Phase Separation Boundary Research Articles

Generic Nature of Interfacial Phenomena in Solutions of Nonionic Hydrotropes.

Nonionic hydrotropes (low-molecular-weight amphiphiles) demonstrate striking dual actions in bulk solutions and interfaces, exhibiting both surfactant-like and co-solvent properties. We report on peculiar, strongly affected by this duality, liquid-liquid and air-liquid-liquid interfacial behavior in aqueous ternary systems, containing hydrotropes and hydrocarbons, in a broad range of compositions and at various temperatures. Phase diagrams of the studied systems, containing tertiary butanol (TBA), as a hydrotrope, are of Type 1: the hydrotrope, at the experimental conditions, is completely miscible with water and with all investigated hydrocarbons [cyclohexane (CHX), toluene (TOL), and n-decane (DEC)], whereas the ternary mixtures exhibit liquid-liquid phase separation terminated at corresponding critical points. The shape and location of the phase separation boundary are only weakly dependent on temperature and the hydrocarbon's nature; however, the critical point in the water-TBA-DEC system is significantly shifted toward a higher TBA concentration. For the experimentally studied systems and for available data reported in the literature, we confirmed an apparently generic (for nonionic hydrotropes) phenomenon of a dual action at water-oil interfaces (earlier found in water-TBA-CHX [J. Phys. Chem. C 2017, 121, 16423]): at low concentrations, hydrotropes saturate the water-oil interface like a surfactant, whereas at higher concentrations they act as co-solvents, resulting in vanishing interfacial tension at the liquid-liquid critical point. We suggest a universal crossover function that accurately interpolates the two theoretically based limits of interfacial behavior. This crossover function also accounts for earlier deviations from Langmuir-von Szyszkowski limiting behavior in the water-TBA-DEC system, caused by lower solubility (relative to other studied hydrocarbons) of DEC in water. An intriguing correlation between the dual action of hydrotropes at the water-oil interface and the behavior of the liquid-air interfaces is also discussed.

Сonceptual Fundamentals for Technology of Sand Disperse-Reinforced Asphalt Concrete

A problem of efficient resource usage in road branch continues to be one of the most complicated issues and requires an intensification in investigation process pertaining to possibilities for production of road construction materials of low resource intensity with high physical and mechanical properties. Technogenic wastes of the Belarusian enterprises are rather various and they need a detailed investigation. Application of such methods as IR spectrometry, probe microscopy, study of of geometric characteristics of particles and fibers make it possible to determine more active centres and reveal micro-defects that influence on strength of adhesion bond at the boundary of “fiber – binder” and physical and mechanical properties of ready-mixed asphalt concrete. Nature of basalt fiber presupposes mainly physical character of adhesion interaction at the boundary of phase separation. An increase of technogenic waste activity to enhance adhesion contacts up to chemisorption level is possible only due to preliminary fiber processing which includes cleaning, removal of foreign inclusions, etching, drying, probable sorting-out and fluffing. Industrial approbation of such technological process is not possible without development of a corresponding module or a plant. Disperse reinforment causes changes in composition and technology of sand asphalt concrete. An increase in specific surface of an aggregate, necessity of uniform distribution of fiber in terms of volume determine the required need in a binder, procedure and regimes for component mixing. Grain composition of the aggregate can be represented by crush screening and natural sand of mixture of these materials. Requirements to properties of sand disperse-reinforced asphalt concrete are formed on the basis of operational conditions and layer arrangement of the material in the design of a surface dressing. The disperse-reinforced sand asphalt concrete can perform functions of a superfine protective layer, a levelling layer or a crack stopping layer which is resistant to fatigue crack formation.

Electrophoretic NMR Characterization of Charged Side Chain Cationic Polyelectrolytes and Their Interaction with the Anionic Surfactant, Sodium Dodecyl Sulfate.

Oppositely charged polymers and surfactants show a complex phase behavior with large regions of solubility and insolubility dependent on the concentrations of the species present. Here, a series of quaternized hydroxyethyl cellulose (cationic) polymers have been characterized by pulsed-gradient spin-echo NMR (PGSE-NMR) and electrophoretic NMR (eNMR) in simple aqueous (D2O) solutions and in combination with the oppositely charged (anionic) surfactant, sodium dodecyl sulfate (SDS). Analysis of the effective charge on the polymer derived from both the eNMR and PGSE-NMR results yields a readily interpretable insight into the polymer behavior; the effective charge on the polymer at infinite dilution shows a linear relationship with the degree of modification. On addition of low concentrations of SDS, typically Csurf < 5 mM, the surfactant interacts with the charged polymers, leading to substantial changes in the dynamics of the system (polymer diffusion, viscosity). At these levels of surfactant addition, there is no macroscopic phase separation. Further, with the absence of an interaction with the parent, the uncharged polymer strongly suggests that the SDS only interacts with the charged moieties present on the functionalized side groups and not the polymer backbone. Ultimately, the charge on the soluble polymer/surfactant complex was found to depend linearly on the level of surfactant binding across a series of polymers with differing levels of modification with the charge becoming effectively zero at the macroscopic phase separation boundary.

Automation of sedimentation test.

This paper reports on the development of an automated method to perform sedimentation tests on a suspension, to study the settling and sedimentation behaviour of particle suspension. The standard method for measuring sedimentation rate is the jar test, but this is burdened with some errors: the possibility of misinterpretation of the interface or subjective readings by technicians. In order to overcome these problems, there are many different methods that exclude subjective mistakes. The proposed solution automatically detects the phase separation boundary and, by use of a moving camera, plots the real-time sedimentation curve. The good agreement of settling curves between the manual method, another CCD image processing method and the current technique demonstrates the reliability of the system. This system can be used for testing different types of suspensions. The article presents a comparison of the commonly used method of image analysis and the proposed solution with a tracking camera, based on the example of a coal suspension.

Polymerization-Induced Phase Separation Formation of Structured Hydrogel Particles via Microfluidics for Scar Therapeutics

Excessive scar formation can form disabling contractures that result in a debilitating psychological outcome. Sustainable hydrophobic corticosteroid release in vivo is essential to regulate the wound healing process. Functional hydrogel particles are widely applied for sustainable release. However, due to the limited aqueous solubility of hydrophobic compounds, most of the corticosteroid is released from the hydrogels within seconds, causing undesirable scar formation and recurrence. In this study, a novel polymerization-induced phase separation is investigated to form well-defined polyethylene glycol diacrylate (PEGDA) core/alginate shell structured hydrogel particles using microfluidics without toxic organic solvents. Based on their wettability preference, hydrophobic corticosteroid-loaded poly(lactic-co-glycolic acid) (PLGA) nanoparticles are compartmentalized in the PEGDA core during polymerization to control the corticosteroid release. The distribution of the PLGA nanoparticles is precisely regulated by the phase separation boundary and characterized using a fluorescent dye. The thickness of the shell and partition coefficients are determined using the UV intensity and irradiation period. Upon encapsulation of the PLGA nanoparticles within the poly(PEGDA) core, a long-term corticosteroid treatment is developed and effective scar therapeutic outcomes are evaluated using both in vitro and in vivo models.

Spontaneously formed high-performance charge-transport layers of organic single-crystal semiconductors on precisely synthesized insulating polymers

Charge-transporting semiconductor layers with high carrier mobility and low trap-density, desired for high-performance organic transistors, are spontaneously formed as a result of thermodynamic phase separation from a blend of π-conjugated small molecules and precisely synthesized insulating polymers dissolved in an aromatic solvent. A crystal film grows continuously to the size of centimeters, with the critical conditions of temperature, concentrations, and atmosphere. It turns out that the molecular weight of the insulating polymers plays an essential role in stable film growth and interfacial homogeneity at the phase separation boundary. Fabricating the transistor devices directly at the semiconductor-insulator boundaries, we demonstrate that the mixture of 3,11-didecyldinaphtho[2,3-d:2′,3′-d′]benzo[1,2-b:4,5-b′]dithiophene and poly(methyl methacrylate) with the optimized weight-average molecular weight shows excellent device performances. The spontaneous phase separation with a one-step fabrication process leads to a high mobility up to 10 cm2 V−1 s−1 and a low subthreshold swing of 0.25 V dec−1 even without any surface treatment such as self-assembled monolayer modifications on oxide gate insulators.

Enhanced dielectric and piezoelectric responses in Zn1-xMgxO thin films near the phase separation boundary

Dielectric and piezoelectric properties for Zn1-xMgxO (ZMO) thin films are reported as a function of MgO composition up to and including the phase separation region. Zn1-xMgxO (0.25 ≤ x ≤ 0.5) thin films with c-axis textures were deposited by pulsed laser deposition on platinized sapphire substrates. The films were phase pure wurtzite for MgO concentrations up to 40%; above that limit, a second phase with rocksalt structure evolves with strong {100} texture. With increasing MgO concentration, the out-of-plane (d33,f) and in-plane (e31,f) piezoelectric coefficients increase by 360% and 290%, respectively. The increase in piezoelectric coefficients is accompanied by a 35% increase in relative permittivity. Loss tangent values fall monotonically with increasing MgO concentration, reaching a minimum of 0.001 for x ≥ 0.30, at which point the band gap is reported to be 4 eV. The enhanced piezoelectric response, the large band gap, and the low dielectric loss make Zn1-xMgxO an interesting candidate for thin film piezoelectric devices, and demonstrate that compositional phase transformations provide opportunities for property engineering.

Dynamics of partially miscible polylactide-poly(ε-caprolactone) blends in the presence of cold crystallization

Previous studies on polylactide (PLA)/poly(e-caprolactone) (PCL) biodegradable blends revealed enhanced nucleation of PLA. The mechanism by which this enhancement of nuclei density occurs attracted significant interest. In this study, precursors’ transportation from PCL into PLA phase is invoked in order to interpret the experimental findings related to phase separation and crystallization. This mechanism is supported by differential scanning calorimetry (DSC) and polarized optical microscopy (POM). The DSC data revealed that PCL crystallinity within the blends is decreased with PLA content. In addition, POM data showed more nuclei within PLA as the PCL weight fraction is increased. The linear viscoelastic properties of these blends in the vicinity of the phase separation and cold crystallization boundary are examined. It is shown that the combination of POM and rheometry allows determining the phase diagram of the blend and identifying changes occurring due to phase separation and crystallization. Thus, the complete phase diagram of such systems can be fully determined, essential in process design and optimization.

Interplay of magnetic order, pairing, and phase separation in a one-dimensional spin-fermion model

We consider a lattice model of itinerant electrons coupled to an array of localized classical Heisenberg spins. The nature of the ground state ordered magnetic phases that result from the indirect spin-spin coupling mediated by the electrons is determined as a function of density and the spin-fermion coupling $J$. At a fixed chemical potential, spiral phases exist only up to values of $J$ which are less than roughly half the electronic bandwidth. At a fixed electron density and near half filling, the system phase separates into a half-filled antiferromagnetic phase and a spiral phase. The ferromagnetic phases are shown to be fully polarized, while the spiral phases have equal admixture of up and down spins. Phase separation survives in the presence of weak pairing field $\Delta$ but disappears when $\Delta$ exceeds a critical value $\Delta_c$. If pairing fields are large enough, an additional spiral state arises at strong coupling $J$. The relevance of this study, especially the phase separation, to artificially engineered systems of adjacent itinerant electrons and localized spins is discussed. In particular, we propose a method which might allow for the braiding of Majorana fermions by changing the density and moving their location as they are pulled along by a phase separation boundary.

Sol–gel transition and phase separation in ternary system of gelatin-water–poly(ethylene glycol) oligomer

The phase behaviors are studied in the ternary system of gelatin-water–poly(ethylene glycol) oligomer. It is found that both the phase separation and the sol–gel transition occur simultaneously when the poly(ethylene glycol) oligomers are added to the aqueous gelatin solution. The phase separation boundary is found to shift in the higher temperature than the sol–gel transition line when the higher molecular weight oligomers of poly(ethylene glycol) coexist in the solution. The competition of these two transitions creates two new phases in the system, the phase separated solution of gelatin and poly(ethylene glycol) and the opaque gelatin gel in which the density fluctuation due to the phase separation is frozen in.

Phase behaviors of agarose gel

We present evidence for the existence of phase separation in the gel state of agarose having the mixture of water and methanol as the gelsolvent. Firstly, the sol-geltransition line and the cloud point line are determined independently as a function of the concentration of agarose as well as the concentration of methanol in the mixed solvent by the quasi-equilibrium cooling of the solutions. Then the spinodal line is determined by quenching the solutions below the sol-geltransition line. We find that the spinodal line appears below the cloud point line and both lines are entirely buried below the sol-geltransition line in the aqueous agarose system. The concentration fluctuations are, therefore, frozen into the polymer network of agarose gel that promotes the opacity of the resultant gel. The structure of agarose gel is observed by the confocal laser scanning microscope (CLSM)imaging technique that reveals that the density fluctuations are grown up to micrometer scale in space. The phase separationboundary is found to shift to the higher temperature region than the sol-geltransition line when the concentration of methanol in the mixed solvent is increased. The results indicate that the position of the phase separation boundary in relative to the sol-geltransition line varies with the quality of solvent.These results are in agreement with the theory of the sol-geltransition in which both the divergence of the connectivity and the thermodynamic instability are taken into account.

Structural and elemental characterization of high efficiency Cu2ZnSnS4 solar cells

We have carried out detailed microstructural studies of phase separation and grain boundary composition in Cu2ZnSnS4 based solar cells. The absorber layer was fabricated by thermal evaporation followed by post high temperature annealing on hot plate. We show that inter-reactions between the bottom molybdenum and the Cu2ZnSnS4, besides triggering the formation of interfacial MoSx, results in the out-diffusion of Cu from the Cu2ZnSnS4 layer. Phase separation of Cu2ZnSnS4 into ZnS and a Cu–Sn–S compound is observed at the molybdenum-Cu2ZnSnS4 interface, perhaps as a result of the compositional out-diffusion. Additionally, grain boundaries within the thermally evaporated absorber layer are found to be either Cu-rich or at the expected bulk composition. Such interfacial compound formation and grain boundary chemistry likely contributes to the lower than expected open circuit voltages observed for the Cu2ZnSnS4 devices.

The Study of Phase Separation in Amorphous Freeze-Dried Systems. Part I: Raman Mapping and Computational Analysis of XRPD Data in Model Polymer Systems

Phase separation in amorphous freeze-dried mixtures is likely in many systems. However, suitable detection methodology has been lacking, as the classical technique, differential scanning calorimetry (DSC), relies upon detection of multiple glass transition temperatures (T(g)), each of which is characteristic of a given amorphous phase. The lack of a detectable glass transition temperature in protein-rich phases, limits the application of DSC. Here, we focus on evaluating new methods for detection of phase separation in amorphous freeze-dried mixtures. A novel Raman mapping technique has been evaluated using model binary polymer mixtures of PVP and dextran known to phase separate. The sensitivity of this Raman technique in detecting phase separation was comparable to DSC. Phase separation was detected in compositions of 1:9 to 3:2 (PVP 10,000/dextran 5000) and 3:7 to 4:1 (PVP 29,000/dextran 10,000) by DSC and Raman. Computational methodologies applied to X-ray powder diffraction (XRPD) data from these systems are also shown to reliably detect the presence of phase separation. However, some differences between techniques were observed in cases lying on the boundary of phase separation. Thus, Raman and XRPD show promise for detecting phase separation in systems, which do not exhibit detectable glass transitions by calorimetry.

Phase transitions in a solution of solvated oligomers

Phase diagrams of oligomer solutions have been constructed within the mean-field approximation. The free energy includes the configuration entropy and the formation free energy of both solvation shells of the oligomers and bonds between them, where this formation free energy depends upon the oligomer-solvent and solvent-solvent bonding energies. The equations for spinodal (phase separation boundary) and percolation threshold (solution-to-gel transition) in the oligomer concentration-temperature coordinates have been found. The model makes it possible to determine the position of phase boundaries by quantum-chemical calculations of these energies and to explain the change in the composition of colloid particles and gel, depending on the solvent. The phase separation region has been predicted to narrow and to be displaced toward higher oligomer concentrations in a series of solvents with progressively increasing intermolecular bond energy.

Structure peculiarities and optical properties of nanocomposite: 5CB liquid crystal–CTAB-modified montmorillonite clay

The effects of the modification of natural layered montmorillonite (MMT) clay by cetyltrimethylammonium bromide (CTAB) cations on the structure and optical properties of the composite material based on this mineral (4.5%mass) and a nematic liquid crystal (LC), 4-pentyl-4'-cyanobiphenyl (5CB), have been investigated. As shown by small-angle X-ray diffraction and infrared (IR) spectroscopy experiments, this modification results in a significant expansion of the interplane spaces in the MMT nanoparticles and a considerable growth of their surface affinity to the 5CB molecules, which allows the LC molecules to penetrate into the MMT galleries and additionally expand these galleries. According to IR studies, this heterosystem possesses van der Waals interactions between its components on the phase separation boundary and, as a result, orientation alignment of the molecules in the near-surface layers occurs. These interactions specify the electro-optical properties of the composite. When an electric field is applied to a system, the light transmittance of the material increases due to the induced orientation of the LC dimers. This LC ordering remains even after the voltage is shut off, i.e. the system shows an electro-optical memory effect.

Non-aqueous foams in lubricating oil systems

We have investigated the foaming properties of mixtures of a hydrocarbon oil solvent with various low molar mass, polymeric and overbased detergent particle additives used in lubricating oils. Foam formation occurs only when the additive concentration and temperature are such that the single-phase mixtures are close to a phase separation boundary when solvent affinity for the solute is low. This is likely to maximise the tendency of the solute to adsorb at the liquid–air surface and thereby promote foam formation. Multi-phase mixtures either maintain or suppress the foamability of the single-phase mixtures. The foams formed contain spherical, polydisperse gas bubbles and liquid volume fractions greater than about 20 vol.% indicating they are “wet”, transient foams in which the adsorbed solute films at the liquid–air surface can affect liquid drainage but are incapable of resisting coalescence between contacting bubbles. Consistent with this model, the foam half-life is found to scale with the kinematic viscosity of the liquid.

Arrested fluid-fluid phase separation in depletion systems: Implications of the characteristic length on gel formation and rheology

We investigate the structural, dynamical, and rheological properties of colloid-polymer mixtures in a volume fraction range of ϕ=0.15–0.35. Our systems are density-matched, residual charges are screened, and the polymer-colloid size ratio is ∼0.37. For these systems, the transition to kinetically arrested states, including disconnected clusters and gels, coincides with the fluid-fluid phase separation boundary. Structural investigations reveal that the characteristic length, L, of the networks is a strong function of the quench depth: for shallow quenches, L is significantly larger than that obtained for deep quenches. By contrast, L is for a given quench depth almost independent of ϕ; this indicates that the strand thickness increases with ϕ. The strand thickness determines the linear rheology: the final relaxation time exhibits a strong dependence on ϕ, whereas the high frequency modulus does not. We present a simple model based on estimates of the strand breaking time and shear modulus that semiquantit...

Explaining the phase behaviour of the pharmaceutically relevant polymers poly(ethylene glycol) and poly(vinyl pyrrolidone) in semi-fluorinated liquids

Phase behaviour studies of low molecular weight poly(ethylene glycol) (denoted PEG 600 and PEG 1000, corresponding to molecular weights of 600 and 1000 g mol(-1), respectively) have been carried out in 2H,3H-perfluoropentane (HPFP) with and without added poly(vinyl pyrrolidone). The concentration and temperature dependencies of their phase behaviour and the effect of moisture on these systems have been established. Furthermore, the solubility of PEG 600 in binary mixtures of HPFP and perfluoropentane (PFP), as well as HPFP and perfluorodecalin (PFD) have been considered at high HPFP contents. A phase separation phenomenon in fluorinated non-aqueous media is reported for the first time: PEG 600 and PEG 1000 both show a lower critical solution temperature type phase separation boundary. The size of the PEGs was obtained from small-angle neutron scattering (radius of gyration) and pulsed-gradient spin-echo NMR (hydrodynamic radius) measurements. It is shown that polymer conformation follows a regular trend with solution concentration; the size increases from <10 A at 3 wt% in HPFP to 45 +/- 2 A at 20 wt% PEG. On changing the solvent composition by substitution of HPFP by PFP or PFD, the size decreases, consistent with a decrease in the hydrogen-bonding capacity of the solvent mixture. Computer modelling indicates an interaction between the PEG oxygen and the hydrogen of HPFP, an interaction that is absent for the fully fluorinated solvents. This indicates that hydrogen bonding is the driving force for polymer solubility in these solvents.

Collective Diffusion in Colloid−Polymer Suspensions: Relative Role of Thermodynamics and Hydrodynamics

Theories such as the mode coupling theory (MCT) have seen recent success in predicting the kinetic arrest boundaries and resultant flow properties of colloidal suspensions. A key assumption of such theories is that interparticle forces and equilibrium structure control slow dynamics and gelation, not long-time many-body hydrodynamics. Here we report measurements of short-time collective diffusivities of colloid-polymer suspensions aimed at elucidating the relative contributions of hydrodynamics and thermodynamics as a phase transition or gelation boundary is approached. The experimental system is a hard sphere octadecyl silica suspension to which nonadsorbing polystyrene is added. Two different polymer molecular weights are chosen such that they give rise to a liquid-liquid or a gel transition as the colloid volume fraction or polymer concentration is increased. The short-time diffusivities are measured for each polymer molecular weight as a function of polymer concentration and colloid volume fraction. At a fixed polymer molecular weight and concentration, the colloid volume fraction is varied from dilute to concentrated and near the phase separation boundary. It is found for all measured colloid volume fractions that the diffusivities decrease linearly with increasing strength of the polymer-mediated depletion attraction at a fixed polymer molecular weight. Comparisons are made with theoretical predictions in the dilute limit. When the effects of thermodynamics are normalized out by multiplying the measured diffusivities with the suspension structure factor, it is found that the hydrodynamic effects are essentially those of hard spheres independent of the range and strength of depletion attraction.

NMR and quantum chemistry study of mesoscopic structuring in 3-methylpyridine/water/NaBr mixture in the vicinity of the phase separation boundary

23Na and 81Br NMR spin-lattice relaxation times and signal half widths (Δ1/2) have been measured in 3-methylpyridine (3MP)/H2O/NaBr mixture along T = 294 and 301 K isotherms gradually increasing the mass fractions of salt (X) up to the phase separation boundary. The extreme narrowing condition and thus 1/T 1 = 1/T 2 = πΔ 1/2 was found to be valid in all cases. Discontinuous changes in slope of 1/T 1,2 = f(X) were detected, and then corresponding points on the phase diagram (X, T) were attributed to the borderline between the molecular-ionic solution and the area of enhanced mesoscopic structuring. A very strong relaxation effect was observed for 81Br nuclei reaching relaxation rates of 14,000 s–1. 23Na and 81Br NMR relaxation data together with calculations of quantum chemistry model of electrical field gradient tensor evidence the migration of 3-methylpyridinium at increasing X from the anions hydration shells towards cations. An interchange from migration to steady distribution regimes is observed for anions and vice versa for cations at the borderline of the structured phase.