Bimodal Dispersion Research Articles

Precipitation behavior of γ′ phase with a multi-model morphology in the Ni-based superalloy GH4720Li during water quenching and subsequent artificial aging and related mechanisms

The microstructure evolution of the γ′ precipitates in GH4720Li superalloy during the heat treatment processes of water quenching and subsequent aging at temperatures of 760 °C, 800 °C, and 850 °C was investigated with particular emphasis on the variation in the morphology, size, and size distribution of the precipitates and related mechanisms. Influence of aging temperature and time on the nucleation, growth, and coarsening behavior of the bimodal dispersion of secondary and tertiary γ′ precipitates were discussed. Results showed that only spherical-shaped secondary γ′ precipitates with sizes ranging from 10 to 50 nm formed during the cooling process of quenching. During aging, the nucleation of tertiary γ′ precipitate, growth of both secondary and tertiary γ′ precipitates follow the typical solid-diffusion-assisted precipitation mechanism, while the abnormal coarsening of the secondary precipitates occurs through coalescing adjacent particles. Aging temperature has a less effect on the precipitation of the tertiary γ′ precipitate but substantially influences the coarsening of the secondary γ′ precipitates. At higher aging temperatures such as 850 °C, the abnormal coarsening of the secondary γ′ precipitates, which always takes place at 760 °C and 800 °C, are significantly suppressed. The aging time mainly influences the growth rate of the secondary γ′ but shows little effect on the evolution of the tertiary γ′ phase. Precipitates strengthen the alloy through strong coupling interaction mechanism. An optimal aging strategy heating at 850 °C for 8 h is proposed for the GH4720Li superalloy, yielding the best uniform dispersion of the precipitates, maximum hardness of the sample, and being considered time and energy-saving.

Heterodyne dynamic light scattering for the characterization of particle dispersions.

Particle self-diffusivities in unimodal and bimodal aqueous dispersions are characterized by dynamic light scattering (DLS) applying a heterodyne detection scheme. For unimodal dispersions close to infinite dilution, it could be evidenced that pure homodyne conditions cannot be realized, leading to an increasing underestimation of diffusivity with a decreasing concentration. Even for bimodal dispersions and neglecting any local oscillator field, the coherent superposition of scattered light from different particle species hinders a clear assignment of the measured signals and their evaluation for diffusivity. In this case, the impact of a crossterm on the determined diffusivities cannot be neglected. The results emphasize that the use of a heterodyne detection scheme in DLS experiments is a key aspect for an accurate determination of particle diffusivities in low-concentrated unimodal and bimodal dispersions.

Tunable distribution of silica nanoparticles in water-borne coatings via strawberry supracolloidal dispersions

HypothesisWater-borne coatings are rapidly expanding as sustainable alternatives to organic solvent-borne systems. Inorganic colloids are often added to aqueous polymer dispersions to enhance the performance of water-borne coatings. However, these bimodal dispersions have many interfaces which can result in unstable colloids and undesirable phase separation. The covalent bonding between individual colloids, on a polymer-inorganic core-corona supracolloidal assembly, could reduce or suppress instability and phase separation during drying of coatings, advancing its mechanical and optical properties. MethodsAqueous polymer-silica supracolloids with a core-corona strawberry configuration were used to precisely control the silica nanoparticles distribution within the coating. The interaction between polymer and silica particles was fine-tuned to obtain covalently bound or physically adsorbed supracolloids. Coatings were prepared by drying the supracolloidal dispersions at room temperature, and their morphology and mechanical properties were interconnected. FindingsCovalently bound supracolloids provided transparent coatings with a homogeneous 3D percolating silica nanonetwork. Supracolloids having physical adsorption only, resulted in coatings with a stratified silica layer at interfaces. The well-arranged silica nanonetworks strongly improve the storage moduli and water resistance of the coatings. These supracolloidal dispersions offer a new paradigm for preparing water-borne coatings with enhanced mechanical properties and other functionalities, like structural color.

A user-friendly graphical user interface for dynamic light scattering data analysis.

Dynamic light scattering (DLS) is a commonly used analytical tool for characterizing the size distribution of colloids in a dispersion or a solution. Typically, the intensity of a scattering produced from the sample at a fixed angle from an incident laser beam is recorded as a function of time and converted into time autocorrelation data, which can be inverted to estimate the distribution of colloid diffusivity to estimate the colloid size distribution. For polydisperse samples, this inversion problem, being a Fredholm integral equation of the first kind, is ill-posed and is typically handled using cumulant expansions or regularization methods. Here, we introduce a user-friendly graphical user interface (GUI) for analyzing the measured scattering intensity time autocorrelation data using both the cumulant expansion method and regularization methods, with the latter implemented using various commonly employed algorithms, including NNLS, CONTIN, REPES, and DYNALS. The GUI allows the user to modulate any and all of the fit parameters, offering extreme flexibility. Additionally, the GUI also enables a comparison of the size distributions generated by various algorithms and an evaluation of their performance. We present the fit results obtained from the GUI for model monomodal and bimodal dispersions to highlight the strengths, limitations, and scope of applicability of these algorithms for analyzing time autocorrelation data from DLS.

Fragmentation dynamics of single agglomerate-to-wall impaction

The de-agglomeration characteristics of single agglomerate-wall impaction are examined using high-resolution shadowgraph imaging. Experiments are performed to investigate the effects of constituent particle size (D50 from 3 to 7 μm) and air velocity on the individual size and velocity of de-agglomerated fragments at conditions relevant to dry powder inhalation systems. De-agglomerated fragment area and trajectories were used to differentiate between pseudo-elastic and inelastic collisions during de-agglomeration. Advanced image processing techniques have enabled provision of joint population distributions of fragment area and aspect ratio, which identify a bimodal dispersion of fragments during de-agglomeration. The bimodality is destroyed with increasing air velocity and also generally diminishes with time after impact. The experiment presented forms a platform for the detailed quantitative characterisation of de-agglomeration behaviour and can be useful towards the development and validation of related computational models for pharmaceutical dry powder inhalers.

Flow of quasi-spherical nanoparticles in liquid composite molding processes. Part II: Modeling and simulation

This paper focuses on the modeling and simulation of the flow and filtration behavior of quasi-spherical nanoparticles (NPs) during liquid composite molding (LCM), as a succession to the experimental studies in Part I. The influence of the bimodal dispersion size characteristic of NPs and the dual-scale characteristic of the preform porous structure on the viscosity of the suspension, the permeability of the preform, and the impregnation behavior is investigated. The modeling and simulation helps not only to predict the impregnation behavior of the NP-modified matrix systems, but also to inversely study the critical particle size that may lead to cake filtration.

Structure and Dynamics of Bimodal Colloidal Dispersions in a Low-Molecular-Weight Polymer Solution.

We present an experimental study of the structural and dynamical properties of bimodal, micrometer-sized colloidal dispersions (size ratio ≈ 2) in an aqueous solution of low-molecular-weight polymer (polyethylene glycol 2000) using synchrotron ultra-small angle X-ray scattering (USAXS) and USAXS-based X-ray photon correlation spectroscopy. We fixed the volume fraction of the large particles at 5% and systematically increased the volume fraction of the small particles from 0 to 5% to evaluate their effects on the structure and dynamics. The bimodal dispersions were homogenous through the investigated parameter space. We found that the partial structure factors can be satisfactorily retrieved for the bimodal colloidal dispersions using a Percus-Yevick hard-sphere potential when the size distributions of the particles were taken into account. We also found that the partial structure factor between the large particles did not exhibit a significant variation with increasing volume fraction of the small particles, whereas the isothermal compressibility of the binary mixture was found to decrease with increasing volume fraction of the small particles. The dynamics of single-component large-particle dispersion obey the principles of de Gennes narrowing, where the wave vector dependence of the interparticle diffusion coefficient is inversely proportional to the interparticle structure factor. The dynamics of the bimodal dispersions demonstrate a strong dependence on the fraction of small particles. We also made a comparison between the experimental effective dynamic viscosity of the bimodal dispersion with the theoretical predictions, which suggest that the complex mutual interactions between the large and small particles have a strong effect on the dynamic behaviors of bimodal dispersions.

An extension of mean-field coarsening theory to include particle coalescence using nearest-neighbour functions

A mean field description of particle coalescence and Ostwald ripening is presented. The inclusion of particle coalescence events is shown to influence the evolution of the size distribution function and the time taken to reach the steady state particle coarsening regime. Nearest neighbour functions are used to represent the spatial arrangement of particles within multi-modal particle radius distributions and to calculate the frequency of coalescence events. The impact of particle coalescence upon long term coarsening kinetics has been studied. By tracking the evolution of a unimodal and bimodal dispersions in phase space, it is demonstrated that coalescence affects the paths of particle dispersion towards the steady state particle coarsening regime as well as the time scales to reach it.

Pattern formation in thin films of polymer solutions: Theory and simulations.

Self-assembly has been recognized as an efficient tool for generating a wide range of functional, chemically, or physically textured surfaces for applications in small scale devices. In this work, we investigate the stability of thin films of polymer solutions. For low concentrations of polymer in the solution, long length scale dewetting patterns are obtained with wavelength approximately few microns. Whereas, for concentrations above a critical value, bimodal dispersion curves are obtained with the dominant wavelength being up to two orders smaller than the usual dewetting length scale. We further show that the short wavelength corresponds to the phase separation in the film resulting in uniformly distributed high and low concentration regions. Interestingly, due to the solvent entropy, at very high concentration values of polymer, a re-entrant behaviour is observed with the dominant length scale now again corresponding to the dewetting wavelength. Thus, we show that the binary films of polymer solutions provide additional control parameters that can be utilized for generating functional textured surfaces for various applications.

Dielectric Relaxation Spectroscopy of Lysozyme Aqueous Solutions: Analysis of the δ-Dispersion and the Contribution of the Hydration Water

The dielectric properties of lysozyme aqueous solutions have been investigated over a wide frequency range, from 1 MHz to 50 GHz, where different polarization mechanisms, at a molecular level, manifest. The dielectric relaxation spectra show a multimodal structure, reflecting the complexity of the protein-water interactions, made even more intricate with the increase of the protein concentration. The deconvolution of the spectra into their different components is not unambiguous and is generally a delicate process which requires caution. We have analyzed the whole relaxation region, on the basis of the sum of simple Debye-type relaxation functions, considering three main contributions. Particular attention has been payed to the δ-dispersion, intermediate between the β-dispersion (rotational dynamics of the protein) and the γ-dispersion (orientational polarization of the water molecules). This intermediate contribution to the dielectric spectrum is attributed to the orientational polarization of water molecules in the immediate vicinity of the protein surface (hydration water). Our measurements clearly demonstrate that, at least at high protein concentrations, the δ-dispersion has a bimodal structure associated with two kinds of hydration water, i.e., tightly bound and loosely bound hydration water. In the concentration range investigated, the existence of a three-modal δ-dispersion, as recently suggested, is not supported, on the basis of statistical tests, by the analysis of the dielectric relaxations we have performed and a bimodal dispersion is accurate enough to describe the experimental data. The amount of the hydration water has been evaluated both from the dielectric parameters associated with the δ-dispersion and from the decrement of the loss peak of the γ-dispersion. The relative weight of tightly bound and loosely bound hydration water is briefly discussed.

Possibilities and limitations of different analytical methods for the size determination of a bimodal dispersion of metallic nanoparticles

Silver nanoparticles (about 70 nm) and gold nanoparticles (about 15 nm) were prepared and colloidally stabilized with poly(vinylpyrrolidone) (PVP). The pure nanoparticles as well as a 1:1 mixture (w:w) were analysed with a variety of methods which probe the size distribution: Scanning electron microscopy, transmission electron microscopy, dynamic light scattering, analytical disc centrifugation, and Brownian motion analysis (nanoparticle tracking analysis). The differences between the methods are highlighted and their ability to distinguish between silver and gold nanoparticles in the mixture is demonstrated. The size distribution data from the different methods were clearly different, therefore it is recommended to apply more than one method to characterize the nanoparticle dispersion. In particular, the smaller particles were undetectable by dynamic light scattering and nanoparticle tracking analysis in the presence of the large particles. For the 1:1 mixture, only electron microscopy and analytical disc centrifugation were able to give quantitative data on the size distribution. On the other hand, it is not possible to make statements about an agglomeration in dispersion with electron microscopy because an agglomeration may also have occurred during the drying process.

One-pot synthesis of organo-functionalized monodisperse silica particles in W/O microemulsion and the effect of functional groups on addition into polystyrene

The direct synthesis from TEOS and organosilanes is carried out in W/O microemulsion in order to prepare monodisperse functionalized silica nanoparticles. The well monodisperse particles are obtained successfully from a wide range of concentration of 3-aminopropyltriethoxysilane (APTES), 3-mercaptopropyltrimethoxysilane (MPTMS), phenyltrimethoxysilane (PTMS), vinyltriethoxysilane (VTES) and 3-cyanoethyltriethoxysilane (CETES) in the solution of TEOS and polyoxyethylene nonylphenol ether (NP-5). The particle size can be controlled without widening the distributions. On the other hand, the direct synthesis with these organosilanes and TEOS by conventional Stöber method using no surfactant provides colloidal solutions with DLS plots with wide or bimodal dispersions. NP-5 is removed by washing the colloids with DEGDEE and the decline of IR absorptions due to the benzene ring stretching is observed. The resultant colloidal powder is occluded into polystyrene by the polymerization of styrene monomer in the presence of these functionalized silica nanoparticles. The heat resistance of modified polystyrene is investigated by TG–DTA in dry air. The position of DTA peak due to combustion of the polymer is shifted to a higher temperature with the addition of silica nanoparticles. The considerably large shift is found in silica nanoparticles prepared with VTES and PTMS, whose difference is higher than that by the addition of simple silica nanoparticle with no functional groups.

Dissipative curvature fluctuations in bilayer vesicles: Coexistence of pure-bending and hybrid curvature-compression modes

We have studied the relaxation dynamics of shape fluctuations in unilamellar lipid vesicles by neutron spin echo (NSE). The presence of a hybrid curvature-compression mode coexisting with the usual bending one has been revealed in the experimental relaxation functions at high q . Differently to the conventional relaxation approximately q (3) typical for bending modes, the hybrid mode was found to relax as approximately q (2) , which is compatible with a dissipation mechanism arising from intermonolayer friction. Complementary data obtained from flickering spectroscopy (FS) in giant unilamellar vesicles confirm the existence of both modes coexisting together. By combining NSE and FS data we have depicted the experimental bimodal dispersion diagram, which is found compatible with theoretical predictions for reliable values of the material parameters. From the present data two conventional dynamical methods (NSE and FS) have been shown to be suitable for measuring intermonolayer friction coefficients in bilayer vesicles.

In situ bimodal or broad particle size distribution using miniemulsion polymerization

AbstractCalculations for maximum volume fraction (φm) for a monomodal and a bimodal dispersion are given. These are extended to express the volume fraction of dispersed phase (φ < φm) for a bimodal distribution. By substituting the volume fraction, so obtained, various semiempirical laws relating relative viscosity to the volume fraction of the dispersed phase for monomodal dispersions can be extended to bimodal dispersions also. It was mathematically shown that the viscosity of a bimodal dispersion shows a minimum for a particular size ratio of small to large particles for a given relative number concentrations of small to large particles and the interspacing between the small and the large particles. Also, it was shown that an increase in the relative number concentrations of small to large particles, keeping the size ratio of small to large particles and the interspacing between the small and the large particles constant, always increases viscosity. These findings also have practical significance because they can be used to obtain high solid content dispersions with minimum viscosity. Candidate recipe and operating variables that can be varied to obtain either bimodal or very broad distributions through miniemulsion polymerization are finally identified. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009

Study of the magnetorheology of aqueous suspensions of extremely bimodal magnetite particles

In this paper we describe the magnetorheological behavior of aqueous suspensions consisting of magnetite particles of two size populations, in the micrometer and nanometer scale, respectively. Previous works on the magnetorheology of oil-based fluids demonstrated that the addition of nanoparticles has a very significant effect on the intensity of the magnetorheological effect. The present contribution confirms such results in the case of aqueous fluids, based on the dependence of the yield stress and the viscosity of the bimodal suspensions on both the composition of the mixtures and the magnetic field strength. It is demonstrated that for a given concentration of micrometer particles, increasing the amount of nanometer magnetite provokes a clear enhancement in the yield stress for all the magnetic fields applied. This is proposed to be due to the formation of heterogeneous aggregates that improve the stability of the suspensions and ease the building of well-arranged field-induced structures. The behavior of both the yield stress and the post-yield viscosity agrees better with the predictions of standard chain models when the relative proportion of both types of particles confers optimum stability to the bimodal dispersions.

A Physical Basis for Stability in Bimodal Dispersions Including Micrometer-sized Particles and Nanoparticles using Both Linear and Non-linear Models to Describe Yield

This work investigates the settling response of bi-disperse silicone oil-based magnetorheological fluids with varying solids loading (content) of Fe magnetic particles at three ratios of nanoparticles to micron size particles. The solid loading (content) of Fe magnetic particles in silicone oil was 50 or 60% by weight with nanoparticle fractions of 0, 10, or 15% by weight of the total solids loading. Sedimentation experiments are conducted using Z-axis translating laser light scattering at ambient temperature. Sedimentation velocities are determined from clear layer separation and functional particulate transport by creeping flow. Settling rates of 1—3 μm/s have been observed in the dispersions without nanoparticles. Viscosity testing shows lower yield stress with nanoparticle inclusion and the typical rise in shear stress with increasing shear rate and applied magnetic field using both the linear Bingham and the non-linear Hershel—Bulkley models. Adding nanoparticles also reduced sedimentation velocity by roughly two orders of magnitude from those without nanoparticles. The nanoparticles act as plugs or otherwise interact in forming soft gel particulates leading to a denser sedimentation front yielding fewer percolation holes through which the fluid can permeate. Either way, the addition of nanoparticles leads to a more effective stabilization mechanism for the dispersion.

New method for strength improvement of silica optical fibers

The reliability and the expected lifetime of optical fibers used in telecommunication technologies are closely related to the chemical environment action on the silica network. To ensure the long-term mechanical strength of the optical fibers, a polymer coating was applied onto the fiber surface during fiber fabrication. This external coating is vital to ensure a long optical fiber lifetime. Its protective action includes several functions, such as to protect glass fiber from any external damage, to limit chemical attack, in particular that of water, and finally to ensure fatigue protection and bending insensitivity, especially during handling and in-service installation. Since the mechanical strength of the fiber is controlled by its surface characteristics, we propose a new method for increasing fiber strength. The silica optical fibers used were 125 μm in diameter, with a 62.5 μm thick epoxy-acrylate coating. Fibers were rolled up around two similar cylinders. Using a screw, these cylinders moved away from one another and thus subjected the fibers to stretching. Submitted to this mechanical loading, the distended fibers were plunged into hot water at 65 or 85 °C and aged for several days. Then, the fibers were removed from the water and various weights were suspended on the fiber ends. Thus, the fibers were subjected to a tensile loading in static fatigue for several days. Just before fiber rupture, the fibers were unloaded and subjected to dynamic tensile tests at different velocities. Result analysis proved that the aging in hot water increased the fiber strength. The Weibull's diagram study shows a bimodal dispersion of defects on the fiber surface and the important role of polymer coating.

Ostwald ripening of precipitates during two successive heat treatments performed at different temperatures

Two-stage Ostwald ripening of precipitates has been investigated experimentally and theoretically. A nickel-base alloy in which spherical nano-scale precipitates of the γ′-phase form served as a model system. Each specimen was heat treated at two successive temperatures T1 and T2 in the range 949–1119K. Thus, monodal as well as bimodal precipitate dispersions were produced. On the basis of an equation published by Wagner, Lifshitz, and Slyozov for isothermal ageing, the function r(t1,T1,t2,T2)¯ is modeled, where r(t1,T1,t2,T2)¯ is the average precipitate radius after double ageing and ti is the ageing time at Ti. In the case of bimodal γ′-precipitate dispersions, two average radii are considered. The agreement between measured and calculated values for r(t1,T1,t2,T2)¯ is within 7%, which is about the same accuracy as that of experimental data determined by transmission electron microscopy. The quoted agreement holds for monodal γ′-precipitate dispersions as well as for each γ′-population of bimodal dispersions.

Structural and optical properties of InP quantum dots grown on GaAs(001)

We investigated structural and optical properties of type-II InP/GaAs quantum dots using reflection high energy electron diffraction, transmission electron microscopy, atomic force microscopy, grazing incidence x-ray diffraction, and photoluminescence techniques. The InP dots present an efficient optical emission even when they are uncapped, which is attributed to the low surface recombination velocity in InP. We compare the difference in the optical properties between surface free dots, which are not covered by any material, with dots covered by a GaAs capping layer. We observed a bimodal dispersion of the dot size distribution, giving rise to two distinct emission bands. The results also revealed that the strain accumulated in the InP islands is slightly relieved for samples with large InP amounts. An unexpected result is the relatively large blue shift of the emission band from uncapped samples as compared to capped dots.

Viscosity of Electrostatically Stabilized Dispersions of Monodispersed, Bimodal, and Trimodal Silica Particles

Effect of particle size and polydispersity on the viscosity and maximum packing fraction of aqueous colloidal dispersions has been studied. For dispersions of mono‐sized particles, the results indicate that there is a linear relationship between the log(η) (viscosity) and particle size at a fixed shear rate and volume fraction of solids. However, there is a particle diameter at which there is a decrease in the dependency of viscosity on particle size as the slope of the linear plots of log(η) versus particle diameter changes to a smaller value. Preliminary calculations indicate that this particle size may correspond to a separation distance at which electrostatic energy as compared with the thermal energy of the particles can be ignored. In the case of bimodal dispersions, the viscosity is affected by both absolute size and the ratio of the two sizes. The effect of particle size ratio on the viscosity was investigated using bimodal dispersions of the same size coarse particles, but fines of different sizes. There is a critical volume ratio below which bimodal dispersions of larger size ratios show lower viscosities than systems of smaller size ratios. Above this volume ratio of the two sizes, the trend becomes reversed and the fines will have a dominant effect on the viscosity behavior of the bimodal system. Statistically designed experiments were carried out using trimodal mixtures of monodispersed silica particles and it was shown that tridispersed suspensions demonstrate similar behavior as bidispersed suspensions, with a minimum in viscosity observed as a function of particle volume ratio.