Quench Depth Research Articles

Phase separation dynamics of gluten protein mixtures.

We investigate by time-resolved synchrotron ultra-small X-ray scattering the dynamics of liquid-liquid phase-separation (LLPS) of gluten protein suspensions following a temperature quench. Samples at a fixed concentration (237 mg ml-1) but with different protein compositions are investigated. In our experimental conditions, we show that fluid viscoelastic samples depleted in polymeric glutenin phase-separate following a spinodal decomposition process. We quantitatively probe the late stage coarsening that results from a competition between thermodynamics that speeds up the coarsening rate as the quench depth increases and transport that slows down the rate. For even deeper quenches, the even higher viscoelasticity of the continuous phase leads to a "quasi" arrested phase separation. Anomalous phase-separation dynamics is by contrast measured for a gel sample rich in glutenin, due to elastic constraints. This work illustrates the role of viscoelasticity in the dynamics of LLPS in protein dispersions.

Characterization and phase‐transition behavior of thermoresponsive PVME nanogels in the presence of cellulose nanowhiskers: Rheology, morphology, and FTIR studies

The effects of cellulose nanowhiskers (CNWs) and irradiation dose on phase separation behavior as well as rheological and physical properties of Poly vinyl methyl ether (PVME) nanogels are investigated. Interactions between CNWs and polymer chains lead to the dehydration of PVME chains. Increasing the irradiation dose or CNW weight fraction enhances the VPTT, due to the decreased chain mobility. The phase separation behaviors of hybrid and nonhybrid nanogels are investigated at two different quench depths. At the shallow quench depth, the samples phase separate through nucleation and growth (NG) mechanism. However in the case of hybrid nanogels with a higher temperature, as a result of the enhanced dynamic asymmetry induced by the increased quench depth and the interaction of PVME chains with CNWs, the phase separation mechanism changes from NG to viscoelastic phase separation (VPS). The linear rheological behavior of nanogels was well correlated with the evolution of corresponding phase‐separating morphologies. At 40°C, a shoulder appeared in the storage modulus curve in the intermediate frequency range, due to shape relaxation of the droplets formed by NG mechanism. However, a solid‐like behavior was observed due to the existence of a percolated network structure induced by VPS at 60°C. POLYM. ENG. SCI., 59:899–912, 2019. © 2018 Society of Plastics Engineers

Quenching to the Percolation Threshold in Organic Solar Cells

Summary The general lack of knowing the quench depth and the convolution with key kinetic factors has confounded deeper understanding of the respective importance of these factors in the morphology development of organic solar cells. Here, we determine the quench depth of a high-efficiency system and delineate the need to kinetically quench the mixed domains to a composition close to the percolation threshold. Importantly, the ability to achieve such a quench is very sensitive to structural parameters in polymer solar cells (PSCs) of the polymer PBDB-TF. Only the highest-molecular-weight polymer is able of earlier liquid-solid transition to “lock in” a high-performing PSC morphology with a composition above the miscibility limit and with an efficiency of over 13%. Systems with deep quench depths are therefore sensitive to molecular weight and the kinetic factors of the casting, likely impacting fabrication yield and reliability. They also need to be vitrified for stable performance.

Dynamics of liquid-liquid phase separation of wheat gliadins

During wheat seeds development, storage proteins are synthetized and subsequently form dense protein phases, also called Protein Bodies (PBs). The mechanisms of PBs formation and the supramolecular assembly of storage proteins in PBs remain unclear. In particular, there is an apparent contradiction between the low solubility in water of storage proteins and their high local dynamics in dense PBs. Here, we probe the interplay between short-range attraction and long-range repulsion of a wheat gliadin isolate by investigating the dynamics of liquid-liquid phase separation after temperature quench. We do so using time-resolved small angle light scattering, phase contrast microscopy and rheology. We show that gliadins undergo liquid-liquid phase separation through Nucleation and Growth or Spinodal Decomposition depending on the quench depth. They assemble into dense phases but remain in a liquid-like state over an extended range of temperatures and concentrations. The analysis of phase separation kinetics reveals that the attraction strength of gliadins is in the same order of magnitude as other proteins. We discuss the respective role of competing interactions, protein intrinsic disorder, hydration and polydispersity in promoting local dynamics and providing this liquid-like behavior despite attractive forces.

Close-packed block copolymer micelles induced by temperature quenching

Close-packed structures of uniformly sized spheres are ubiquitous across diverse material systems including elements, micelles, and colloidal assemblies. However, the controlled access to a specific symmetry of self-assembled close-packed spherical particles has not been well established. We investigated the ordering of spherical block copolymer micelles in aqueous solutions that was induced by rapid temperature changes referred to as quenching. As a function of quench depth, the quenched self-assembled block copolymer micelles formed three different close-packed structures: face-centered cubic (fcc), random stacking of hexagonal-close-packed layers (rhcp), and hexagonal-close-packed (hcp). The induced hcp and rhcp structures were stable for at least a few weeks when maintained at their quench temperatures, but heating or cooling these hcp and rhcp structures transformed both structures to fcc crystallites with coarsening of the crystal grains, which suggests that these noncubic close-packed structures are intermediate states. Time-resolved scattering experiments prove that the micellar rhcp structures do not originate from the rapid growth of competing close-packed structures. We speculate that the long-lived metastable hcp and rhcp structures originate from the small size of crystal grains, which introduces a nonnegligible Laplace pressure to the crystal domains. The reported transitions from the less stable hcp to the more stable rhcp and fcc are experimental observations of Ostwald's rule manifesting the transition order of the key close-packed structures in the crystallization of close-packed uniform spheres.

Dynamic Scaling of Colloidal Gel Formation at Intermediate Concentrations.

We have examined the formation and dissolution of gels composed of intermediate volume-fraction nanoparticles with temperature-dependent short-range attractions using small-angle x-ray scattering, x-ray photon correlation spectroscopy, and rheology to obtain nanoscale and macroscale sensitivity to structure and dynamics. Gel formation after temperature quenches to the vicinity of the rheologically determined gel temperature, T_{gel}, was characterized via the slowdown of dynamics and changes in microstructure observed in the intensity autocorrelation functions and structure factor, respectively, as a function of quench depth (ΔT=T_{quench}-T_{gel}), wave vector, and formation time t_{f}. We find the wave-vector-dependent dynamics, microstructure, and rheology at a particular ΔT and t_{f} map to those at other ΔTs and t_{f}s via an effective scaling temperature, T_{s}. A single T_{s} applies to a broad range of ΔT and t_{f} but does depend on the particle size. The rate of formation implied by the scaling is a far stronger function of ΔT than expected from the attraction strength between colloids. We interpret this strong temperature dependence in terms of cooperative bonding required to form stable gels via energetically favored, local structures.

Heterogeneity Assisted Damping Enhancement of Low and High Frequency Mechanical Waves in a Soft Polymer Nanocomposite

Low-amplitude dynamic and morphological heterogeneities of a biphasic copolymeric matrix were amplified by soft nanoparticle loading and thermally induced phase separation (TIPS). The evolution of system concentration fluctuation size (ξ) was quantified as a function of quench depth in its closed-loop like phase diagram. The system characterization was then complemented by extracting its bimodal heterogeneity index as normalized interface length over area (L/A) from phase imaging analysis of atomic force microscopy (AFM). Both criteria were amplified by annealing temperature rise, resulting in damping enhancement under low and high frequency mechanical waves, shown by dynamic mechanical thermal analysis (DMTA) and ultrasound spectroscopy, respectively. At the highest annealing temperature, 160 °C, the morphogenesis led to simultaneous increase of effective damping temperature range (ΔTeff) and maximum tan δ to 190 °C and 2, respectively. Finally, damping efficacy (Deff, i.e., ΔTeff[tan δ]max) and the ultr...

Effect of selective localization of cellulose nanowhiskers on viscoelastic phase separation

Viscoelastic phase separation (VPS) is a fundamental physical phenomenon that creates percolated network structure in dynamically asymmetric mixtures. The object of this study was to investigate the effect of rod shape nanoparticles with different surface chemistries on VPS in the polystyrene/poly(vinyl methyl ether), PS/PVME, blend. For this purpose, hydrophilic (CNWs) and hydrophobic (M‐CNWs) cellulose nanowhiskers (CNWs) were prepared to be used as nanorods. Rheological measurments were employed to investigate the effect of nanowhiskers on phase separation temperature, kinetics of phase separation, and dynamic asymmetry. The evolution of morphology during the phase separation at a fixed quench depth was assessed using polarized optical microscopy. The nanowhiskers were effective in decreasing the correlation length, which slowed down the phase separation. CNWs self‐assembled into the PVME‐rich phase during the phase separation, which led to a decrease in the dynamic asymmetry and beyond a critical volume fraction of CNWs, the VPS mechanism changed to spinodal decomposition (SD). However, in the presence of M‐CNW, the localization of M‐CNWs into the PS‐rich phase enhanced the dynamic asymmetry and at 2 vol% M‐CNWs, the induced PS‐rich network by VPS was arrested. The linear and non‐linear viscoelastic behavior of the samples were studied as well. POLYM. ENG. SCI., 58:928–942, 2018. © 2017 Society of Plastics Engineers

Viscoelastic phase separation of polystyrene/poly(vinyl methyl ether) blends with different dynamic asymmetry

Viscoelastic phase separation (VPS) can be induced in dynamically asymmetric polystyrene/poly(vinyl methyl ether) (PS/PVME) blend in which there is a large difference between glass transition temperature of the components (about 125 °C). In this study, the effect of molecular weight of the slower component, PS, on VPS mechanism is investigated. The correlation between the time evolution of the phase-separating morphologies and their linear and nonlinear rheological behavior is studied for blends with three different PSs. Rheological measurements and morphological observations are carried out at quench depth of 14 °C. While it was previously found that depending on composition of blend, three different types of VPS behavior can be observed due to self-induced stresses in the early stage of phase separation—(i) the transient gel induced VPS (TG-VPS), (ii) coalescence induced VPS (C-VPS), and (iii) aggregating nucleation and growth (ANG)—in this study, we show that different types of VPS can be observed for a single composition by changing the molecular weight of PS. In other words, dynamic asymmetry between PS-rich and PVME-rich phases decreases with a decrease of molecular weight of PS which results in weaker transient gel in the early stage of phase separation. Consequently, the phase separation mechanism changes for 10/90 blend from TG-VPS to C-VPS and, for 5/95 blend from C-VPS to ANG or NNG (normal nucleation and growth). Furthermore, the variation of fractal dimension by phase separation is studied for 10/90 blends containing PS with different molecular weights.

Kinetics of polymer collapse: effect of temperature on cluster growth and aging.

Using state of the art Monte Carlo simulations of a bead-spring model we investigate both the equilibrium and the nonequilibrium behavior of the homopolymer collapse. The equilibrium properties obtained via multicanonical sampling recover the well-known finite-size scaling behavior of collapse for our model polymer. For the nonequilibrium dynamics we study the collapse by quenching the homopolymer from an expanded coiled state into the globular phase. The sequence of events observed during the collapse is independent of the quench depth. In particular, we focus on finding out universal scaling behaviors related to the growth or coarsening of clusters of monomers, by drawing phenomenological analogies with ordering kinetics. We distinguish the cluster coarsening stage from the initial stage of primary cluster formation. By successful application of a nonequilibrium finite-size scaling analysis we show that at all quench temperatures, during the coarsening stage, the cluster growth is roughly linear and can be characterised by a universal finite-size scaling function. In addition, we provide evidence of aging by constructing a suitable autocorrelation function and its corresponding dynamical power-law scaling with respect to the growing cluster sizes. The predicted theoretical bound for the exponent governing such scaling is strictly obeyed by the numerical data irrespective of the quench temperature. The results and methods presented here in general should find application in similar phenomena such as the collapse of a protein molecule preceding its folding.

Molecular Dynamics Simulation of Surface Nucleation during Growth of an Alkane Crystal

Crystal growth from the melt of n-pentacontane (C50) was studied by molecular dynamics simulation. Quenching below the melting temperature gives rise to propagation of the crystal growth front into the C50 melt from a crystalline polyethylene surface. By tracking the location of the crystal–melt interface, crystal growth rates between 0.02 and 0.05 m/s were observed, for quench depths of 10–70 K below the melting point. These growth rates compare favorably with those from a previous study by Waheed et al. [Polymer 2005, 46, 8689−8702]. Next, surface nucleation was identified with the formation of two-dimensional clusters of crystalline sites within layers parallel to the propagating growth front. Critical nucleus sizes, waiting times, and rates for surface nucleation were estimated by a mean first passage time analysis. A surface nucleation rate of ∼0.05 nm–2 ns–1 was observed, and it was nearly temperature-independent. Postcritical “spreading” of the surface nuclei to form a completely crystallized layer...

Structure Development via Reaction-Induced Phase Separation in Polymer Mixtures: Analysis of Early- and Late-Stage Demixing and Computer Simulations at Non-Isoquench Depths

ABSTRACTThe effects of phase separation during polymerization of a monomer/polymer mixture were studied. The kinetics of the spinodal decomposition of glycidyl phenyl ether/polystyrene (95/5) during polymerization was investigated using a light-scattering technique. This phase separation during polymerization was comparatively different from the one observed at the isoquench depth such that (i) there was significantly more time before any observable fluctuation, and (ii) the periodic distance of the resulting two-phase structure in the later stages decreased with time. To further investigate the influence of a continually increasing quench depth on phase separation, a diglycidyl aminophenol/diglycidyl ether of bisphenol A (50/50) system with a simple phase diagram was investigated using ultra-small-angle X-ray scattering analysis, and a similar phase separation behavior was observed. Furthermore, computer simulations using the dynamic self-consistent field method were performed to interpret polymer morphology during the demixing driven by chemical reactions. The simulation results suggested that the periodic distance of the resulting two-phase structure formed in the later stages decreases with time. The time dependence of the concentration fluctuations observed in these simulations provided a satisfying explanation for the morphologies formed as a result of a continuously increasing quench depth.

Designing disordered materials using DNA-coated colloids of bacteriophage fd and gold.

DNA has emerged as an exciting binding agent for programmable colloidal self-assembly. Its popularity derives from its unique properties: it provides highly specific short-ranged interactions and at the same time it acts as a steric stabilizer against non-specific van der Waals and Coulomb interactions. Because complementary DNA strands are linked only via hydrogen bonds, DNA-mediated binding is thermally reversible: it provides an effective attraction that can be switched off by raising the temperature only by a few degrees. In this article we introduce a new binary system made of DNA-functionalized filamentous fd viruses of ∼880 nm length with an aspect ratio of ∼100, and 50 nm gold nanoparticles (gold NPs) coated with the complementary DNA strands. When quenching mixtures below the melt temperature Tm, at which the attraction is switched on, we observe aggregation. Conversely, above Tm the system melts into a homogenous particulate 'gas'. We present the aggregation behavior of three different gold NP to virus ratios and compare them to a gel made solely of gold NPs. In particular, we have investigated the aggregate structures as a function of cooling rate and determine how they evolve as function of time for given quench depths, employing fluorescence microscopy. Structural information was extracted in the form of an effective structure factor and chord length distributions. Rapid cooling rates lead to open aggregates, while slower controlled cooling rates closer to equilibrium DNA hybridization lead to more fine-stranded gels. Despite the different structures we find that for both cooling rates the quench into the two-phase region leads to initial spinodal decomposition, which becomes arrested. Surprisingly, although the fine-stranded gel is disordered, the overall structure and the corresponding length scale distributions in the system are remarkably reproducible. Such highly porous systems can be developed into new functional materials.

Percolation of Phase-Separating Polymer Mixtures.

We study the percolation problem in a binary phase-separating polymer mixture. By well-designed experiments, we can delineate the percolation line on the phase diagram with sufficient accuracy. Our experiments show that the percolation thresholds start from the random percolation limit (Φ ∼ 0.15) located near spinodal point at T → Tc and then converge toward the geometric coalescence limit (Φ ∼ 0.36) with an increase in the quench depth. This apparent percolation difficulty comes about largely from the Rayleigh instability accompanied by large-amplitude, short-wavelength fluctuations during the spinodal decomposition at deeper quench depth. As a result, the broken "rigid" domains tend to pack closely, and the so-called droplet spinodal decomposition occurs. On the other hand, we observe that, between the selectively attractive walls, the surface-drying percolating phase will break up into droplets prematurely, thereby shifting its percolation line rather considerably. To our knowledge, such an effect is not yet predicted by theory or simulation.

A computational study of long range surface-directed phase separation in polymer blends under a temperature gradient

The surface-directed phase separation phenomena of a model binary polymer blend quenched into the unstable region of its binary symmetric phase diagram was studied numerically using the nonlinear Cahn–Hilliard theory coupled with the Flory–Huggins–de-Gennes theory. Long range surface potential within a square geometry, where one side of the domain is exposed to a surface with preferential attraction to one component of a binary polymer blend under a temperature gradient in the x-direction, was incorporated in the model. No transition from complete wetting to partial wetting for all quench depths and/or long range surface potentials was observed. The structure factor analysis for the bulk presented an exponential growth rate at the early stage of phase separation, which slowed down at the intermediate stage with a slope of 0.33, which is in agreement with the Lifshitz–Slyozov power law. As the diffusion coefficient increased, the rate of phase separation increased accordingly in the bulk. This led to faster transition time from the early to intermediate stage within the bulk. In deeper quenches, a higher rate of phase separation was observed along with lower surface enrichment. Deeper quenches also led to the faster rupture of spinodal waves in the bulk. The process of surface enrichment, however, was continuous for all quench depths studied. The effect of different temperature gradient values on the surface enrichment rate was studied for the first time within a long range surface potential setting. No noticeable change in surface enrichment was observed for different temperature gradients.

A computational study of multiple surface-directed phase separation in polymer blends under a temperature gradient

The surface-directed phase separation (SDPS) phenomena of a model binary polymer blend quenched into the unstable region of its binary symmetric upper critical solution temperature phase diagram is numerically investigated using a mathematical model composed of the nonlinear Cahn–Hilliard (CH) theory for phase separation along with the Flory–Huggins–de Gennes (FHdG) free energy functional. The SDPS occurs in a square domain with a linear temperature gradient along the horizontal direction and with all sides having short range surface potential h1. The effects of different quench depth, diffusion coefficient, surface potential, and temperature gradient were studied numerically. The numerical results indicate that there is a simultaneous competition between the four surfaces in attracting the preferred polymer. The side with a higher surface potential would win the competition against the side with a lower surface attraction in the case of a uniform quench. The numerical results also indicated a later transition time for higher values of h1. As surface potential increased, the transition time from complete wetting to partial wetting occurred at a later time on the surface. The impact of different temperature gradient ΔT*/Δx* values on the surface enrichment rate with fixed temperature at one surface and higher temperature at the opposite surface was studied for the first time within a multiple surface potential set up. The results showed that higher values of ΔT*/Δx* increased the growth rate of the preferred polymer on the surface adding to the thickness of the wetting layer. The transition time from complete wetting to partial wetting occurred slightly later at the lower temperature side.

Unusual Phase Separation Kinetics in Poly(Methyl Methacrylate)/Poly(Styrene-co-Acrylonitrile) (PMMA/SAN) Blends with PMMA of Different Molecular Weights

The influence of molecular weight of poly (methyl methacrylate) (PMMA) on the thermodynamics and dynamics of phase separation in PMMA/poly (styrene-co-acrylonitrile) (SAN) blends was investigated via optical microscopy, time-resolved small-angle light scattering (SALS), and dynamic rheological measurements. It was found that the cloud point temperature of the blends decreased with an increase in the molecular weight of the PMMA. The phase separation rates of PMMA 48K/SAN and PMMA 85K/SAN blends with the near-critical composition were almost the same at small quench depths due to the limited mobility of molecular chains at low temperatures. However, an unexpected phase separation dynamics was observed at larger quench depths. Not only the morphology evolution but also the apparent diffusion coefficient Dapp calculated from SALS revealed that the phase separation rate was faster in the PMMA 85K/SAN blend than in the PMMA 48K/SAN blend. The possible reasons for this unusual rapid kinetics of phase separation observed in the higher molecular weight blend were discussed in terms of molecular mobility and viscoelasticity.

Effects of chain entanglement on liquid-liquid phase separation behavior of LCST-type polymer blends: Cloud point and decomposition rate

By preparing homogenous blend samples with different degrees of chain entanglement, we report an anomalous contribution of chain entanglement to phase separation temperature and rate of poly(methyl methacrylate)/poly(styrene-co-maleic anhydride) (PMMA/SMA) blends presenting a typical lower critical solution temperature (LCST) behavior. The meltmixed PMMA/SMA blends with a higher chain entanglement density present a lower cloud point (Tc) and shorter delay time, but lower phase separation rate at the given temperature than solution-cast ones, suggesting that for the polymer blends with different condensed state structure, thermodynamically more facilitation to phase separation (lower Tc) is not necessarily equivalent to faster kinetics (decomposition rate). The experimental results indicate that the lower Tc of melt-mixed sample is ascribed to smaller concentration fluctuation wavelength (Λm) induced by higher entanglement degree, while higher entanglement degree in melt-mixed sample leads to a confined segmental dynamics and consequently a slower kinetics (decomposition rate) dominated by macromolecular diffusion at a comparable quench depth. These results reveal that the chain packing in polymer blends can remarkably influence the liquid-liquid phase separation behavior, which is a significant difference from decomposition of small molecular mixtures.

Coarsening of stripe patterns: variations with quench depth and scaling.

The coarsening of stripe patterns when the system is evolved from random initial states is studied by varying the quench depth ε, which is a measure of distance from the transition point of the stripe phase. The dynamics of the growth of stripe order, which is characterized by two length scales, depends on the quench depth. The growth exponents of the two length scales vary continuously with ε. The decay exponents for free energy, stripe curvature, and densities of defects like grain boundaries and dislocations also show similar variation. This implies a breakdown of the standard picture of nonequilibrium dynamical scaling. In order to understand the variations with ε we propose an additional scaling with a length scale dependent on ε. The main contribution to this length scale comes from the "pinning potential," which is unique to systems where the order parameter is spatially periodic. The periodic order parameter gives rise to an ε-dependent potential, which can pin defects like grain boundaries, dislocations, etc. This additional scaling provides a compact description of variations of growth exponents with quench depth in terms of just one exponent for each of the length scales. The relaxation of free energy, stripe curvature, and the defect densities have also been related to these length scales. The study is done at zero temperature using Swift-Hohenberg equation in two dimensions.

Electromagnetic shielding materials and coatings derived from gelation of multiwall carbon nanotubes in an LCST mixture

Thermally induced demixing in an LCST mixture, polystyrene (PS)/poly[vinyl methyl ether] (PVME), was used as a template to design materials with high electrical conductivity. This was facilitated by gelation of multiwall carbon nanotubes (MWNTs) in a given phase of the blends. The MWNTs were mixed in the miscible blends and the thermodynamic driven demixing further resulted in selective localization in the PVME phase of the blends. This was further confirmed by atomic force microscopy (AFM). The time dependent gelation of MWNTs at shallow quench depth, evaluated using isochronal temperature sweep by rheology, was studied by monitoring the melt electrical conductivity of the samples in situ by an LCR meter coupled to a rheometer. By varying the composition in the mixture, several intricate shapes like gaskets and also coatings capable of attenuating the EM radiation in the microwave frequency can be derived. For instance, the PVME rich mixtures can be molded in the form of a gasket, O-ring and other intricate shapes while the PS rich mixtures can be coated onto an insulating polymer to enhance the shielding effectiveness (SE) for EM radiation. The SE of the various materials was analyzed using a vector network analyzer in both the X-band (8.2 to 12 GHz) and the Ku-band (12 to 18 GHz) frequency. The improved SE upon gelation of MWNTs in the demixed blends is well evident by comparing the SE before and after demixing. A reflection loss of −35 dB was observed in the blends with 2 wt% MWNTs. Further, by coating a layer of ca. 0.15 mm of PS/PVME/MWNT, a SE of −15 dB at 18 GHz could be obtained.