a microfluidic method to measure the kinetics of adsorption of surfactants to the droplet interface, a key process involved in foaming, emulsification, and droplet coarsening. The method is based on the pH decay in the droplet as a direct measurement of the adsorption of a carboxylic acid surfactant to the interface. From the kinetic measurement of the bulk equilibration of the pH, we fully determine the adsorption process of the surfactant. The small droplet size and the convection during the droplet flow ensure that the transport of surfactant through the bulk is not limiting the kinetics of adsorption. To validate our measurements, we show that the adsorption process determines the timescale required to stabilize droplets against coalescence, and we show that the interface should be covered at more than [Formula: see text] to prevent coalescence. We therefore quantitatively link the process of adsorption/desorption, the stabilization of emulsions, and the kinetics of solute partitioning-here through ion exchange-unraveling the timescales governing these processes. Our method can be further generalized to other surfactants, including nonionic surfactants, by making use of fluorophore-surfactant interactions.

Controlling molecular transport in minimal emulsions.

Emulsions are metastable dispersions in which molecular transport is a major mechanism driving the system towards its state of minimal energy. Determining the underlying mechanisms of molecular transport between droplets is challenging due to the complexity of a typical emulsion system. Here we introduce the concept of 'minimal emulsions', which are controlled emulsions produced using microfluidic tools, simplifying an emulsion down to its minimal set of relevant parameters. We use these minimal emulsions to unravel the fundamentals of transport of small organic molecules in water-in-fluorinated-oil emulsions, a system of great interest for biotechnological applications. Our results are of practical relevance to guarantee a sustainable compartmentalization of compounds in droplet microreactors and to design new strategies for the dynamic control of droplet compositions.

Structural recovery in plastic crystals by time-resolved non-linear dielectric spectroscopy.

The dielectric relaxation of several different plastic crystals has been examined at high amplitudes of the ac electric fields, with the aim of exploring possible differences with respect to supercooled liquids. In all cases, the steady state high field loss spectrum appears to be widened, compared with its low field limit counterpart, whereas peak position and peak amplitude remain almost unchanged. This field induced change in the loss profile is explained on the basis of two distinct effects: an increased relaxation time due to reduced configurational entropy at high fields which affects the low frequency part of the spectrum, and accelerated dynamics at frequencies above the loss peak position resulting from the added energy that the sample absorbs from the external electric field. From the time-resolved assessment of the field induced changes in fictive temperatures at relatively high frequencies, we find that this structural recovery is slaved to the average rather than mode specific structural relaxation time. In other words, the very fast relaxation modes in the plastic crystal cannot adjust their fictive temperatures faster than the slower modes, the equivalent of time aging-time superposition. As a result, an explanation for this single fictive temperature must be consistent with positional order, i.e., translational motion or local density fluctuations do not govern the persistence time of local time constants.

The homogeneous ice nucleation rate of water droplets produced in a microfluidic device and the role of temperature uncertainty.

Ice nucleation was investigated experimentally in water droplets with diameters between 53 and 96 micrometres. The droplets were produced in a microfluidic device in which a flow of methyl-cyclohexane and water was combined at the T-junction of micro-channels yielding inverse (water-in-oil) emulsions consisting of water droplets with small standard deviations. In cryo-microscopic experiments we confirmed that upon cooling of such emulsion samples ice nucleation in individual droplets occurred independently of each other as required for the investigation of a stochastic process. The emulsion samples were then subjected to cooling at 1 Kelvin per minute in a differential scanning calorimeter with high temperature accuracy. From the latent heat released by freezing water droplets we inferred the volume-dependent homogeneous ice nucleation rate coefficient of water at temperatures between 236.5 and 237.9 Kelvin. A comparison of our newly derived values to existing rate coefficients from other studies suggests that the volume-dependent ice nucleation rate in supercooled water is slightly lower than previously thought. Moreover, a comprehensive error analysis suggests that absolute temperature accuracy is the single most important experimental parameter determining the uncertainty of the derived ice nucleation rates in our experiments, and presumably also in many previous experiments. Our analysis, thus, also provides a route for improving the accuracy of future ice nucleation rate measurements.