Phase Separation Crystallization Research Articles

Laboratory-based correlated X-ray imaging and scattering of inhomogeneous glass-ceramics

Nuclear waste glasses often contain complex microstructures, and understanding these are key to predicting and engineering glass durability, since heterogeneity may exist over multiple length scales. Here we use laboratory-based, spatially-resolved X-ray characterization methods that span length scales (10-10-10-2 m): Wide angle X-ray Scattering (WAXS) provides atomic-scale crystallography; Small Angle X-ray Scattering (SAXS) provides nanoscale phase data; X-ray Computed Tomography and projection X-ray radiography map the materials structure over the micrometer and millimeter scales. The pairing of X-ray radiography with SAXS/WAXS in the same instrument enables specific regions on the sample to be characterized with precise spatial resolution. Two molybdenum- and lanthanum-containing simulated nuclear waste glasses were examined, enabling exploration of hierarchal glassy phase separation and spatial partitioning of crystals of powellite and zircon of different morphologies and sizes 10 nm to 1 mm. The tools described in this study offer means of broadly understanding multi-scale structural attributes of multi-phase materials.

Robust Crystal Phase Separation with Distinct Charge, Orbital, and Spin Orders in AgMn7O12.

An AA'3B4O12-type A-site-ordered quadruple perovskite oxide AgMn7O12 was prepared by high-pressure and high-temperature methods. At room temperature, the compound crystallizes into a cubic Im3̅ symmetry with a charge distribution of AgMn33+Mn43.5+O12. With the temperature decreasing to TCO,OO ≈ 180 K, the compound undergoes a structural phase transition toward a monoclinic C2/m symmetry, giving rise to a B-site charge- and orbital-ordered AgMn33+Mn23+Mn24+O12 phase. Moreover, this charge-/orbital-ordered main phase coexists with the initial cubic AgMn33+Mn43.5+O12 phase in the wide temperature range we measured. The charge-/orbital-ordered phase shows two antiferromagnetic phase transitions near 125 and 90 K, respectively. Short-range ferromagnetic correlations are found to occur for the initial B-site mixed cubic phase around 35 K. Because of the robust phase separation, considerable magnetoresistance effects are observed below TCO,OO in AgMn7O12.

Morphologies, structures, and properties on blends of triblock copolymers and linear low-density polyethylene

Abstract Focusing on the study of the phase separation behavior of triblock copolymer and linear low-density polyethylene (LLDPE) systems helps to understand the influence of microstructure on the properties of poly(vinylcyclohexane)-b- poly(ethylene)-b-poly(vinylcyclohexane) (PVCH-PE-PVCH/LLDPE) blends. We prepared a series of blends of LLDPE and PVCH-PE-PVCH and explained their compatibility from the microstructure. The research findings indicate that despite having similar block compositions, PVCH-PE-PVCH with a higher molecular weight exhibits significantly stronger phase separation and crystallization ability compared to PVCH-PE-PVCH with lower molecular weight. In PVCH-PE-PVCH/LLDPE blends, the addition of 10 %, 20 %, and 30 % LLDPE induces earlier crystallization and crystal phase separation of polyethylene (PE) fragments. In addition, compared to the lower molecular weight of PVCH-PE-PVCH, the higher molecular weight of PVCH-PE-PVCH exhibits a higher tendency for independent crystallization and shows significant crystal phase separation during the cooling crystallization process when blended with LLDPE. The PE segments in the lower molecular weight of PVCH-PE-PVCH can more easily enter the nanoscale domain of LLDPE. Impact fracture electron microscopy also reveals better compatibility between the lower molecular weight of PVCH-PE-PVCH and LLDPE compared to the higher molecular weight of PVCH-PE-PVCH. Furthermore, the blends of lower molecular weight of PVCH-PE-PVCH and LLDPE exhibit a greater growth rate in elongation at break.

Morphologies of Comb-like Polyacrylic Acid/Polyacrylate Copolymers as Functions of the Degree of Derivatization with n-C22H45 Side Chains.

Polymers with crystallizable side chains have numerous applications, and their properties depend on their crystal morphologies and phase separation. Structural analysis on a wide spatial scale plays an important role in controlling the thermal properties and higher-order structures of these polymers. In this study, we elucidated the melting and crystallization processes of copolymers with varying crystallizable side-chain fractions over a wide spatial range. Differential scanning calorimetry revealed that the enthalpies of melting and crystallization increased linearly with increasing crystallizable side-chain fraction. The results of wide-angle X-ray scattering indicated that the crystal lattice was hexagonal. Conversely, spherulite-like higher-order architectures with linear structures and radial spreading were observed in the highly crystallizable components, but no micrometer-scale structures were observed in the less crystallizable components. In situ small-angle X-ray scattering was used to elucidate the phase separation and mixing processes. Lamellar crystallites were observed at crystallizable side-chain fractions of >55 wt.%, whereas small crystallites were observed at fractions of <45 wt.%. At temperatures above the order-disorder transition temperature, density fluctuations caused by correlation holes were observed. These properties have a strong effect on the crystallizable side-chain fraction.

Freeze-Concentrated Layers as a Unique Field for the Formation of Hydrogels

Abstract The phase separation of ice crystals and solutes and bound water that occurs during freezing can be used as a reaction field to control a hierarchical structure of hydrogels. Here, we present a study of carboxymethyl cellulose nanofiber (CMCF) hydrogels formed using solid-quasi liquid phase separation. CMCF hydrogels were formed simply by adding citric acid to frozen CMCF and thawing the mixture. The compressive strength of the freeze crosslinked CMCF was 200,000 times higher than that of CMCF hydrogel formed by a conventional crosslinking method. It was found that rearrangement of CMCF structures via hydrogen bonding proceeds in the freeze concentration layer before the ice crystals melt. Under freeze concentration, CMCF and bound water are confined at high concentrations. The crosslinking reaction in such a unique space contributed to the formation of CMCF hydrogel with high mechanical strength. We discuss the gelation behavior and properties of freeze crosslinked CMCF hydrogels and their applications.

Thermodynamically controlled multiphase separation of heterogeneous liquid crystal colloids

Phase separation is a universal physical transition process whereby a homogeneous mixture splits into two distinct compartments that are driven by the component activity, elasticity, or compositions. In the current work, we develop a series of heterogeneous colloidal suspensions that exhibit both liquid-liquid phase separation of semiflexible binary polymers and liquid crystal phase separation of rigid, rod-like nanocellulose particles. The phase behavior of the multicomponent mixture is controlled by the trade-off between thermodynamics and kinetics during the two transition processes, displaying cholesteric self-assembly of nanocellulose within or across the compartmented aqueous phases. Upon thermodynamic control, two-, three-, and four-phase coexistence behaviors with rich liquid crystal stackings are realized. Among which, each relevant multiphase separation kinetics shows fundamentally different paths governed by nucleation and growth of polymer droplets and nanocellulose tactoids. Furthermore, a coupled multiphase transition can be realized by tuning the composition and the equilibrium temperature, which results in thermotropic behavior of polymers within a lyotropic liquid crystal matrix. Finally, upon drying, the multicomponent mixture undergoes a hierarchical self-assembly of nanocellulose and polymers into stratified cholesteric films, exhibiting compartmentalized polymer distribution and anisotropic microporous structure.

Dynamic light scattering analysis of size-selected graphene oxide 2D colloids fractioned via liquid crystal phase separation.

Exfoliated platelets of graphene oxide (GO) can be considered as polydisperse 2D colloids that form nematic colloidal liquid crystal phases in aqueous suspension even at very low concentrations thanks to their extremely high aspect ratios. However, with the rapidly emerging scientific interest in these GO-based liquid crystals, it became clear that the precise analysis and control of the GO sheet size distribution is essential, both for their scientific understanding and for potential applications, e.g., in optoelectronic devices, nanocomposites, or catalysis. In this work, we show that the mean effective (hydrodynamic) GO platelet width can be determined from the translational diffusion coefficient with depolarized dynamic light scattering by using a model for circular, infinitely thin disks. We further studied the phase separation process of biphasic isotropic-nematic GO dispersions and developed a simple fractionation protocol, which can be used to prepare relatively monodisperse fractions of GO sheets with widths ranging from 2.0-12.4 μm. Overall, we expect that the combined application of these relatively simple fractionation and analysis methods will advance the fabrication of well-defined and size-selected GO-based systems.

Highly efficient and stable numerical algorithm for a two-component phase-field crystal model for binary alloys

This paper considers the numerical approximation of a two-component phase-field crystal model consisting of two coupled nonlinear Cahn–Hilliard equations of binary alloys. We develop a highly efficient time-marching scheme with second-order accuracy based on the SAV approach, in which two additional stabilization terms are introduced to improve stability, thus allowing large time steps. Unconditional energy stability is then proved strictly. By simulating a large number of numerical simulations in 2D and 3D, including binary crystal growth and phase separation with vacancies, we then verify the stability and accuracy of the scheme.

Comparative study of charge characteristics in PCPDTBT:fullerenes solar cells

• Spectral signal of PCPDTBT + species was obtained by spectroelectrochemistry. • Fullerene downwards shifts the HOMO level of PCPDTBT + near the D-A interface. • Fullerene promotes hole transport from near the D-A interface to polymer bulk phase. • Charge charateristics in PCPDTBT:fullerene solar cells were studied. PCPDTBT is a representative donor material for polymer solar cells, and the performance of PCPDTBT-based devices depends on the type of acceptors. To study the effect of fullerene structure on the performance of PCPDTBT-based device, the correlations among morphology, optical and electrical properties of photovoltaic devices were analyzed. The results showed that PCPDTBT:PC 71 BM had pronounced crystal order and phase separation comparing to that of PCPDTBT:PC 61 BM, which could be helpful for charge transport. Furthermore, we find the HOMO energy level of PCPDTBT + near the donor–acceptor interface was down-shifted due to interaction between donor and acceptor. The bended energy level at the interface could facilitate the hole transport from near the donor–acceptor interface to the bulk-phase of polymer, and thus reducing the charge recombination at the interface. Impedance test demonstrated that PCPDTBT:PC 71 BM device had smaller leakage current and better carrier transport, so that it showed higher power conversion efficiency than PCPDTBT:PC 61 BM device.

Formulating and Retaining the Structure of Polymerized Surfactant Phases Using a Microemulsion Curvature Framework.

Nanostructured polymers contain features smaller than 100 nm that are useful in a wide range of areas, including photonics, biomedical materials, and environmental applications. Out of the myriad of nanostructured polymers, surfactant-templated polymers are versatile because of their ability to have tunable domain sizes, structure, and composition. This work addresses the gap between the formulation with industrial-grade polymerizable surfactants and the final structure of the polymer, using the hydrophilic-lipophilic difference (HLD) and net-average curvature (NAC) frameworks. HLD indicates the proximity of the formulation (surfactant and oil monomer selection, temperature, electrolyte concentration) to the phase inversion point, where HLD = 0. NAC uses the HLD to determine the curvature of the surfactant-oil-water interface, leading not only to the size and shape of micelles and bicontinuous isotropic (L3) systems but also to defining the most likely regions for lyotropic liquid crystal (LLC) existence and phase separation in ternary phase diagrams. Polymerizing LLC fluids produced nanostructured polymers with similar LLC structures that were highly swellable, but with low compressive strength. Polymerizing L3 fluids produced strong, but less water-swellable nanostructured polymers with a similar characteristic length to the parent L3 microemulsion. The relatively small scale of the parent LLC (∼6-8 nm) or L3 (∼3-4 nm) systems is consistent with the translucent nature of the polymers produced and the HLD-NAC predicted sizes.

Effective Control of Liquid–Liquid Phase Separation and Nucleation of Vanillin Single Crystals through a Vapor Diffusion Crystallization Process in Selected Solvent Environments

An effective way of controlling the occurrence of liquid–liquid phase separation (LLPS) and nucleation of vanillin from aqueous solution was achieved through a vapor diffusion crystallization proce...

Influence of temperature on high molecular weight poly(lactic acid) stereocomplex formation

The influence of temperature on the formation of high molecular weight poly(lactic acid) (PLA) stereocomplex was studied by evaluation of the precipitates from dioxane solutions of PLA enantiomers (PLLA and PDLA). The racemic mixtures were characterized by Gel Permeation Chromatography, Infrared Spectroscopy, Differential Scanning Calorimetry, Scanning Electronic Microscopy, Wide-Angle X-ray Scattering and Vicat Softening Temperature. Precipitation was carried out under different solution temperatures, keeping constant the mixing ratio (XD), the molecular weight, the optical purity of both PLA enantiomers and the stirring rate. It was found that the precipitates contained only pure stereocomplex crystallites (racemic crystallites), without observing crystal phase separation between both homocrystals. The kinetics of the insoluble phase formation could be adjusted with the Avrami model, classically used for polymer crystallization in molten state. It was observed that the maximum PLA stereocomplex production rate was at about 40°C. However, more thermally stable racemic crystallites were formed at high solution temperatures. It was found that all the precipitates were sphere-like at 10 g·dl–1 at the solution temperature of 25, 40, 60 and 80°C

Synthesis and Characterization of Isoindigo‐Based Polymers with Thermocleavable Side Chains

AbstractStability of bulk heterojunction films for organic solar cells is a critical factor for commercial viability. One method to stabilize these films is to include cleavable side chains, which reduce the solubility of the polymers when removed. In order to study the stabilizing effect of cleavable side chains, a series of random copolymers using isoindigo with 0, 10, 20, 50, and 100% thermally cleavable side chains based on the tert‐butyloxycarbonyl (t‐BOC) group are synthesized. The polymers show a distinct one‐step thermal cleavage of the side chains, with no separable dealkylation and decarboxylation steps. The thermal stability in film is studied with transmission electron microscopy and atomic force microscopy. The polymer with all t‐BOC side chains on isoindigo significantly improves thermal stability with regard to crystal growth and phase separation in film. These results suggest BOC‐substitution can be used for large scale processing to produce insoluble polymer films with a high degree of thermal stability.

Fabrication of nano copper oxide evenly patched on cubic sodium tantalate for oriented photocatalytic reduction of carbon dioxide

A synthetic process was exploited to fabricate patchy CuO evenly planted on cubic NaTaO3 for photocatalytically reducing CO2 in isopropanol. The nano patches of CuO with about 15 nm in size were uniformly distributed on the surface of NaTaO3 via a phase-transfer protocol and solvothermal synthesis. The crystal phase, morphology, composition, optical absorption and charge separation of as-prepared CuO-NaTaO3 were characterized by XRD, SEM, TEM, EDX, XPS, UV–Vis and PL. The results of photocatalytic reduction of CO2 confirmed that the CuO patched NaTaO3 possessed better ability to separate charge carriers and selectively reduce CO2 to methanol than CuO directly loaded NaTaO3 using the traditional liquid phase reduction procedure after comparing the methanol yields. Furthermore, 5 wt% CuO patched NaTaO3 led to the highest methanol yield of 1302.22 μmol g−1 h−1. A redox mechanism was proposed and illustrated in a schematic diagram.

Suppression of the antiferromagnetic order when approaching the superconducting state in a phase-separated crystal of KxFe2−ySe2

We have combined elastic and inelastic neutron scattering techniques, magnetic susceptibility and resistivity measurements to study single-crystal samples of K$_x$Fe$_{2-y}$Se$_2$, which contain the superconducting phase that has a transition temperature of $\sim$31 K. In the inelastic neutron scattering measurements, we observe both the spin-wave excitations resulting from the block antiferromagnetic ordered phase and the resonance that is associated with the superconductivity in the superconducting phase, demonstrating the coexistence of these two orders. From the temperature dependence of the intensity of the magnetic Bragg peaks, we find that well before entering the superconducting state, the development of the magnetic order is interrupted, at $\sim$42 K. We consider this result to be evidence for the physical separation of the antiferromagnetic and superconducting phases; the suppression is possibly due to the proximity effect of the superconducting fluctuations on the antiferromagnetic order.

Enhanced thermal stability of a polymer solar cell blend induced by electron beam irradiation in the transmission electron microscope

We show by in situ microscopy that the effects of electron beam irradiation during transmission electron microscopy can be used to lock microstructural features and enhance the structural thermal stability of a nanostructured polymer:fullerene blend. Polymer:fullerene bulk-heterojunction thin films show great promise for use as active layers in organic solar cells but their low thermal stability is a hindrance. Lack of thermal stability complicates manufacturing and influences the lifetime of devices. To investigate how electron irradiation affects the thermal stability of polymer:fullerene films, a model bulk-heterojunction film based on a thiophene-quinoxaline copolymer and a fullerene derivative was heat-treated in-situ in a transmission electron microscope. In areas of the film that exposed to the electron beam the nanostructure of the film remained stable, while the nanostructure in areas not exposed to the electron beam underwent large phase separation and nucleation of fullerene crystals. UV–vis spectroscopy shows that the polymer:fullerene films are stable for electron doses up to 2000kGy.

Enhanced thermal stability of a polymer solar cell blend induced by electron beam irradiation in the transmission electron microscope

We show by in situ microscopy that the effects of electron beam irradiation during transmission electron microscopy can be used to lock microstructural features and enhance the structural thermal stability of a nanostructured polymer:fullerene blend. Polymer:fullerene bulk-heterojunction thin films show great promise for use as active layers in organic solar cells but their low thermal stability is a hindrance. Lack of thermal stability complicates manufacturing and influences the lifetime of devices. To investigate how electron irradiation affects the thermal stability of polymer:fullerene films, a model bulk-heterojunction film based on a thiophene-quinoxaline copolymer and a fullerene derivative was heat-treated in-situ in a transmission electron microscope. In areas of the film that exposed to the electron beam the nanostructure of the film remained stable, while the nanostructure in areas not exposed to the electron beam underwent large phase separation and nucleation of fullerene crystals. UV–vis spectroscopy shows that the polymer:fullerene films are stable for electron doses up to 2000kGy.

X-ray nanoscopy study on metal nano-structure formation at a metal-organic interface

Scanning transmission X-ray microscopy (STXM) with ~30-nm spatial resolution revealed at annealing effect on the metal-organic interface of an Al layer with a poly (3-hexylthiophene) (P3HT) organic semiconducting layer with and without phenyl-C61-butyric acid methyl ester (PCBM). In the case of a P3HT/Al layer with a high-tensile-strain organic over-layer, the overall interface changed to a zagged morphology with Al nano pillars after thermal annealing. On the contrary, a P3HT:PCBM/Al layer with a less-tensile-strain organic over-layer showed a smooth interface except for a few nano pillars. These interfacial morphology changes were related to the initial strain status and to the relaxation process and the phase separation of P3HT crystals relating to the PCBM. Grazing-incident wide-angle X-ray scattering (GI-WAXS) measurements were also conducted to examine the residual strain and the crystalline properties of P3HT in the presence of PCBM.

Insulating and metallic spin glass in Ni-dopedKxFe2−ySe2single crystals

We report electron doping effects by Ni in K$_{x}$Fe$_{2-\delta-y}$Ni$_{y}$Se$_{2}$ (0.06 $\leq$ $y$ $\leq$ 1.44) single crystal alloys. A rich ground state phase diagram is observed. Small amount of Ni ($\sim$ 4\%) suppressed superconductivity below 1.8 K, inducing insulating spin glass magnetic ground state for higher Ni content. With further Ni substitution, metallic resistivity is restored. For high Ni concentration in the lattice the unit cell symmetry is high symmetry $I4/mmm$ with no phase separation whereas both $I4/m + I4/mmm$ space groups were detected in the phase separated crystals when concentration of Ni $<$ Fe. The absence of superconductivity coincides with the absence of crystalline Fe vacancy order.

Anisotropic transport property anomaly in K0.8Fe1.65Se2 crystal

The anisotropic transport properties of K0.8Fe1.65Se2 crystal have been investigated with the angle θ (between the magnetic field H and c-axis) varied from 0° to 180°. It is found that the angle dependencies of the mixed state resistivities near Tc0 show a small anomalous peak on the resistive valley for H//ab, probably due to the kinked vortex structure with a lower pinning energy in the phase-separated crystal. In the normal state, the resistivities increase with increasing angles and take a maximum at H//ab, which may be related to the larger resistivity when carriers move along the c-axis driven by Lorentz force.