Molecular dynamics simulation of the structural configuration of binary colloidal monolayers

Molecular dynamics simulations of binary colloidal monolayers, i.e., monolayers consisting of mixtures of two different particle sizes, are presented. In the simulations, the colloid particles are located at an oil-water interface and interact via an effective dipole-dipole potential. In particular, the influence of the particle ratio on the configurations of the binary monolayers is investigated for two different relative interaction strengths between the particles, and the pair correlation functions corresponding to the binary monolayers are calculated. The simulations show that the binary monolayers can only form two-dimensional crystals for certain particle ratios, for example, 2:1, 6:1, etc., while, for example, for a particle ratio of 7:1 the monolayers are found to be in a disordered, glassy state. The calculations also reveal that in analogy to the Wigner lattice the configurations are very sensitive to the relative interaction strength between the particles but not to the absolute magnitude of the interaction strength, even when particle size effects are taken into account. Consequently, it is argued that a comparison between the calculated configurations and actual binary particle monolayer systems could provide useful information on the relative interaction strength between large and small particles. Possible mechanisms giving rise to disparities in the interaction strength between large and small particles are described briefly.     

Effect of colloidal particle size on adsorbed monodisperse and bidisperse monolayers

Coating hydrogel films or microspheres by an adsorbed colloidal shell is one synthesis method for forming colloidosomes. The colloidal shell allows control of the release rate of encapsulated materials, as well as selective transport. Previous studies found that the packing density of self-assembled, adsorbed colloidal monolayers is independent of the colloidal particle size. In this paper we develop an equilibrium model that correlates the packing density of charged colloidal particles in an adsorbed shell to the particle dimensions in monodisperse and bidisperse systems. In systems where the molar concentration in solution is fixed, the increase in adsorption energy with increasing particle size leads to a monotonic increase in the monolayer packing density with particle radius. However, in systems where the mass fraction of the particles in the adsorbing solutions is fixed, increasing particle size also reduces the molar concentration of particles in solution, thereby reducing the probability of adsorption. The result is a nonmonotonic dependence of the packing density in the adsorbed layer on the particle radius. In bidisperse monolayers composed of two particle sizes, the packing density in the layer increases significantly with size asymmetry. These results may be utilized to design the properties of colloidal shells and coatings to achieve specific properties such as transport rate and selectivity.     

Nucleation rate measurement of colloidal crystallization using microfluidic emulsion droplets

An emulsion crystallization method has been demonstrated to measure the nucleation rate of a thermoresponsive colloidal poly-N-isopropylacrylamide (PNIPAM) system. The colloidal PNIPAM suspension was injected into a microfluidic flow-focusing device to generate monodispersed droplets in oil. The temperature was controlled to fine tune the volume fraction of the PNIPAM particles, and the microfluidic flow rate was varied to change the droplet sizes, thus altering the nucleation volume. Using independent droplets, we can isolate the nucleation events to eliminate the interactions among crystallites that existed in bulk or large droplet systems. Therefore, we were able to carry out accurate nucleation rate measurements of colloidal crystals. This emulsion crystallization method is promising for bridging the gap among theories, simulations, and experiments for nucleation kinetics studies.     

Conglomerate crystallization on self-assembled monolayers

In this communication, we demonstrate that chiral self-assembled monolayers can be used for polymorphism control of chiral crystals. We studied the crystallization of DL-glutamic acid on chiral self-assembled monolayers and showed that crystallization of DL-glutamic acid on the chiral SAMs resulted in stabilization of the metastable conglomerate form.     

Effect of bicarbonate ions on the crystallization of calcite on self-assembled monolayers

We use molecular dynamics simulations to investigate the nucleation of calcite crystals on self-assembled monolayers. We show how the presence of bicarbonate ions adsorbed on the monolayer surface can both aid nucleation and control the orientation of the growth of the crystal. Using a simple model of the nucleation process and calculated interfacial energies, we calculate the enhancement (with respect to the homogeneous nucleation rate) of the nucleation of calcite on the (012) and (0001) faces. The calculations show clearly that the (012) face is favored over the (0001) face and that the nucleation rate is enhanced for self-assembled monolayers made from molecules containing an even number of carbon atoms in the alkyl chain over those containing an odd number.     

Chemical, electrochemical, and structural stability of low-density self-assembled monolayers

The stability of low-density self-assembled monolayers of mercaptohexadecanoic acid on gold is studied under a variety of storage conditions--air at room temperature, argon at room temperature and 4 degrees C, and ethanol at room temperature. The structural monotony of the low-density monolayers was assessed by monitoring the alkyl chains of LDSAMs by grazing-angle Fourier transform infrared spectroscopy as a function of time. Independently of the storage conditions, both symmetric and asymmetric methylene stretches at 2923 and 2852 cm-1 decreased after 4 weeks to 2919 and 2849 cm-1, respectively. These data suggest an increased ordering of the alkyl chains that is distinctly different from that of conventional high-density monolayers of mercaptohexadecanoic acid included as a reference in this study. As a further extension of this observation, the electrochemical barrier properties of the low-density monolayers were assessed by electrochemical impedance spectroscopy and did not change significantly for any of the storage conditions over a period of 4 weeks. Moreover, X-ray photoelectron spectroscopy was used to assess the chemical changes in the low-density monolayers over time. The chemical composition was essentially unaltered for all storage conditions. Specifically, oxidation of the sulfur headgroup, a common cause of monolayer degradation, was excluded for all test conditions on the basis of XPS analysis. This study confirms excellent storage stability for low-density monolayers under commonly used storage conditions and bridges an important technological gap between these systems and conventional high-density systems.     

Simulations of calcite crystallization on self-assembled monolayers

This paper presents simulations of calcium carbonate ordering in contact with self-assembled monolayers. The calculations use potential-based molecular dynamics to model the crystallization of calcium carbonate to calcite expressing both the (00.1) and (01.2) surfaces. The effect of monolayer properties: ionization; epitaxial matching; charge density; and headgroup orientation on the crystallization process are examined in detail. The results demonstrate that highly charged surfaces are vital to stimulate ordering and crystallization. Template directed crystallization requires charge epitaxy between both the crystal surface and the monolayer. The orientation of the headgroup appears to make no contribution to the selection of the crystal surface.     

In situ monitoring of structural changes during colloidal self-assembly

Reflectance spectroscopy is utilized to monitor structural changes during the self-assembly of a monodisperse colloidal system at the meniscus of a sessile drop on an inert substrate. Treating the ordered colloidal structure as a photonic crystal is equivalent to monitoring the changes in the photonic band gap (PBG) as the colloidal system self-assembles heterogeneously into a crystal through solvent evaporation in ambient conditions. Using a modified Bragg's law model of the photonic crystal, we can trace the structural evolution of the self-assembling colloidal system. After a certain induction period, a face-centered cubic (FCC) structure emerges, albeit with a lattice parameter larger than that of a true close-packed structure. This FCC structure is maintained while the lattice parameter shrinks continuously with further increase in the colloidal concentration due to drying. When the structure reaches a lattice parameter 1.09 times the size of that of a true close-packed structure, it undergoes an abrupt decrease in lattice spacing, apparently similar to those reported for lattice-distortive martensitic transformations. This abrupt final lattice shrinkage agrees well with the estimated Debye screening length of the electric double layer of charged colloids and could be the fundamental reason behind the cracking commonly seen in colloidal crystals.     

Visualization of structural rearrangements during annealing of solvent-crazed isotactic polypropylene

Structural rearrangements taking place upon the annealing of solvent-crazed isotactic PP are studied by the direct microscopic method. Independently of the type of its crystalline structure, solvent-crazed PP undergoes shrinkage in a wide temperature interval, starting even from room temperature and up to its melting temperature. This shrinkage is a result of the structural processes in crazes and proceeds via shutting down of the walls of individual crazes. This low-temperature shrinkage of solvent-crazed PP is assumed to have an entropy nature. This process involves the contraction of extended polymer chains and their transition into thermodynamically favorable conformations. This contraction is allowed because, upon annealing, the entropy contracting force increases. As a result, the crystalline framework of oriented PP melts down (amorphization), extended chains appear contracted, stored stresses relax, and subsequent recrystallization in the unstressed state takes place.     

Kinetic stages of single-component colloidal crystallization

To harness the full potential of colloidal self-assembly, the dynamics of the transition between colloids in suspension to a colloidal crystalline film should be better understood. In this report, the structural changes during the self-assembly process in a vertical configuration for colloids in the size range 200-400 nm are monitored in situ, using the transmission spectrum of the colloidal assembly treated as an emergent photonic crystal. It is found that there are several sequential stages of colloidal ordering: in suspension, with a larger lattice parameter than the solid state, in a close-packed wet state with solvent in the interstices, and, finally, in a close-packed dry state with air in the interstices. Assuming that these stages lead continuously from one to another, we can interpret colloidal crystallization as being initiated by interparticle forces in suspension first, followed by capillary forces. This result has implications for identifying the optimum conditions to obtain high-quality nanostructures of submicrometer-sized colloidal particles.     

Effect of acidification rate,acidification temperature,final pH,and stabilizer content on colloidal stability of whey-based pomegranate beverage

The effect of acidification rate (during 0, 30, and 60 minutes), acidification temperature (25, 50, and 75°C), final pH (3.4, 3.6, and 3.8), and pectin content (0.2, 0.4, and 0.6%) on the stabilization of whey-based pomegranate beverage was studied. Serum separation, particle size distribution, viscosity, zeta potential, pH, and acidity of beverage samples were observed during storage. Results revealed that acidification rate, acidification temperature, and pectin content had a significant effect; however, final pH (of the studied range) had no significant effect on the phase separation. The amount of phase separation decreased and the stability increased with increasing acidification rate, acidification temperature, and stabilizer content. In addition, the results of particle size, zeta potential, and viscosity confirmed the results of phase separation and also the most stable beverage had a pH near 3.8.     

Effect of hydrocarbon chain and pH on structural and topographical characteristics of phospholipid monolayers

Structural characteristics (structure, elasticity, topography, and film thickness) of dipalmitoyl phosphatidylcholine (DPPC) and dioleoyl phosphatidylcholine (DOPC) monolayers were determined at the air-water interface at 20 degrees C and pH values of 5, 7, and 9 by means of surface pressure (pi)-area (A) isotherms combined with Brewster angle microscopy (BAM) and atomic force microscopy (AFM). From the pi-A isotherms and the monolayer elasticity, we deduced that, during compression, DPPC monolayers present a structural polymorphism at the air-water interface, with the homogeneous liquid-expanded (LE) structure; the liquid-condensed structure (LC) showing film anisotropy and DPPC domains with heterogeneous structures; and, finally, a homogeneous structure when the close-packed film molecules were in the solid (S) structure at higher surface pressures. However, DOPC monolayers had a liquid-expanded (LE) structure under all experimental conditions, a consequence of weak molecular interactions because of the double bond of the hydrocarbon chain. DPPC and DOPC monolayer structures are practically the same at pH values of 5 and 7, but a more expanded structure in the monolayer with a lower elasticity was observed at pH 9. BAM and AFM images corroborate, at the microscopic and nanoscopic levels, respectively, the same structural polymorphism deduced from the pi-A isotherm for DPPC and the homogeneous structure for DOPC monolayers as a function of surface pressure and the aqueous-phase pH. The results also corroborate that the structural characteristics and topography of phospholipids (DPPC and DOPC) are highly dependent on the presence of a double bond in the hydrocarbon chain.     

Acyl chain ordering and crystallization in lipid monolayers

The condensed phases of phospholipid monolayers on an air/water interface are described by means of a microscopic interaction model which incorporates intra-chain flexibility as well as crystal orientation variables. The phase transitions and microstructures are studied as functions of lateral pressure. The model predicts, in accordance with recent synchrotron X-ray experiments, that the chain-ordering transition and the crystallization of the monolayer need not take place at the same lateral pressure.     

Block polyelectrolytes and colloidal stability

The interactions of sodium dodecyl sulfate (SDS) with poly(ethylene oxide)/poly(alkylene oxide) (E/A) block copolymers are explored in this study. With respect to the specific compositional characteristics of the copolymer, introduction of SDS can induce fundamentally different effects to the self-assembly behavior of E/A copolymer solutions. In the case of the E(18)B(10)-SDS system (E = poly(ethylene oxide) and B = poly(butylene oxide)) development of large surfactant-polymer aggregates was observed. In the case of B(20)E(610)-SDS, B(12)E(227)B(12)-SDS, E(40)B(10)E(40)-SDS, E(19)P(43)E(19)-SDS (P = poly(propylene oxide)), the formation of smaller particles compared to pure polymeric micelles points to micellar suppression induced by the ionic surfactant. This effect can be ascribed to a physical binding between the hydrophobic block of unassociated macromolecules and the non-polar tail of the surfactant. Analysis of critical micelle concentrations (cmc(*)) of polymer-surfactant aqueous solutions within the framework of regular solution theory for binary surfactants revealed negative deviations from ideal behavior for E(40)B(10)E(40)-SDS and E(19)P(43)E(19)-SDS, but positive deviations for E(18)B(10)-SDS. Ultrasonic studies performed for the E(19)P(43)E(19)-SDS system enabled the identification of three distinct regions, corresponding to three main steps of the complexation; SDS absorption to the hydrophobic backbone of polymer, development of polymer-surfactant complexes and gradual breakdown of the mixed aggregates.     

String formation and demixing in monolayers of dipolar colloidal mixtures

Employing hypernetted chain (HNC) integral equations and a stability analysis we investigate the structure and phase behavior of bidisperse mixtures of dipolar hard spheres with different size ratios s=σ(S)/σ(L) confined to a plane. The dipole moments of the particles are perfectly ordered along an in-plane direction, yielding anisotropic interactions favoring chain formation. Exploring a range of size ratios and compositions, our study predicts a complex interplay between aggregation phenomena, on the one hand, and volume phase transitions, on the other hand. In dilute, strongly asymmetric systems (s = 0.5), our HNC analysis indicates chain formation of the large particles, while the small particles act as a weakly correlated background. According to our fluctuation analysis, this aggregation behavior results in combined condensation-demixing transitions, with a trend towards pure demixing when the concentration of the large particles, c(L), becomes small. In dense systems, the most interesting results are found for intermediate size ratios, s ~ 0.7-0.8. Here we find signatures of a concentration-driven transition from pure chains of large particles (large c(L)) to mixed chains with alternating order of large and small particles (small c(L)). The two regimes are separated by a characteristic "jump" in the HNC non-solution line.     

Stability and growth of nuclei during the crystallization of polymers

During the crystallization of linear flexible chain molecules a boundary phase necessarily develops which has a volume of its own. The boundary phase, however, is not autonomous so that Gibbs' phase rule loses its validity. The 2-phase system {crystal; boundary phase} is bivariant, the 3-phase system {crystal, boundary phase; melt} is monovariant. At quasistatic cooling the ability of the crystal nuclei to grow demands the formation of loose loops or tie-molecules. This leads to the final state of the crystallization to be an arrested equilibrium state. The internal equilibrium state cannot be reached under normal circumstances.Dedicated to H.-G. Kilian on the occasion of his 60th birthday.     

Kinetic analyses of colloidal crystallization in shear flow

Colloidal crystallization kinetics is studied in the shear flow of a suspension of colloidal silica spheres (110 nm in diameter), using a continuously-circulating type of stopped flow cell system. The crystallization rate from a suspension containing a small amount of nuclei and/or single crystals is high compared with that from a suspension containing no nuclei and/or single crystals. Crystal growth takes place at shear rates smaller than 3.4 s^–1 and at sphere concentrations higher than a volume fraction of 0.004.     

Effect of reaction media on the growth and photoluminescence of colloidal CdSe nanocrystals

Using cadium oxide (CdO) as the Cd precursor and tri-n-octylphosphine selenide (TOPSe) as the Se source, TOP-capped and TOP/tri-n-octylphosphine oxide (TOPO)-capped CdSe nanocrystals were synthesized without the use of an acid. The synthetic approach involved the addition of a TOPSe/TOP solution into a CdO/TOP solution with or without TOPO at one temperature and subsequent growth at a lower temperature. The temporal evolution of the optical properties, namely, absorption and luminescence, of the growing nanocrystals was monitored in detail. A comprehensive examination on the control of the photoluminescence (PL) properties was performed by systematically varying the TOP/TOPO weight ratio of the reaction media. Surprisingly, a rational choice of 100% TOP or 80% TOP was found to produce "quality" nanocrystals when monitored under the present experimental conditions and growth-time scale. The term "quality" is mainly based on the sharp features and rich substructure exhibited in the absorption spectra of the growing nanocrystals, as well as the sharp features in the emission spectra with narrow full width at half-maximum (fwhm). There are two distinguishable stages of growth: an early stage (<5 min) and a later stage. TOP plays a major role in the control of a slow growth rate in the early stage, while TOPO controls slow growth in the later stage. The optical sensitivity of the growing nanocrystals when dispersed in nonpolar or polar solvents was studied, including two size-dependent parameters, namely, the solvent sensitivity (PL intensity) and nonresonant Stokes shift (NRSS). The insights gained from the present study enable a synthetic approach in which high-quality CdSe nanocrystals are achieved with high synthetic reproducibility.