Quench Depth Research Articles

Reconstructing the timing and conditions of fragmentation from water speciation in ash during a deep submarine eruption: 2012 eruption of Havre, Kermadec Arc

The lack of visual observations and difficulty recreating ambient conditions in the laboratory mean deep subaqueous volcanic eruptions (>500 m water depth) remain enigmatic. However, the pressure and temperature dependency of water speciation and solubility in volcanic melts and glasses, and water's high diffusion rate, offers a potential window into the processes and conditions during deep subaqueous volcanism.The 2012 submarine eruption of Havre Volcano is the ideal laboratory in which to use water species distributions to understand submarine eruption processes. Post-eruption AUV mapping, and ROV observation and sampling generated an unprecedented amount of contextual information for a deep submarine eruption including on the magma ascent conditions, eruption sequence, and magma fragmentation. Here we present high spatial resolution synchrotron-FTIR measurements of water speciation in glassy ash (125–500 μm) from several subunits (1, 2 and 3) of a widespread ash with lapilli deposit produced in the 2012 eruption.Measurements record OH depletion profiles around vesicles, along with H2Omol enrichment profiles. In several thick vesicle walls far-field regions unaffected by processes at the bubble margins have also been identified. By focusing on OH concentrations, which is effectively non-diffusing below the glass transition, we can remove the effects of secondary rehydration and calculate the pressure and water depth at which ash grain quenched.Far-field regions record quench depths within the 650–900 m water depth range for pre- and post- eruption vent depth, suggesting ash grains equilibrated at vent depth. OH depletion profiles produce quench pressures on vesicle margins typically corresponding to 200–400 m water depth shallower, suggesting a 2–4 MPa decompression before ash quench. Diffusion modelling suggests that at eruption temperature the observed OH depletion profiles formed through exsolution in <2 s. The difference in quench pressure within the ash is not reflective of a difference in the depth of quenching. Rather it is reflective of the rapidity of the quench process relative to the diffusion rate.The results imply transient low-pressure conditions formed during ash generation in the 2012 Havre eruption. We discuss several physical processes in the context of submarine volcanism that may explain the formation of transient low-pressure regions. The results have implications for how we understand submarine eruption processes and highlight the potential of high resolution FTIR for studying submarine volcanism.

An experimental study on droplet quench and steam explosion in boric acid solutions

Boric acid (H3BO3) is widely adopted as an additive in the coolant of light water reactors for reactivity control, but its effect on fuel coolant interactions (FCI) during severe accidents (especially on steam explosion) was rarely investigated. To examine the effect of the boric acid additive in coolant on steam explosion, a series of molten droplet-coolant interaction tests using H3BO3 solutions (with concentration ranging from 0–3.2% by weight) is carried out in the present study. The characteristics of melt-coolant interactions are the occurrence probability of typical phenomena (no fragmentation, minor fragmentation, or spontaneous steam explosion), lateral deformation ratio, quench depth, pressure impulse and debris particle size distribution. The statistical data of such characteristics are obtained through repeating 20 runs of the same test category. The experimental results show that the H3BO3 addition in coolant has various impacts on the above-mentioned characteristics of melt-coolant interactions, depending on the H3BO3 concentration. In particular, the probability of steam explosion sightly decreases as the H3BO3 concentration increases from zero to 1.2 wt.%, but significantly increases as the H3BO3 concentration further increases to 3.2 wt.% trough 2.2 wt.%. Namely, the inhibiting effect of boric acid on steam explosion is diminishing with increasing H3BO3 concentration beyond 1.2 wt.%. It is also found that both melt and coolant temperatures are crucial parameters impacting the likelihood and energetics of steam explosion.

Gelation Time of Network-Forming Polymer Solutions with Reversible Cross-Link Junctions of Variable Multiplicity.

The gelation time tg necessary for a solution of functional (associating) molecules to reach its gel point after a temperature jump, or a sudden concentration change, is theoretically calculated on the basis of the kinetic equation for the stepwise cross-linking reaction as a function of the concentration, temperature, functionality f of the molecules, and multiplicity k of the cross-link junctions. It is shown that quite generally tg can be decomposed into the product of the relaxation time tR and a thermodynamic factor Q. They are functions of a single scaled concentration x≡λ(T)ϕ, where λ(T) is the association constant and ϕ is the concentration. Therefore, the superposition principle holds with λ(T) as a shift factor of the concentration. Additionally, they all depend on the rate constants of the cross-link reaction, and hence it is possible to estimate these microscopic parameters from macroscopic measurements of tg. The thermodynamic factor Q is shown to depend on the quench depth. It generates a singularity of logarithmic divergence as the temperature (concentration) approaches the equilibrium gel point, while the relaxation time tR changes continuously across it. Gelation time tg obeys a power law tg-1∼xn in the high concentration region, whose power index n is related to the multiplicity of the cross-links. The retardation effect on the gelation time due to the reversibility of the cross-linking is explicitly calculated for some specific models of cross-linking to find the rate-controlling steps in order for the minimization of the gelation time to be easier in the gel processing. For a micellar cross-linking covering a wide range of the multiplicity, as seen in hydrophobically-modified water-soluble polymers, tR is shown to obey a formula similar to the Aniansson-Wall law.

Phase separation kinetics of binary mixture in the influence of bond disorder: sensitivity to quench temperature

ABSTRACT Morphologies in phase-separating systems can significantly influence final material properties. We present extensive Monte Carlo simulation results on segregation kinetics of critical binary mixture (-Ising system) with a fraction of bond disorder introduced regularly. The effect of various quench temperatures is studied on growth kinetics and scaling properties of evolved morphologies. The morphology changes from their usual bicontinuous isotropic patterns at zero disorder to short strips and lamellar patterns (anisotropy) with the increasing disorder at shallow quench depth. The domain evolution at lower disorder remains at a transient growth regime for deep quench; however, the lamellar pattern is observed at high disorder for the same quench depth. The scaling behavior changes significantly with quench depths at the higher fraction of disorder. Though, a tiny deviation is observed at lower disorder fractions for shallow quench depths. The length scale freezes () to finite size at the higher disorder asymptotically.

The Effect of Conductive Heat Transfer on the Morphology Formation in Polymer Solutions Undergoing Thermally Induced Phase Separation.

Owing to the fact that heat transfer during the thermally induced phase separation process is limited, a quench rate is inevitably entailed, which leads to the existence of temporal and spatial variations in temperature. Hence, it is of great importance to take into account the nonisothermality during the phase separation process, especially in high viscosity polymer solutions. In this study, the influence of conductive heat transfer on the morphology formation during the thermally induced phase separation process was investigated theoretically in terms of quench depth, boundary conditions, and enthalpy of demixing to elucidate the interaction between temperature and concentration through incorporating the nonlinear Cahn-Hilliard equation and the Fourier heat transfer equation in two dimensions. The Flory-Huggins free energy theory for the thermodynamics of phase separation, slow mode theory, and Rouse law for polymer diffusion without entanglements were taken into account in the model development. The simulation results indicated a strong interaction between heat transfer and phase separation, which impacted the morphology formation significantly. Results confirmed that quench depth had an indispensable impact on phase separation in terms of higher characteristic frequency by increasing the driving force for heat transfer. Applying quench from various boundaries led to a difference in the quench rate due to the high viscosity of the polymer solution. This led to a gradation in pore size and anisotropic morphology formation. The degree and direction of anisotropy depended on quench depth and rate, quench time, heat conduction rate inside the solution, solution viscosity, temperature evolution, and the enthalpy of demixing. It was also verified that the influence of enthalpy of demixing on phase separation could not be neglected as it increased the solution temperature and led to phase separation being accomplished at a higher temperature than the initial quench temperature.

Anomalous rheological aging of a model thermoreversible colloidal gel following a thermal quench.

We investigate the aging behavior in a well-studied model system comprised of a colloidal suspension of thermoreversible adhesive hard spheres (AHS) but thermally quenched below the gel transition to much larger depths than previously studied. The aging behavior in the model AHS system is monitored by small amplitude oscillatory shear rheology measurements conducted while rapidly quenching from the liquid state at 40 °C to a temperature below the gel temperature, and new, anomalous aging behaviors are observed. Shallow quenches lead to monotonic development of the elastic modulus with time, consistent with prior reports for the development of a homogeneous gel [Gordon et al., J. Rheol. 61, 23-34 (2017)]. However, for deeper quenches, a unique and new phenomenon is reported, namely, after an initial rise in the modulus, a reproducible drop in the modulus is observed, followed by a plateau in the modulus value. This drop can be gradual or sudden and the extent of the drop depends on the quench depth. After this drop in the modulus, AHS gel evolves toward a quench-path independent state over the experimental timescale. These effects of the extent of quenching on aging behavior are hypothesized to be a consequence of quenching into different underlying thermodynamic states of colloidal gels and the possible influence of the adhesive glass dynamical arrest for the deepest quenches. The research connects homogeneous gelation with heterogeneous gel formation due to phase separation and shows that the extent of quench can be used as an independent parameter to govern the rheological response of the arrested gel.

Past eruptions of a newly discovered active, shallow, silicic submarine volcano near Tokyo Bay, Japan

Abstract Oomurodashi is a newly discovered active, shallow, silicic submarine volcano only 60 km from Tokyo Bay. We reveal its past eruptive activity, and potential future hazards, by examining volatile contents of its subaerial and submarine pumice and lava deposits. These novel data for shallow silicic submarine eruption products were obtained using new Fourier transform infrared spectroscopy (FTIR) analytical techniques for vesicular and hydrated glasses. All matrix glasses have H2O species data consistent with low-temperature hydration following eruption. We therefore used unaltered OH data to investigate past eruptions. Geochemistry confirmed that Oomurodashi was the source of a ca. 13.5 ka subaerial tephra deposit on nearby inhabited islands. We infer from pumice OH contents and tephra characteristics that this deposit was formed by explosive submarine phreatomagmatic activity that produced the shallow crater in the submarine edifice. OH contents of in-place submarine lavas are lower than expected for their current water depth; comparison with past sea level implies that these lavas erupted at ca. 7–10 ka and ca. 14 ka when sea level was lower. Oomurodashi has also erupted submarine pumice with different densities, quench depths, and dispersal histories; however, any pumice sufficiently buoyant to produce floating pumice rafts will have been lost from the local geological record, so pumice rafts remain a potential future hazard.

Gelation Dynamics upon Pressure-Induced Liquid-Liquid Phase Separation in a Water-Lysozyme Solution.

Employing X-ray photon correlation spectroscopy, we measure the kinetics and dynamics of a pressure-induced liquid-liquid phase separation (LLPS) in a water-lysozyme solution. Scattering invariants and kinetic information provide evidence that the system reaches the phase boundary upon pressure-induced LLPS with no sign of arrest. The coarsening slows down with increasing quench depths. The g2 functions display a two-step decay with a gradually increasing nonergodicity parameter typical for gelation. We observe fast superdiffusive (γ ≥ 3/2) and slow subdiffusive (γ < 0.6) motion associated with fast viscoelastic fluctuations of the network and a slow viscous coarsening process, respectively. The dynamics age linearly with time τ ∝ tw, and we observe the onset of viscoelastic relaxation for deeper quenches. Our results suggest that the protein solution gels upon reaching the phase boundary.

Grafted Nanoparticle Surface Wetting during Phase Separation in Polymer Nanocomposite Films.

Wetting of polymer-grafted nanoparticles (NPs) in a polymer nanocomposite (PNC) film is driven by a difference in surface energy between components as well as bulk thermodynamics, namely, the value of the interaction parameter, χ. The interplay between these contributions is investigated in a PNC containing 25 wt % polymethyl methacrylate (PMMA)-grafted silica NPs (PMMA-NPs) in poly(styrene-ran-acrylonitrile) (SAN) upon annealing above the lower critical solution temperature (LCST, 160 °C). Atomic force microscopy (AFM) studies show that the areal density of particles increases rapidly and then approaches 80% of that expected for random close-packed hard spheres. A slightly greater areal density is observed at 190 °C compared to 170 °C. The PMMA-NPs are also shown to prevent dewetting of PNC films under conditions where the analogous polymer blend is unstable. Transmission electron microscopy (TEM) imaging shows that PMMA-NPs symmetrically wet both interfaces and form columns that span the free surface and substrate interface. Using grazing-incidence Rutherford backscattering spectrometry (GI-RBS), the PMMA-NP surface excess (Z*) initially increases rapidly with time and then approaches a constant value at longer times. Consistent with the areal density, Z* is slightly greater at deeper quench depths, which is attributed to the more unfavorable interactions between the PMMA brush and SAN segments. The Z* values at early times are used to determine the PMMA-NP diffusion coefficients, which are significantly larger than theoretical predictions. These studies provide insights into the interplay between wetting and phase separation in PNCs and can be utilized in nanotechnology applications where surface-dependent properties, such as wettability, durability, and friction, are important.

Spinodal-assisted nucleation in the two-dimensional q-state Potts model with short-to-long-range interactions.

We study homogeneous nucleation in the two-dimensional q-state Potts model for q=3,5,10,20 and ferromagnetic couplings J_{ij}∝Θ(R-|i-j|) by means of Monte Carlo simulations employing heat bath dynamics. Metastability is induced in the low-temperature phase through an instantaneous quench of the magnetic field coupled to one of the q spin states. The quench depth is adjusted, depending on the value of temperature T, interaction range R, and number of states q, in such a way that a constant nucleation time is always obtained. In this setup, we analyze the crossover between the classical compact droplet regime occurring in the presence of short-range interactions R∼1 and the long-range regime R≫1 where the properties of nucleation are influenced by the presence of a mean-field spinodal singularity. We evaluate the metastable susceptibility of the order parameter as well as various critical droplet properties, which along with the evolution of the quench depth as a function of q,T and R are then compared with the field theoretical predictions valid in the large R limit to find the onset of spinodal-assisted nucleation. We find that, with a mild dependence of the values of q and T considered, spinodal scaling holds for interaction ranges R≳8-10 and that signatures of the presence of a pseudospinodal are already visible for remarkably small interaction ranges R∼4-5. The influence of spinodal singularities on the occurrence of multistep nucleation is also discussed.

Microscopic Dynamics of Liquid-Liquid Phase Separation and Domain Coarsening in a Protein Solution Revealed by X-Ray Photon Correlation Spectroscopy.

While the interplay between liquid-liquid phase separation (LLPS) and glass formation in biological systems is highly relevant for their structure formation and thus function, the exact underlying mechanisms are not well known. The kinetic arrest originates from the slowdown at the molecular level, but how this propagates to the dynamics of microscopic phase domains is not clear. Since with diffusion, viscoelasticity, and hydrodynamics, distinctly different mechanisms are at play, the dynamics needs to be monitored on the relevant time and length scales and compared to theories of phase separation. Using x-ray photon correlation spectroscopy, we determine the LLPS dynamics of a model protein solution upon low temperature quenches and find distinctly different dynamical regimes. We observe that the early stage LLPS is driven by the curvature of the free energy and speeds up upon increasing quench depth. In contrast, the late stage dynamics slows down with increasing quench depth, fingerprinting a nearby glass transition. The dynamics observed shows a ballistic type of motion, implying that viscoelasticity plays an important role during LLPS. We explore possible explanations based on the Cahn-Hilliard theory with nontrivial mobility parameters and find that these can only partially explain our findings.

The effect of phase separation on crystallization of polyethylene/poly(ethylene-alt-propylene) blend

The influence of liquid–liquid phase separation (LLPS) on crystallization kinetics in off-critical and near-critical blends of polyethylene/poly(ethylene-alt-propylene) (PE/PEP) is studied to explore the origin of the two crystallization peaks in differential scanning calorimetry with the same long period. The PE/PEP blend systems show upper critical solution temperature (UCST) type of phase diagram and the crystallization temperature of PE component is much lower than the UCST, LLPS occurs first. The crystal nuclei first form at the interface region of two phases and then it is necessary for the PE chains to diffuse there to continue the crystallization process from both PE-rich and PEP-rich regions. As a result, the crystallization kinetics pathway is dynamically influenced by LLPS period of time, quench depth and initial composition because they control inter-diffusion coefficient in both phases. In the off-critical blend, the LLPS is extremely slow. The area ratio of the two DSC crystallization peaks doesn't fit with the ratio of coexistence compositions of PE in PE-rich and PEP-rich phases until LLPS has reached its equilibrium before crystallization. The crystallization of PE dominates the final morphology. Small and randomly dispersed crystals could be observed because the inter-diffusion of PE chains in PEP-rich phase is greatly hindered and they could not contribute to the formation of more perfect crystals. In the near-critical blend, LLPS kinetics is comparatively much faster, so the area of the two DCS crystallization peaks agrees with the coexistence compositions of PE. LLPS is the key factor to determine the final morphology.

Crystal Comets: A Geometric Model for Sculpting Anisotropic Particles from Emulsions.

Microscopic high aspect ratio particles have many applications including enhanced delivery of active ingredients and food stability. Here, we develop a simple, scalable process that produces particles with a continuously controllable aspect ratio. Oil-in-water emulsion droplets are quenched and crystallize in the presence of surfactants that facilitate the ejection of the solid oil phase from its liquid precursor. Tuning the ejection and crystallization rates to be comparable, by adjusting the surfactant concentration and quench depth, promotes anisotropic particle growth by continuously ejecting solidified oil from the precursor droplet as the crystallization proceeds. We predict the accessible morphologies using an analytical geometric model that indicates a nonconstant contact angle during the crystallization process. We see that the crystal aspect ratio is dependent on the surfactant concentration, which can be explained as a variation of the maximum growth angle achieved during crystallization.

Thermodynamic Properties and Molecular Packing Explain Performance and Processing Procedures of Three D18:NFA Organic Solar Cells.

Organic solar cells (OSCs) based on D18:Y6 have recently exhibited a record power conversion efficiency of over 18%. The initial work is extended and the device performance of D18-based OSCs is compared with three non-fullerene acceptors, Y6, IT-4F, and IEICO-4Cl, and their molecular packing characteristics and miscibility are studied. The D18 polymer shows unusually strong chain extension and excellent backbone ordering in all films, which likely contributes to the excellent hole-transporting properties. Thermodynamic characterization indicates a room-temperature miscibility for D18:Y6 and D18:IT-4F near the percolation threshold. This corresponds to an ideal quench depth and explains the use of solvent vapor annealing rather than thermal annealing. In contrast, D18:IEICO-4Cl is a low-miscibility system with a deep quench depth during casting and poor morphology control and low performance. A failure of ternary blends with PC71 BM is likely due to the near-ideal miscibility of Y6 to begin with and indicates that strategies for developing successful ternary or quaternary solar cells are likely very different for D18 than for other high-performing donors. This work reveals several unique property-performance relations of D18-based photovoltaic devices and helps guide design or fabrication of yet higher efficiency OSCs.

Dynamic Self-Consistent Field Approach for Studying Kinetic Processes in Multiblock Copolymer Melts.

The self-consistent field theory is a popular and highly successful theoretical framework for studying equilibrium (co)polymer systems at the mesoscopic level. Dynamic density functionals allow one to use this framework for studying dynamical processes in the diffusive, non-inertial regime. The central quantity in these approaches is the mobility function, which describes the effect of chain connectivity on the nonlocal response of monomers to thermodynamic driving fields. In a recent study, one of us and coworkers have developed a method to systematically construct mobility functions from reference fine-grained simulations. Here we focus on melts of linear chains in the Rouse regime and show how the mobility functions can be calculated semi-analytically for multiblock copolymers with arbitrary sequences without resorting to simulations. In this context, an accurate approximate expression for the single-chain dynamic structure factor is derived. Several limiting regimes are discussed. Then we apply the resulting density functional theory to study ordering processes in a two-length scale block copolymer system after instantaneous quenches into the ordered phase. Different dynamical regimes in the ordering process are identified: at early times, the ordering on short scales dominates; at late times, the ordering on larger scales takes over. For large quench depths, the system does not necessarily relax into the true equilibrium state. Our density functional approach could be used for the computer-assisted design of quenching protocols in order to create novel nonequilibrium materials.

Nucleation and growth of cholesteric collagen tactoids: A time-series statistical analysis based on integration of direct numerical simulation (DNS) and long short-term memory recurrent neural network (LSTM-RNN)

HypothesisLiquid-crystalline phase separation by nucleation and growth (NG) is a crucial step in the formation of collagen-based biomaterials. However, the fundamental mechanisms are not completely understood for chiral lyotropic colloidal mesogens such as collagen. MethodologyTo capture the dynamics of NG under a quenching process into the biphasic equilibrium zone, we use direct numerical simulation based on the time-dependent Ginzburg-Landau model allowing minimization of the total free energy comprised of five key contributions: phase separation (Flory-Huggins), ordering (Landau-de Gennes), chiral orientational elasticity (Frank-Oseen-Mermin), interfacial and coupling effects. LSTM-RNN is applied as a surrogate model to greatly enrich the results. Significant correlations are established using Symbolic Regression. FindingsWe quantify the NG boundaries existing in the collagen phase diagram that has recently been developed and validated by our thermodynamic model (Khadem and Rey, 2019 [1]). We characterize the three NG stages (induction, nucleation, and coarsening) in terms of tactoids’ shape, morphology, growth laws, and population across the NG zone. Wide-range generic correlations are developed, revealing the quench depth dependence of NG characteristics and connecting the sequential NG stages. We confirm experimental observations on time-dependent growth law exponent changes from an initial n≈0.5 for the mass transfer limited regime to n≈1 for the volume-driven phase ordering regime upon increasing quench depth during the nucleation period and having exclusively a value of n≈0.5 for the coarsening period regardless of quench depth. We lastly uncover the underlying physics behind the NG phenomena.

Interplay between Glass Formation and Liquid-Liquid Phase Separation Revealed by the Scattering Invariant.

The interplay of the glass transition with liquid-liquid phase separation (LLPS) is a subject of intense debate. We use the scattering invariant Q to probe how approaching the glass transition affects the shape of LLPS boundaries in the temperature/volume fraction plane. Two protein systems featuring kinetic arrest with a lower and an upper critical solution temperature phase behavior, respectively, are studied varying the quench depth. Using Q we noninvasively identify system-dependent differences for the effect of glass formation on the LLPS boundary. The glassy dense phase appears to enter the coexistence region for the albumin-YCl3 system, whereas it follows the equilibrium binodal for the γ-globulin-PEG system.

"Dense diffusion" in colloidal glasses: short-ranged long-time self-diffusion as a mechanistic model for relaxation dynamics.

Despite decades of exploration of the colloidal glass transition, mechanistic explanation of glassy relaxation processes has remained murky. State-of-the-art theoretical models of the colloidal glass transition such as random first order transition theory, active barrier hopping theory, and non-equilibrium self-consistent generalized Langevin theory assert that relaxation reported at volume fractions above the ideal mode coupling theory prediction φg,MCT requires some sort of activated process, and that cooperative motion plays a central role. However, discrepancies between predicted and measured values of φg and ambiguity in the role of cooperative dynamics persist. Underlying both issues is the challenge of conducting deep concentration quenches without flow and the difficulty in accessing particle-scale dynamics. These two challenges have led to widespread use of fitting methods to identify divergence, but most a priori assume divergent behavior; and without access to detailed particle dynamics, it is challenging to produce evidence of collective dynamics. We address these limitations by conducting dynamic simulations accompanied by experiments to quench a colloidal liquid into the putative glass by triggering an increase in particle size, and thus volume fraction, at constant particle number density. Quenches are performed from the liquid to final volume fractions 0.56 ≤ φ ≤ 0.63. The glass is allowed to age for long times, and relaxation dynamics are monitored throughout the simulation. Overall, correlated motion acts to release dynamics from the glassy plateau - but only over length scales much smaller than a particle size - allowing self-diffusion to re-emerge; self-diffusion then relaxes the glass into an intransient diffusive state, which persists for φ < 0.60. We observe similar relaxation dynamics up to φ = 0.63 before achieving the intransient state. We find that this long-time self-diffusion is short-ranged: analysis of mean-square displacement reveals a glassy cage size a fraction of a particle size that shrinks with quench depth, i.e. increasing volume fraction. Thus the equivalence between cage size and particle size found in the liquid breaks down in the glass, which we confirm by examining the self-intermediate scattering function over a range of wave numbers. The colloidal glass transition can hence be viewed mechanistically as a shift in the long-time self-diffusion from long-ranged to short-ranged exploration of configurations. This shift takes place without diverging dynamics: there is a smooth transition as particle mobility decreases dramatically with concomitant emergence of a dense local configuration space that permits sampling of many configurations via local particle motion.

Delineation of Thermodynamic and Kinetic Factors that Control Stability in Non-fullerene Organic Solar Cells

Summary Although non-fullerene small molecular acceptors (NF-SMAs) are dominating current research in organic solar cells (OSCs), measurements of thermodynamics drivers and kinetic factors determining their morphological stability are lacking. Here, we delineate and measure such factors in crystallizable NF-SMA blends and discuss four model systems with respect to their meta-stability and degree of vitrification. We determine for the first time the amorphous-amorphous phase diagram in an NF-SMA system and show that its deep quench depth can result in severe burn-in degradation. We estimate the relative phase behavior of four other materials systems. Additionally, we derive room-temperature diffusion coefficients and conclude that the morphology needs to be stabilized by vitrification corresponding to diffusion constants below 10−22 cm2/s. Our results show that to achieve stability via rational molecular design, the thermodynamics, glass transition temperature, diffusion properties, and related structure-function relations need to be more extensively studied and understood.

Path-Dependent Preparation of Complex Micelle Packings of a Hydrated Diblock Oligomer.

Small-angle X-ray scattering analyses reveal that the hydrated diblock oligomer n-C16H23(OCH2CH2)20-OH (C16E20 or Brij 58) forms lyotropic liquid crystals (LLCs) exhibiting face-centered cubic (FCC), body-centered cubic (BCC), Frank–Kasper (FK) A15, and cylindrical (HI) morphologies over the concentration range 30–65 wt % amphiphile. Heating LLCs comprising 54–59 wt % C16E20 drives the temperature-dependent phase transition sequence: A15 → BCC → HI. However, rapidly quenching the resulting HI phase from 70 to 25 °C initially forms a BCC phase that isothermally transforms into a complex, tetragonal FK σ phase comprising 30 quasispherical micelles. The metastability of this micellar σ phase is shown to depend on the sample cooling rate, thermal quench depth, and isothermal annealing temperature. We rationalize the preference for the A15 structure at 25 °C in terms of minimizing unfavorable water/hydrophobic contacts, while maximizing local particle sphericity. The symmetry breaking transition kinetics in these micellar LLCs apparently stem from the temperature-dependent activation barriers for phase nucleation and growth, which are intimately coupled to the time scales for micelle reconfiguration by amphiphile chain exchange and their spatial rearrangement. These findings highlight how thermal processing influences nucleation and growth of the self-assembled morphologies of intrinsically reconfigurable, soft spherical particles.