Kinetics of binary condensation on the droplet growing in diffusion regime

A relaxation equation determining the regular tendency of the concentration of binary solution in the growing droplet to the stationary value, at which there is a self-similar solution to the problem of the condensation in a binary mixture, is derived. An analytical solution of the relaxation equation is obtained and it is demonstrated that the stationary value of concentration is achieved via the power law. The time interval that elapses from the emergence of the droplet until the diffusion regime of droplet growth and derived relaxation equation become effective is revealed. The stationary value of concentration is found for the model of ideal solution.     

Analysis of the Results of Numerical Simulation of the Supersaturated Vapor Condensation Relaxation

The process of bulk vapor condensation from the vapor-gas mixture after the fast creation of the supersaturated state as a result of vapor expansion is discussed. Scaling relations are derived for the time of condensation relaxation and droplet number density. The principal possibility of the experimental determination of nucleation rate is demonstrated based on the results obtained. The effect of initial phase, frequency, and pulsation amplitude on the condensation relaxation is analyzed for the case, when thermodynamic parameters of a mixture in the process of condensation are subjected to perturbations in the form of low-amplitude harmonic pulsations. The domain of applicability of results obtained on the scale of pulsation frequencies is determined.     

Dynamics of the droplet size distribution function during the gradual creation of a supersaturation state under different regimes of droplet growth

The method of the direct numerical integration of kinetic equations of droplet size distribution functions that was previously proposed by the authors is employed to solve the problem of condensation relaxation in a vapor-gas mixture during the creation of a supersaturation state at a finite rate. Two relaxation regimes are considered. In the static regime, the mixture is expanded at a constant rate until a preset supersaturation ratio is achieved; in the dynamic regime, the expansion is continued. Solutions are obtained for argon-cesium and argon-ethane mixtures, thus making it possible to study the dependence of the process character on the Knudsen number. The effects of the rate of the supersaturation creation and the relaxation regime on the droplet size distribution function are analyzed.     

NMR as a Probe into the Local and Semilocal Order in Cooperative Interactions of Polyelectrolytes

Polyelectrolytes such as poly(N-diallyldimethylammonium chloride) (PDADMAC) exhibit some local and semilocal order both in their conformation dynamics (dynamic correlations) and the average density of their counterion cloud (the radial density distribution). Both aspects of order are subject to cooperative fluctuations as well as mutual reinforcement. They can be observed in particular in dilute solutions, i.e. at concentrations of the charged groups less than 5 mmol/L. At such dilution, ¹H NMR is the method of choice for the study of conformation dynamics. In addition to the recently published analysis of transverse relaxation and saturation transfer experiments, relaxations of double-quantum coherence, pseudo-solid echo and solid echo responses and exchange 2D spectra are reported here. For the radial distribution of counterions with spin-3/2 nuclei (⁷Li, ²³Na, ³⁵Cl, ⁸¹Br), the relaxation model proposed by Halle, Wennerstrom and Picullel is applied and the use of either combined longitudinal and transverse relaxation or DQC ( T ₂ ³ ) relaxation is shown. The results show that the counterion condensation, i.e. relative ordering of the counterion cloud, decreases in less densely charged polyions and vanishes for the charge separation about 2.5 nm.     

Dynamics of variations in size and composition of supercritical droplet at binary condensation

A general analytical solution is found in quadratures for the radius and concentration of a solution droplet, which isothermally grows or evaporates in a diffusion or free-molecular regime in a binary mixture of vapors. The obtained solution describes the dynamics of variations in the size and composition of a super-critical droplet during the binary condensation in mixed vapors at an arbitrary initial droplet composition. It is shown that, at small (linear) deviations of the growth regime and droplet composition from the stationarity, these quadratures lead to the results that were recently obtained for the composition relaxation in a growing droplet. Moreover, it is demonstrated that, in terms of the nonlinear theory, when the deviation of solution concentration in a droplet from its stationary value is not small, it is invalid to use the law of stationary variations in the size of a droplet with time to describe the relaxation process for its chemical composition.     

Vapor phase nucleation on neutral and charged nanoparticles: condensation of supersaturated trifluoroethanol on Mg nanoparticles

A new technique is described to study the condensation of supersaturated vapors on nanoparticles under well-defined conditions of vapor supersaturation, temperature, and carrier gas pressure. The method is applied to the condensation of supersaturated trifluoroethanol (TFE) vapor on Mg nanoparticles. The nanoparticles can be activated to act as condensation nuclei at supersaturations significantly lower than those required for homogeneous nucleation. The number of activated nanoparticles increases with increasing the vapor supersaturation. The small difference observed in the number of droplets formed on positively and negatively charged nanoparticles is attributed to the difference in the mobilities of these nanoparticles. Therefore, no significant charge preference is observed for the condensation of TFE vapor on the Mg nanoparticles.     

Radiofrequency dielectric loss relaxation in polyion-induced liposome aggregates

In this note, we present a set of dielectric loss relaxation measurements of aqueous charged liposome suspensions during the whole aggregation process induced by oppositely charged adsorbing polyions. The system experiences two concomitant effects known as "reentrant condensation" and "charge inversion," resulting in the formation of liposome aggregates whose average size reaches a maximum in the vicinity of the electroneutrality condition, accompanied to a progressive reduction of their overall electrical charge. Far from the neutrality, from both sides, polyion-coated liposomes exist with a charge of opposite sign. The dielectric loss relaxation in these complex aggregating systems has never been measured so far and we report here, for the first time, the dielectric loss behavior of liposomes built up by a cationic lipid and stuck together by poly(acrylate), which is a flexible oppositely charged polyion. The data are analyzed in the framework of standard electrokinetic model theory. The evolution of the aggregation process as a function of the polyion content is mainly characterized by a counterion polarization effect, governed by the surface charge density of the aggregates and hence by the zeta-potential.     

Nonideality in diffusion of ionic and neutral solutes and hydrogen bond dynamics in dimethyl sulfoxide-chloroform mixtures of varying composition

Molecular dynamics simulations of charged and neutral solutes in dimethyl sulfoxide (DMSO)-chloroform mixtures reveal pronounced nonideality in the solute diffusion with changes of composition of the mixtures. The diffusion coefficient of the anionic solute first decreases, passes through a minimum at DMSO mole fraction of about 0.50, and then increases to reach its value for pure DMSO. The diffusion coefficients of the cationic and neutral solutes are found to decrease with increase in DMSO content of the solvent mixture. The extent of nonideality in the diffusion and orientational relaxation of solvent molecules is found to be somewhat stronger than that in diffusion of the anionic solute in these mixtures. We have also calculated the relaxation of hydrogen bonds formed between DMSO and chloroform molecules. The lifetimes of DMSO-chloroform hydrogen bonds are found to increase monotonically with increase in DMSO concentration. The average number of hydrogen bonds and their average energies are also computed. It is found that an increase in DMSO concentration causes a decrease in the number of DMSO-chloroform hydrogen bonds per DMSO or chloroform molecules but increases the strength of these hydrogen bonds.     

Kinetics of supersaturated vapor nucleation on molecular condensation nuclei

The kinetics of nucleation is calculated for a supersaturated vapor containing molecular condensation nuclei, that is, foreign molecules able to induce the formation of viable nuclei of a condensed phase by themselves. In contrast to the previous calculation, the possibility of the escape of molecular condensation nuclei from very small clusters containing a few condensed vapor molecules is taken into account. More exact equations are derived for the rate of steady-state nucleation and the concentration of aerosol particles in a quasisteady-state regime of nucleation. The calculation demonstrates that, at a high probability of the escape of a molecular condensation nucleus, the predominating mechanism of cluster formation is the attachment of a molecular condensation nucleus to a cluster formed from vapor molecules rather than their condensation on the nucleus. At the same time, allowances for the possible escape of molecular condensation nuclei from clusters slightly affect the rate of nucleation and the concentration of aerosol particles being formed.     

Kinetics of the Establishment of Quasi-Steady-State Regime of Overcoming Activation Barrier of Nucleation on the Macroscopic Wettable Nuclei

The solution of the kinetic equation of nucleation on macroscopic wettable condensation nuclei was constructed for the initial (incubation) stage. The solution thus constructed determines the times of relaxation to quasi-steady-state distribution of droplets generating on droplet nuclei in the vicinity of maximum of the work of droplet heterogeneous formation as well as the relaxation to quasi-equilibrium droplet distribution throughout the entire region located to the left of this vicinity at the droplet size axis. The dependence of relaxation times on the height of activation barrier of nucleation, size of nuclei, their nature, and characteristics of matter comprising condensate was elucidated. It was shown when the non-steady-state rate of nucleation becomes actually equal to the quasi-steady-state rate of nucleation.     

Counterion condensation and release in micellar solutions

Counterion condensation and release in micellar solutions are investigated by direct measurement of counterion concentration with ion-selective electrode. Monte Carlo simulations based on the cell model are also performed to analyze the experimental results. The degree of counterion condensation is indicated by the concentration ratio of counterions in the bulk to the total ionic surfactant added, alpha< or =1. The ionic surfactant is completely dissociated below the critical micelle concentration (cmc). However, as cmc is exceeded, the free counterion ratio alpha declines with increasing the surfactant concentration and approaches an asymptotic value owing to counterion condensation to the surface of the highly charged micelles. Micelle formation leads to much stronger electrostatic attraction between the counterion and the highly charged sphere in comparison to the attraction of single surfactant ion with its counterion. A simple model is developed to obtain the true degree of ionization, which agrees with our Monte Carlo results. Upon addition of neutral polymer or monovalent salts, some of the surfactant counterions are released to the bulk. The former is due to the decrease of the intrinsic charge (smaller aggregation number) and the degree of ionization is increased. The latter is attributed to competitive counterion condensation, which follows the Hefmeister series. This consequence indicates that the specific ion effect plays an important role next to the electrostatic attraction.     

Clusters in expanding plasma

An analysis is given of processes in a weakly ionized vapor expanding in a space and condensing on ions as nuclei of condensation. Processes including the growth and evaporation of clusters, mutual neutralization of clusters of different charges and coagulation are considered. Evolution of a laser plasma resulting from irradiation of a copper surface is analyzed. In the end a vapor of the plasma is transformed to charged clusters.     

Reaction of methyl acrylate with titanium tetrachloride during the condensation of the vapors on a cold surface

Complex formation between methyl acrylate and titanium tetrachloride during the condensation of the vapors of the reactants on a copper surface cooled to liquid-nitrogen temperature has been studied by IR spectroscopy. It has been established that the mole fraction of reactants entering into reaction depends on the rate of deposition and has an extremal nature. A formal kinetic model is proposed which represents the relationship obtained in the study between the substances participating in complex formation and the rate of condensation of the mixture.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 22. No. 6, pp. 673–679, November–December, 1986.     

Counterion release from adsorbed highly charged polyelectrolyte: an electrooptical study

The adsorption of sodium poly(4-styrene sulfonate) on oppositely charged beta-FeOOH particles is studied by electrooptics. The focus of this paper is on the release of condensed counterions from adsorbed polyelectrolyte upon surface charge overcompensation. The fraction of condensed Na+ counterions on the adsorbed polyion surface is estimated according to the theory of Sens and Joanny and it is compared with the fraction of condensed counterions on nonadsorbed polyelectrolyte. The relaxation frequency of the electrooptical effect from the polymer-coated particle is found to depend on the polyelectrolyte molecular weight. This is attributed to polarization of the layer from condensed counterions on the polyion surface, being responsible for creation of the effect from particles covered with highly charged polyelectrolyte. The number of the adsorbed chains is calculated also assuming counterion condensation on the adsorbed polyelectrolyte and semiquantative agreement is found with the result obtained from the condensed counterion polarizability of the polymer-coated particle. Our findings are in line with theoretical predictions that the fraction of condensed counterions remains unchanged due to the adsorption of highly charged polyelectrolyte onto weakly charged substrate.     

DNA condensations on mica surfaces induced collaboratively by alcohol and hexammine cobalt

We performed systematic studies of λ-DNA condensation on mica surfaces induced by alcohol and hexammine cobalt (III) [Co(NH(3))(6)(3+)] using atomic force microscopy (AFM). The critical condensation concentration for [Co(NH(3))(6)(3+)] was found to be about 10 microM; the DNA molecules extended freely on mica when the concentration was below the critical value. The morphology of condensed DNA became more compact with increasing concentration. At about 500 microM [Co(NH(3))(6)(3+)] concentration, no condensation patterns could be observed due to charge inversion of the compact structures resulting in failure of adhesion to the positively charged surfaces. The critical concentration for alcohol was about 15% (v/v). At this concentration, a few intramolecular loops could be observed in the AFM images. With increasing ethanol concentration the condensation pattern became more complicated ranging from flower-like to pancake-like. When the solution contained both alcohol and hexammine cobalt (III), DNA condensation patterns could be observed even when the concentrations of the two condensation agents were lower than their critical values. We observed this phenomenon by adding mixtures of 10% alcohol and 8 microM hexammine cobalt (III) to DNA solutions. The condensation patterns were more compact than those of the condensation agents separately. Typical toroids were found at an appropriate alcohol and hexammine cobalt (III) concentration. The collaborative condensation phenomenon was analyzed by electrostatic interaction and charge neutralization.     

Effects of pH on dynamics and rheology during association and gelation via the Ugi reaction of aqueous alginate

Effects of solution pH on the physical properties of a semidilute aqueous alginate solution without cross-linker agent and during gelation via the Ugi multicomponent condensation reaction at a fixed cross-linker concentration have been investigated. Both rheology and turbidity results on the alginate solution without cross-linker revealed enhanced associations at low pH. In the course of the cross-linker reaction, the time of gelation is shortest at pH = 3.5 and at pH values above 3.8 no gel is formed but only a viscosification of the solution is observed. The turbidity during the cross-linking reaction rises as the pH increases from 3.5 to 5. Furthermore, the initial change of the turbidity in the course of the cross-linking process is more pronounced at higher pH. The dynamic light scattering (DLS) results of the reaction mixture at pH = 4.0 (ergodic features at this condition) show that the chain relaxation is slowed down as the reaction proceeds. The effect of pH on the kinetics of the Ugi reaction is discussed.     

Simulation Study of the Conformational Properties of Diblock Polyelectrolytes in Salt Solutions

Coarse-grained molecular dynamics simulations are performed to understand the behavior of diblock polyelectrolytes in solutions of divalent salt by studying the conformations of chains over a wide range of salt concentrations. The polymer molecules are modeled as bead spring chains with different charged fractions and the counterions and salt ions are incorporated explicitly. Upon addition of a divalent salt, the salt cations replace the monovalent counterions, and the condensation of divalent salt cations onto the polyelectrolyte increases, and the chains favor to collapse. The condensation of ions changes with the salt concentration and depends on the charged fraction. Also, the degree of collapse at a given salt concentration changes with the increasing valency of the counterion due to the bridging effect. As a quantitative measure of the distribution of counterions around the polyelectrolyte chain, we study the radial distribution function between monomers on different polyelectrolytes and the counterions inside the counterion worm surrounding a polymer chain at different concentrations of the divalent salt. Our simulation results show a strong dependence of salt concentration on the conformational properties of diblock copolymers and indicate that it can tune the self-assembly behaviors of such charged polyelectrolyte block copolymers.     

The Formation and Salt Induced Melting of a Highly Viscoelastic Mixture of Two Oppositely Charged Polyelectrolytes

A quick and convenient route to prepare a highly viscoelastic mixture of two oppositely charged polyelectrolytes is presented. The investigation was essentially performed at a fixed total polyelectrolyte concentration. The phase behaviour was studied at varying ratios between the two oppositely charged polyions. The mixtures phase separated associatively at mixing ratios in the vicinity of overall charge neutrality, while by screening the attractive forces with NaCl the precipitate could be dissolved. At certain mixing ratios off charge neutrality the mixtures were highly viscoelastic single-phase solutions in the absence of screening electrolyte. When NaCl was added to such a solution the viscoelasticity decreased strongly since the attractive forces between the oppositely charged polyions were screened. Therefore, by contacting an initially salt free mixture of polyions with a brine solution of known concentration, the diffusion of salt into the polyion matrices could be monitored by following the rheology of the mixture as a function of the contact time. It is shown that the transport of NaCl inside the polyion matrices was diffusion controlled.     

Hybrid organic/inorganic materials for photonic applications via assembling of nanostructured molecular units

Hybrid organic–inorganic materials exhibit so versatile properties that they can be considered one of the most interesting classes of materials for photonic applications, for the development of both passive and active devices. A synthetic route used for the preparation of nanostructured organic/inorganic (O/I) materials is the assembling of nano-building blocks (NBBs). This approach allows controlling the extent of phase interaction, which in its turn governs the structure-properties relationships. The non-hydrolytic sol–gel process is recognized as a useful route for the preparation of nanostructured molecular units. The condensation reaction of methacryloxypropyl trimethoxysilane and diphenylsilanediol in a non-hydrolytic sol–gel process has been exploited in order to synthesize nanostructured molecular units for the preparation of hybrid organic/inorganic coatings. The non-hydrolytic condensation reactions were run adding different compounds such as triethylamine, titanium isopropoxide, titanium chloride, and dibutyldilauryltin as condensation promoters. The NBB synthesis was also run under controlled hydrolitic conditions, by exploiting the in situ water production using an ethanol/acetic acid mixture. These reactions have been compared in terms of the influence of the employed reagents on the condensation degree and the product structure. Multinuclear NMR, ATR-FTIR and FT-Raman techniques have been used to study the reaction steps and characterize the final condensation products. Hybrid O/I materials have been prepared by assembling methacrylate-based NBBs in the presence of suitable thermal and photo-initiators. The study on the progress of the thermal polymerization process using differential scanning calorimetry (DSC) will be presented, as well as the preliminary results on the two photon polymerization (TPP) process for the preparation of patternable films.     

Nonstationary vapor concentration fields near the growing droplet of binary solution

Nonstationary vapor concentration fields near the droplet of binary solution growing in the vapor—gas mixture are revealed using the concepts of similarity. The revealed fields are determined with the exact account of the motion of droplet surface and refer to the times at which the droplet reaches sizes that provide for the diffusion regime of droplet growth. To obtain the self-similar solution of the problem of binary condensation, it is necessary to ensure a constant (in time) concentration of binary solution in the growing droplet. The velocities of an increase in the number of molecules and the radius of two-component droplet with time are found with allowance for the equation ensuring this solution. The conditions for the transformation of the self-similar solution of the problem of the condensation of two-component mixture into the solution, which was derived previously for the condensation of one component, are elucidated.