Transition In Binary Mixtures Research Articles

Density functional theory of freezing transition in a binary mixture of spheres and soft-ellipsoids

ABSTRACT This study uses the classical density functional theory (DFT) of freezing to investigate phase transitions in ellipsoidal-spherical binary mixtures interacting via a generalised Gay-Berne (GB) intermolecular potential, with a focus on I-N, I-SmA and N-SmA transitions. The mixtures, consisting mainly of ellipsoids, contain spherical additives at concentrations of 5 % , 10 % and 15 % . The pair correlation functions, which are crucial for the DFT, are derived from Percus-Yevick integral equation theory. Our results show a significant influence of spherical additives on liquid crystalline phases formed by ellipsoids. At an ellipsoid length-to-width ratio of 3.0, only the I-N transition is observed, with the SmA phase remaining unstable under all conditions. Increasing the ellipsoidal length-to-width ratio to κ = 4.0 introduces the SmA phase, whose stability depends on the concentration and size of the spherical additives. The stability of the SmA phase decreases with increasing concentration and size of the spheres. Phase diagrams, which are shown in temperature-density and pressure-temperature planes, emphasise the influence of the size of the spherical dopants on the phase stability.

Exploring the nematic to twist-bend nematic phase transition: calorimetric and optical measurements

ABSTRACT We investigate the nematic (N) to twist-bend nematic (NTB) phase transition in binary mixtures of a symmetric liquid crystal dimer (CB7CB) and a calamitic bi-phenyl mesogen (7OCB). As the molar concentration of 7OCB increases, both the Iso–N and N–NTB transition temperatures decrease gradually, consequently, the width of the nematic phase above the NTB phase can suitably be varied from ~12 K to 46 K. Notably, as the nematic range expands, there is a remarkable reduction in transitional entropy, eventually approaching negligible or zero values. Additionally, the heat capacity peak and the phase shift disappear when transitional entropy reaches zero. This behaviour diverges from typical N–SmA and N–SmC phase transitions, where transitional entropy decreases near the tricritical point but the heat capacity peak persists. Our findings indicate a finite positive δ(∆n) across all concentrations at the N–NTB phase transition, suggesting a gradually weakening first-order nature. This contrasts with theoretical predictions of a second-order N–NTB phase transition, as our experimental data consistently supports a first-order nature. The self-consistent mean-field Landau Model successfully validates our experimental data, establishing the universal first-order nature of the N–NTB phase transition, with experimental entropy values in good agreement with theoretical prediction.

Tricritical behavior of the smectic-hexatic phase transitions in binary mixtures using the landau mean field theory

ABSTRACT The smectic-hexatic phase transitions are studied by the Landau mean field theory in binary mixtures, particularly, THI-14 + MPR-6 liquid crystalline system. By considering the phase lines of SmA-Hex B, SmC-SmF (Hex F) and SmF-Hex B as the first order; SmA-SmC and SmC-SmF as the second order, in the presence of the two tricritical points (C-F-B and A-C-B), we calculate the T-X phase diagram of the binary mixture studied. The phase line equations obtained from the free energies of the smectic and hexatic phases, are fitted to the experimental data given in the literature. We find that the Landau mean field theory explains satisfactorily the observed T-X phase diagram for the smectic-hexatic transitions in the binary mixture of THI-14 + MPR-6.

Calculation of the T-X phase diagram for the first-order smectic–hexatic transitions in binary mixtures

This work gives the T-X phase diagram calculated from the Landau mean field model for the smectic–hexatic transitions in binary mixtures, particularly, in THI-13+THI-17. It is calculated near the SmC-SmF (Hex F)–Hex B triple point by considering transitions of SmC-SmF, SmF-HexB, and SmC-Hex B as the first order. The phase line equations are fitted to the experimental T-X phase diagram from the literature for this binary mixture by assuming the temperature and concentration dependence of the coefficients in the Landau free energy expansion. Calculations are given in some detail to describe the smectic–hexatic transitions in the THI-13+THI-17, which can also be considered for other binary mixtures under the Landau mean field model studied here.

Crystal-to-Crystal Transitions in Binary Mixtures of Soft Colloids.

In this article, we demonstrate a method for inducing reversible crystal-to-crystal transitions in binary mixtures of soft colloidal particles. Through a controlled decrease of salinity and increasingly dominating electrostatic interactions, a single sample is shown to reversibly organize into entropic crystals, electrostatic attraction-dominated crystals, or aggregated gels, which we quantify using microscopy and image analysis. We furthermore analyze crystalline structures with bond order analysis to discern between two crystal phases. We observe the different phases using a sample holder geometry that allows both in situ salinity control and imaging through confocal laser scanning microscopy and apply a synthesis method producing particles with high resolvability in microscopy with control over particle size. The particle softness provides for an enhanced crystallization speed, while altering the re-entrant melting behavior as compared to hard sphere systems. This work thus provides several tools for use in the reproducible manufacture and analysis of binary colloidal crystals.

Studying of crystal growth and overall crystallization of naproxen from binary mixtures

Broadband dielectric spectroscopy (BDS) and differential scanning calorimetry (DSC) were applied to investigate the molecular dynamics and phase transitions in binary mixtures composed of naproxen (NAP) and acetylated saccharides: maltose (acMAL) and sucrose (acSUC). Moreover, the application of BDS method and optical microscopy enabled us to study both crystallization kinetics and crystal growth of naproxen from the solid dispersions with the highest content of modified carbohydrates (1:5wt ratio). It was found that the activation barriers of crystallization estimated from dielectric measurements are completely different for both studied herein mixtures. Much higher Ea (=205kJ/mol) was obtained for NAP-acMAL solid dispersion. It is probably due to simultaneous crystallization of both components of the mixture. On the other hand, lower value of Ea in the case of NAP-acSUC solid dispersion (81kJ/mol) indicated, that naproxen is the only crystallizing compound. This hypothesis was confirmed by X-ray diffraction studies. We also suggested that specific intermolecular dipole-dipole interactions between active substance and excipient may be an alternative explanation for the difference between activation barrier obtained for NAP-acMAL and NAP-acSUC binary mixtures. Furthermore, optical measurements showed that the activation energy for crystal growth of naproxen increases in binary mixtures. They also revealed that both excipients: acMAL and acSUC move the temperature of the maximum of crystal growth towards lower temperatures. Interestingly, this maximum occurs for nearly the same structural relaxation time, which is a good approximation of viscosity, for all samples. Finally, it was also noticed that although naproxen crystallizes to the same polymorphic form in both systems, there are some differences in morphology of obtained crystals. Thus, the observed behavior may have a significant impact on the bioavailability and dissolution rate of API produced in that way.

Tracking three-phase coexistences in binary mixtures of hard plates and spheres.

The stability of demixing phase transition in binary mixtures of hard plates (with thickness L and diameter D) and hard spheres (with diameter σ) is studied by means of Parsons-Lee theory. The isotropic-isotropic demixing, which is found in mixtures of large spheres and small plates, is very likely to be pre-empted by crystallization. In contrast, the nematic-nematic demixing, which is obtained in mixtures of large plates and small spheres, can be stabilized at low diameter ratios (σ/D) and aspect ratios (L/D). At intermediate values of σ/D, where the sizes of the components are similar, neither the isotropic-isotropic nor the nematic-nematic demixing can be stabilized, but a very strong fractionation takes place between a plate rich nematic and a sphere rich isotropic phases. Our results show that the excluded volume interactions are capable alone to explain the experimental observation of the nematic-nematic demixing, but they fail in the description of isotropic-isotropic one [M. Chen et al., Soft Matter 11, 5775 (2015)].

Deflagration-to-detonation transition in mixtures of finely divided ammonium perchlorate with submicron aluminum powder

Deflagration-to-detonation transition in binary mixtures of fine ammonium perchlorate (20-μm grains) with submicron ALEX-L aluminum powder (0.2-μm particles) is studied using high-speed photography and pressure recording with quartz crystal sensors. The test mixtures were loaded in thin-walled quartz tubes of inner diameter 10 mm. The charges had a porosity of ~50%. It has been shown that, even under very mild conditions (low-strength shell and a weak source of initiation), the deflagration mode of mixture combustion easily transforms into the detonation mode. The shortest length of the region of transition from deflagration to normal detonation (not more than 30 mm) was observed for a lean mixture, with an aluminum content of ~5%. The mechanism of transition to detonation involves the stage of convective combustion, resulting in the formation of a brightly luminescent crescent-shaped area behind the primary flame front, which, in turn, generates a forward (in the direction of propagation) and a backward wave. The forward wave gives rise to low-speed detonation, which later transforms into normal detonation. The pressure profile within the region of low speed detonation is measured. A comparison with similar experiments in which ALEX-L alu- minum powder was replaced by ASD-4 aluminum (4 μm particles) shows that ALEX-L sensitizes the mixture, resulting in a dramatic reduction of the length of the transition region, making it possible to produce normal detonation in low-strength shells.

Critical wetting, first-order wetting, and prewetting phase transitions in binary mixtures of Bose-Einstein condensates

An ultralow-temperature binary mixture of Bose-Einstein condensates adsorbed at an optical wall can undergo a wetting phase transition in which one of the species excludes the other from contact with the wall. Interestingly, while hard-wall boundary conditions entail the wetting transition to be of first order, using Gross-Pitaevskii theory we show that first-order wetting as well as critical wetting can occur when a realistic exponential optical wall potential (evanescent wave) with a finite turn-on length $\lambda$ is assumed. The relevant surface excess energies are computed in an expansion in $\lambda/\xi_i$, where $\xi_i$ is the healing length of condensate $i$. Experimentally, the wetting transition may best be approached by varying the interspecies scattering length $a_{12}$ using Feshbach resonances. In the hard-wall limit, $\lambda \rightarrow 0$, exact results are derived for the prewetting and first-order wetting phase boundaries.

Thermal and Optical Properties of Some Hydrogen-Bonded Liquid Crystal Mixtures

Phase transition properties of the mixtures of hydrogen-bonded nematic liquid crystals (HBLC) 4-hexylbenzoic acid (6BA), 4-(octyloxy)benzoic acid (8OBA), and 4-(decyloxy)benzoic acid (10OBA) have been investigated by means of differential scanning calorimetry (DSC) and polarize optic microscope (POM). The DSC and POM results clearly indicate the existence of smectic and nematic phase transitions in binary mixtures. The phase transition temperature values of 6BA/10OBA mixtures have clearly increased with increasing heating rate. The activation energies were calculated for the phase transitions of 6BA/10OBA liquid crystal (LC) mixture. The optical transmittance of these mixed hydrogen-bonded nematic liquid crystals was investigated in terms of temperature variations through electrooptic methods. The electrooptic experiments indicate that, while low in the nematic phase, the optical transmittance is very high at the nematic-isotropic phase transition. The transmitted light intensity values of 6BA/8OBA mixture are somewhat higher than those of other binary mixtures, 6BA/10OBA and 8OBA/10OBA, a result associated with the different alkyloxy chain lengths.

Entropy-Theoretical Analysis of Glass Transitions in Binary Mixtures

The entropy theory of binary liquid mixture was extended to include the excess configurational entropy SCE, which reflects the degree of structural change on mixing. The SCE values were obtained for several hydrocarbon-hydrocarbon, alcohol-alcohol and amine-alcohol systems from their mole-fraction dependence of the glass transition temperatures and precise heat capacity data of the pure components. The liquid structures of the systems, especially those related to the formation of the hydrogen bonds, are discussed based on SCE.

Tests of the tricritical point in the SmA-to-N phase transition of binary mixtures of butyloxybenzylidene octylaniline and hexyloxybenzylidene octylaniline

The present work arises from the significant difference between the experimental Landau tricritical point (LTCP) in the Sm A-to-N phase transition in binary mixtures of butyloxybenzylidene octylaniline (4O.8) and hexyloxybenzylidene octylaniline (6O.8) predicted by Stine and Garland, and that arising from the thermodynamic assessment using the Oonk's Equal Gibbs Curve method. By use of specific heat measurements the 4O.8 + 6O.8, phase diagram has been determined anew. The results of the subsequent application of Oonk's thermodynamic analysis are discussed and their compatibility with the behaviour universally exhibited by other liquid crystal binary mixtures for which a LTCP in the SmA-to-N phase transition has been experimentally determined are analysed.

Effect of Saline on Transitions in Poly(ethylene glycol)-Grafted Succinyl-Phosphoethanolamine Monolayers Bearing C16Aliphatic Chains

To investigate the effect of saline on miscibility, phase, and conformational transitions in binary mixtures of a succinyl-phosphoethanolamine bearing C(16) aliphatic chains, DPPE-succinyl, and a poly(ethylene glycol) (PEG)-phospholipid conjugate with a PEG molecular weight of 2000, DPPE-PEG2000, we have compared the properties of monolayers spread on water and on phosphate buffered saline (PBS). A comparative analysis of monolayer surface pressure, surface potential, compressibility, and epifluorescence microscopy data has revealed that spreading on PBS induces unfavorable interactions between the two phospholipids, which stabilizes immiscible phases in mixed monolayers. Strikingly, the conformational transition in grafted PEG2000 chains on PBS could not be easily described by the existing interpretive schemes. Plausibly, this transition becomes partially impaired due to interactions with PBS. Thus, saline has a significant effect on miscibility, phase, and conformational transitions in these PEG-grafted monolayers bearing C(16) aliphatic chains, which may have implications for understanding the behavior of PEG-grafted phospholipid surfaces in aqueous media of biological relevance.

Evolution of the isotropic to nematic phase transition in binary mixtures of octylcyanobiphenyl and n-hexane

High-resolution calorimetry has been performed to study the effect of dilution by a nonmesogenic, low-molecular weight solvent (linear n-hexane) on the isotropic-nematic (I-N) phase transition in the liquid crystal (LC) octylcyanobiphenyl (8CB) as a function of n-hexane concentration. Numerous temperature scans were performed without continuous mixing for pure 8CB and all mixture samples of n-hexane mole fraction ranging from x(hex)=0.02 to 0.12. The I-N specific heat peak remains first-order for all samples and shifts toward lower temperature nonlinearly while the two-phase I+N coexistence width broadens linearly with increasing x(hex). Multiple heating and cooling scans are reproducible and indicate phase separation, if it occurs, must be on very short length scales and is reversible. These results may be a consequence of a competition between random dilution effects and the tendency to phase separate. It is shown that solvent dilution of a LC, if miscible and depending on solvent structure, can lead to a controlled altering of the intermolecular potentials and softening of the LC viscoelastic properties.

Surface and smectic layering transitions in binary mixtures of parallel hard rods

The surface phase behavior of binary mixtures of colloidal hard rods in contact with a solid substrate (hard wall) is studied, with special emphasis on the region of the phase diagram that includes the smectic A phase. The colloidal rods are modeled as hard cylinders of the same diameter and different lengths, in the approximation of perfect alignment. A fundamental-measure density functional is used to obtain equilibrium density profiles and thermodynamic properties such as surface tensions and adsorption coefficients. The bulk phase diagram exhibits nematic-smectic and smectic-smectic demixing, with smectic phases having different compositions; in some cases they are microfractionated. The calculated surface phase diagram of the wall-nematic interface shows a very rich phase behavior, including layering transitions and complete wetting at high pressures, whereby an infinitely thick smectic film grows at the wall via an infinite sequence of stepwise first-order layering transitions. For lower pressures complete wetting also obtains, but here the smectic film grows in a continuous fashion. Finally, at very low pressures, the wall-nematic interface exhibits critical adsorption by the smectic phase, due to the second-order character of the bulk nematic-smectic transition.

Anomalous phase behavior of liquid–vapor phase transition in binary mixtures of DNA-coated particles

We report a Monte Carlo study of a 1 : 1 binary mixture of particles coated with DNA chains with “sticky” ends. The system was modeled using a coarse-grained representation. In order to map out the phase diagram of this model system we combined biased Monte Carlo simulations with histogram reweighting techniques. We find that, at low temperatures (strong hybridization) this system undergoes a phase separation between a dilute vapor-like phase and a dense network-forming liquid-like phase. We observe a surprising non-monotonic dependence of the coexistence pressure on the temperature, or more precisely, on the reduced hybridization free energy (fhyb/kBT). This anomalous behavior can be understood in terms of a cross-over between two distinct regimes for the driving force of the phase transition: a hybridization-free-energy-driven regime and an entropy-driven regime. In the former regime, we observe a “normal” vapor–liquid equilibrium where during condensation, the system gains hybridization free energy but loses entropy. In the entropy-driven regime, the phase transition is driven by the increase in entropy due to the re-arrangement of sticky-end bonds in the liquid phase. Finally, we observe that the system can only undergo phase separation if the valence (i.e., the number of DNA-chains per particle) is larger than two. The coexistence region widens markedly as the valence is increased.

Multiple Glass Transitions in Star Polymer Mixtures: Insights from Theory and Simulations

The glass transition in binary mixtures of star polymers is studied by mode coupling theory and extensive molecular dynamics computer simulations. In particular, we have explored vitrification in the parameter space of size asymmetry δ and concentration ρ2 of the small star polymers at fixed concentration of the large ones. Depending on the choice of parameters, three different glassy states are identified: a single glass of big polymers at low δ and low ρ2, a double glass at high δ and low ρ2, and a novel double glass at high ρ2 and high δ which is characterized by a strong localization of the small particles. At low δ and high ρ2 there is a competition between vitrification and phase separation. Centered in the (δ, ρ2)-plane, a liquid lake shows up revealing reentrant glass formation. We compare the behavior of the dynamical density correlators with the predictions of the theory and find remarkable agreement between the two.

Kinetics of the Isotropic‐Ordered Phase Transition in Binary Mixtures of Mesogenic Monomers and Polymers

Kinetics of the nematic phase growth in the melted liquid crystalline azomethine monomer, siloxane‐azomethine polymer, and their mixtures was studied under a deep cooling using polarizing optical microscopy. The nematic droplets revealed in the optical images across the phase transition were treated statistically and the resulting statistical size distributions were described using principles of irreversible thermodynamics. Analysis of the mean droplet diameter as a function of time allowed recognition of two regimes involved to the nematic phase evolution: (1) nucleation and rapid nucleus growth and (2) nucleus coarsening. Both regimes were quantitatively described with the universal law of the cluster growth.

Structural transition in alcohol-water binary mixtures: A spectroscopic study

The strengthening of the hydrogen bonding (H-bond) network as well as transition from the tetrahedral-like water network to the zigzag chain structure of alcohol upon increasing the alcohol concentration in ethanol-water and tertiary butanol (TBA) — water mixtures have been studied by using both steady state and time resolved spectroscopy. Absorption and emission characteristics of coumarin 153 (C153), a widely used non-reactive solvation probe, have been monitored to investigate the structural transition in these binary mixtures. The effects of the hydrogen bond (H-bond) network with alcohol concentration are revealed by a minimum in the peak frequency of the absorption spectrum of C153 which occur at alcohol mole fraction ∼0·10 for water-ethanol and at ∼0·04 for water-TBA mixtures. These are the mole fractions around which several thermodynamic properties of these mixtures show anomalous change due to the enhancement of H-bonding network. While the strengthening of H-bond network is revealed by the absorption spectra, the emission characteristics show the typical non-ideal alcohol mole fraction dependence at all concentrations. The time resolved anisotropy decay of C153 has been found to be bi-exponential at all alcohol mole fractions. The sharp change in slopes of average rotational correlation time with alcohol mole fraction indicates the structural transition in the environment around the rotating solute. The changes in slopes occur at mole fraction ∼0·10 for TBA-water and at ∼0·2 for ethanol-water mixtures, which are believed to reflect alcohol mole fraction induced structural changes in these alcohol-water binary mixtures.

Texture transitions in binary mixtures of 6OBAC with compounds of its homologous series

Recently the authors have observed in compounds of the 4,n-alkyloxybenzoic acid series, with the homologous index n ranging from 6 to 9, a texture transition in the nematic range which subdivides the nematic phase in two sub-phases displaying different textures in polarised light analysis. To investigate a persistence of texture transitions in nematic phases, we prepared binary mixtures of 4,6-alkyloxybenzoic acid (6OBAC) with other members (7-, 8-, 9-, 12-, 16OBAC) of its homologous series. Binary mixtures exhibit a broadening in the temperature ranges of both smectic and nematic phases. A nematic temperature range of 75°C is observed. In the nematic phase, in spite of the microscopic disorder introduced by mixing two components, the polarised light optics analysis of the liquid crystal cells reveals a texture transition. In the case of the binary mixture of 6OBAC with 12OBAC and with 16OBAC, that is of compounds with monomers of rather different lengths, the texture transition temperature is not homogeneous in the cell, probably due to a local variation in the relative concentrations of compounds.