A method to measure the mean thickness and non-uniformity of non-uniform thin film by alpha-ray thickness gauge (author's transl)

The alpha-ray thickness gauge is used to measure non-destructively the thicknesses of thin films, and up to the present day, a thin film with uniform thickness is only taken up as the object of alpha-ray thickness gauge. When the thickness is determined from the displacement between the absorption curves in the presence and absence of thin film, the absorption curve must be displaced in parallel. When many uniform particles were dispersed as sample, the shape of the absorption curve was calculated as the sum of many absorption curves corresponding to the thin films with different thicknesses. By the comparison of the calculated and measured absorption curves, the number of particles, or the mean superficial density can be determined. This means the extension of thickness measurement from uniform to non-uniform films. Furthermore, these particle models being applied to non-uniform thin film, the possibility of measuring the mean thickness and non-uniformity was discussed. As the result, if the maximum difference of the thickness was more than 0.2 mg/cm2, the non-uniformity was considered to distinguish by the usual equipment. In this paper, an alpha-ray thickness gauge using the absorption curve method was treated, but one can apply this easily to an alpha-ray thickness gauge using alpha-ray energy spectra before and after the penetration of thin film.     

苝酰亚胺功能化聚苯乙烯乳胶粒水凝胶膜

将带有硼酸基团的苝酰亚胺荧光分子引入聚苯乙烯共聚乳胶粒表面,再将其嵌入聚丙烯酰胺水凝胶膜内,合成了对葡萄糖敏感的水凝胶膜。通过扫描电子显微镜、激光粒径分析仪对微球的外观形貌、单分散性进行表征,并用原子吸收光谱法间接测定了微球表面苝酰亚胺的含量,研究了苝酰亚胺功能化聚苯乙烯乳胶粒的紫外-可见吸收光谱图及其水凝胶膜的荧光性能。结果表明:苝酰亚胺功能化聚苯乙烯乳胶粒水凝胶膜经浓度逐渐增大的葡萄糖溶液浸泡后,其荧光强度降低,但发射峰位置不变。当葡萄糖浓度达到200 mmol/L时,其荧光淬灭效率为0.34。     

Effect of Molecular Weight on Packing during Latex Film Formation

A UV-visible technique is used to study the evolution of transparency during film formation from latex particles. Latex particles with high and low molecular weight (HM and LM) polymethyl methacrylate (PMMA) are used to prepare films. Two sets of films with different latex content were prepared from HM and LM particles separately, by annealing PMMA particles above the glass transition temperature. Transmitted photon intensity, I(tr), from HM and LM films increased as the annealing temperature was increased. The increase in the transmitted photon intensity is attributed to the latex content (film thickness) for the annealed film samples. It is suggested that as the latex particles are packed (film thickness is increased) fewer voids or cracks are formed in the films. Positive and negative absorption coefficients are measured below and above 210 and 180 degrees C annealing temperatures for the HM and LM films. Packing coefficients are obtained for films in various latex contents. It is observed that LM particles are packed much easier than HM particles. Copyright 2001 Academic Press.     

Some aspects of polymer colloids I. Preparation and properties of different types of latex particles

The boundary region separating a latex particle from the surrounding medium has a great influence on the properties of latex dispersions. Four types of polystyrene and polystyrene/comonomer latices differing greatly in the structure of the boundary region were prepared. The first part of a series of papers reports on the preparation of the various latex dispersions. Mean particle sizes were obtained from simple turbidity measurements, quasi-elastic light scattering, and electron micrographs. The behavior of the particles in the centrifugal force field is a simple tool for detecting aggregation tendencies that are not directly related to salt stability. The BET-surface area agrees with the area calculated from the mean particle size when a sharp boundary and smooth surface is developed between the particle and the surrounding medium. In the case of particles with extended boundary regions (core/shell particles or particles with hairy envelopes), film formation reduces the specific surface area. Removal of soluble oligomers and polymers from the boundary region during subsequent treatments (purification and centrifugation before freeze-drying) can increase the surface area considerably.     

Effect of depletion interactions on transport of colloidal particles in porous media

The influence of depletion interactions on the transport of micrometer-sized, negatively charged polystyrene latex particles through porous media was studied by analysis of particle breakthrough curves as a response to short-pulse particle injections to the inlet of a packed column of glass beads. The column outlet latex particle concentration profiles and the total amount of particles exiting the column were determined as a function of the concentration of small, silica nanoparticles in the solution and the bulk flow rate. Because of similar charges, the silica particles do not adsorb to either the latex particles or glass beads and thus induce an attractive depletion force between the latex particles and glass bead collectors. The total column outlet latex particle amount was calculated by integrating the measured breakthrough concentration curve and compared to the known amount of injected particles at the column inlet. It was found that the particle recovery was a decreasing function of the silica nanoparticle concentration and the carrier fluid residence time, and an increasing function of the velocity in the bed. In addition, removing the silica nanoparticles from the flowing solution caused a second outlet peak to appear, suggesting that some of the polystyrene particles were captured in secondary energy wells. The experimental data were interpreted using the predicted potential energy profile between a single particle and a glass bead, which was assumed to consist of electrostatic, van der Waals, and depletion components. The results indicate that secondary energy wells significantly affect particle transport behavior through porous media.     

Gas phase electrochemical detection of single latex particles

In this study we describe zero current potentiometric measurements in a gaseous flame electrolyte, for the detection of single latex particles. Combustion of polystyrene latex particles when added to a premixed hydrogen/oxygen/nitrogen flame, results in an increase in charged species relative to the surrounding hydrogen flame. As a consequence of this increase in ionic concentration over background, short-lived potential difference transients were measured between two platinum indicator electrodes placed in a two-compartment flame electrochemical cell (described in Electrochem. Commun., 2001, 3, 675-681). The frequency of the transient events was dependent on the number density of latex particles in solution. It is proposed that each short-lived transient event corresponds to the combustion of single latex particles in a flame. A potential difference maximum of 0.56 V when 3.0 microm diameter particles were added to the flame was measured. Also it was shown that it is possible to detect 0.3 microm diameter latex particles using the same technique. It is postulated that the physical basis of the potential difference is due to the establishment of diffusion/junction potential due to the increase in ionisation from polystyrene combustion at the surface of one indicator electrode. This methodology may be applied to the detection of particulates composed of ionisable species (organic or inorganic) in gaseous environment such as bacteria, viruses, pollen grains and dust.     

Irreversible adsorption of particles at random-site surfaces

Irreversible adsorption of negatively charged polystyrene latex particles (averaged diameter 0.9 microm) at heterogeneous surfaces was studied experimentally. The substrate bearing a controlled number of adsorption sites was produced by precovering mica sheets by positively charged polystyrene latex (averaged diameter of 0.45 microm). Positive latex (site) deposition was carried out under diffusion-controlled transport conditions and its coverage was determined by direct particle counting using the optical microscopy. Deposition kinetics of larger latex particles (averaged diameter 0.9 microm) at heterogeneous surfaces produced in this way was studied by direct optical microscope observations in the diffusion cell (under no-convection transport conditions). It was demonstrated that the structure of larger particle monolayers, characterized in terms of the pair correlation function, showed much more short-range ordering than it was predicted for homogeneous surface monolayers at the same coverage. This was found in agreement with theoretical predictions derived from the Monte Carlo simulations. On the other hand, particle adsorption kinetics was quantitatively interpreted in terms of numerical solutions of the governing diffusion equation with the nonlinear boundary condition derived from Monte Carlo simulations. From these kinetic measurements maximum (jamming) coverage of particles was determined in an accurate way by extrapolation. It was concluded that both the monolayer structure and jamming coverage were strongly influenced by the site multiplicity (coordination) effect.     

Diffusion in glassy polymers. IV. Diffusion of methyl ethyl ketone in atactic polystyrene above the critical concentration

Integral absorption and desorption of methyl ethyl ketone in atactic polystyrene were studied as functions of film thickness at 25 and 45°C. with concentrations above the critical concentration of the system. In all cases investigated, the reduced absorption and desorption curves for films of different thicknesses did not give a single curve, though the individual absorption and desorption curves appeared to have the shape expected from the Fickian diffusion mechanism. The initial slopes of the reduced curves increased with increasing film thickness for both absorption and desorption. The quantity R₀, the value of the reciprocal of the half-time for absorption or desorption extrapolated to zero concentration increment, provides a measure of absorption rate at a given initial concentration. The dependence of R₀, on film thickness was almost unaltered in the concentration region concerned at both temperatures. The values of the mutual diffusion coefficient D of the system were calculated by assuming absorption and desorption processes for hypothetical film of infinite thickness to be controlled by the purely Fickian mechanism. The values of D evaluated by this method agreed quite well with those deduced by Kishimoto from steady-state permeation measurements.     

Single particle analysis using fluidic, optical and electrophoretic force balance in a microfluidic system

A unique microfluidic system is developed which enables the interrogation of a single particle by using multiple force balances from a combination of optical force, hydrodynamic drag force, and electrophoretic force. Two types of polystyrene (PS) particles with almost identical size and refractive index (plain polystyrene (PS) particle - mean diameter: 2.06 μm, refractive index: 1.59; carboxylated polystyrene (PS-COOH) particles - mean diameter: 2.07 μm, refractive index: 1.60), which could not be distinguished by optical chromatography, reveal different electrokinetic behaviors resulting from the difference in their surface charge densities. The PS-COOH particles, despite their higher surface charge density when compared to the PS particles, experience a lower electrophoretic force, regardless of ionic strength. This phenomenon can be understood when the more prominent polarization of the counter ion cloud surrounding the PS-COOH particles is considered. The surface roughness of the carboxylated particles also plays an important role in the observed electrokinetic behavior.     

Capillary force required to detach micron-sized particles from solid surfaces—Validation with bubbles circulating in water and 2 μm-diameter latex spheres

The adhesion forces holding micron-sized particles to solid surfaces can be studied through the detachment forces developed by the transit of an air–liquid interface in a capillary. Two key variables affect the direction and magnitude of the capillary detachment force: (i) the thickness of the liquid film between the bubble and the capillary walls, and (ii) the effective angle of the triple phase contact between the particles and the interface. Variations in film thickness were calculated using a two-phase flow model. Film thickness was used to determine the time-variation of the capillary force during transit of the bubble. The curve for particle detachment was predicted from the calculated force. This curve proved to be non-linear and gave in situ information on the effective contact angle developing at the particle–bubble interface during detachment. This approach allowed an accurate determination of the detachment force. This theoretical approach was validated using latex particles 2 μm in diameter.     

Brownian Dynamics Simulation of Film Formation of Mixed Polymer Latex in the Water Evaporation Stage

Brownian dynamics simulations of the filming process of a mixed polymer latex in the water evaporation stage were performed in order to explore the effect of surface potential on latex particle packing and distribution at a temperature far below the glass transitions of polymers in bulk. Polymer latex particles are modeled as spheres that interact via DLVO potential with various surface charge densities for emulsifier-free emulsion polymerized particles and dispersion polymerized particles. It is found that the distribution of modeled poly(methyl methacrylate) and polystyrene latex particles in the finally formed film exhibits a noticeable dependence of surface potentials of latex particles. When the difference of the surface potentials between binary mixed latex particles is small, the particles distribute randomly. In contrast, when the difference of the surface potentials between binary mixed latex particles is large, heterocoagulation occurs and the polymer latex in which the repulsive electrostatic potential is weak will form clusters in the film. The results are in agreement with laser confocal fluorescence microscopy observations of fluorescent dye labeled poly(methyl methacrylate) and polystyrene mixed latex films. The correlation between latex particles increases with increasing repulsive electrostatic potential, and the spatial order can be obtained at the end of the water evaporation stage. Copyright 2000 Academic Press.     

Aqueous particulate foams stabilized solely with polymer latex particles

In this article, a wide range of latexes are evaluated as possible foam stabilizers. These include near-monodisperse, poly(N-vinyl pyrrolidone)-stabilized polystyrene [PNVP-PS] latexes with diameters ranging from 170 nm to 1.62 microm, submicrometer-sized poly(ethylene glycol)-stabilized polystyrene [PEGMA-PS] latex particles, a PNVP-stabilized poly(4-bromostyrene) [PNVP-PBrS] latex with a mean diameter of 870 nm, two PNVP-stabilized poly(methyl methacrylate) [PNVP-PMMA] latexes with mean diameters of 730 nm and 1.20 microm, a PNVP-stabilized poly(2-hydroxypropyl methacrylate) [PNVP-PHPMA] latex with a mean diameter of 630 nm, and a charge-stabilized anionic PS latex of 220 nm diameter. The effect of varying the particle size, latex concentration, and latex surface composition on foam stability were studied in detail. The larger PNVP-PS latexes, the PNVP-PBrS, and the two PNVP-PMMA latexes gave highly stable foams, whereas PEGMA-PS, PNVP-PHPMA, and the charge-stabilized PS latex produced either no foams or foams with inferior long-term stabilities. Scanning electron microscopy studies revealed hexagonally close-packed latex arrays in the walls of the dried foam, which leads to localized moiré patterns being observed by optical microscopy. Moreover, these dried foams are highly iridescent in bright transmitted light.     

Force measurements between sub-100 nm colloidal particles

Interparticle forces have been measured between polystyrene latex particles as small as 85 nm in diameter in KCl solutions. A variant of the differential electrophoresis technique, called particle force light scattering (PFLS), was used to measure forces between Brownian, nearly touching particles for diameters from 4500 nm down to 85 nm. The forces, some less than 0.1 pN, matched to within a factor of 2 with predictions from depletion and DLVO theory.     

Morphology of peroxide-prevulcanised natural rubber latex: effect of reaction time and deproteinisation

A non-uniform mesh structure, i.e. a dense network near the surface of peroxide-prevulcanised natural rubber latex particles, was observed under transmission electron microscopy. In the initial period of prevulcanisation, the swelling ratio of the latex sheet decreased with longer reaction time while an increase in crosslink density of rubber particles containing polystyrene, prepared using the phase transfer/bulk polymerisation process, was noticed. The modulus of the rubber sheet increased up to maximum crosslinking and thereafter decreased. After removal of proteins from the latex membrane layer, derived from protein-lipid originally existing at the rubber particle surface, could not be detected. The absence of proteins, which act as free radical scavengers, resulted in a rapid diffusion of alkoxy radicals into the rubber phase of deproteinised latex and, therefore, a uniform crosslink distribution inside each particle was obtained.     

Measurement of mobility of adsorbed colloids by lateral force microscopy

The surface mobility of colloidal latex particles adsorbed on mica was measured by moving the particles with an AFM tip in the lateral force microscopy mode. The same particle was repeatedly scanned while the normal force was gradually increased, until the particle was displaced from its location on the substrate. The lateral (friction) force curve obtained for that scan was then used to determine the force needed to displace the particle. The data accumulated for approximately 100 particles indicate a wide distribution in the lateral force required. However, the data show that the mean lateral force is proportional to the particle diameter, with the effect of electrostatic interactions on the mobility of adsorbed particles seen to be weak. These results are consistent with classical theories of friction in macroscopic systems.     

Enhancement of electrochemical activity by small-sizing the vinylferrocene-immobilized polystyrene latex particles

Voltammetry of vinylferrocene (VFc)-immobilized polystyrene(PS)-based latex particles was carried out in aqueous suspensions by changing the size of latex particles in order to investigate the dependence of the electroactivity of the particles on their size. The anodic peak current was controlled by diffusion of the latex. The voltammetric peak currents increased with an increase in the diameter of PS latex particles for a given analytical concentration of the particles, exhibiting the dependence on 1.5 powers of the diameter of the particles. The increase can be explained in terms of combination of the uniform distribution of VFc in the particle, the partial charge transfer, and the Stokes-Einstein equation for diffusion coefficients. The oxidation of VFc occurs in the restricted domain (0.07 microm) from a contact point of the particle with the electrode. The overall reaction mechanism is diffusion of the particle to the electrode, partial oxidation to VFc+, release of VFc+ from the particle to the solution, and reduction of the released VFc+.     

Healing and photon diffusion during sintering of high-T latex particles

A steady-state fluorescence technique was used to examine the annealing of films formed from high-T latex particles above the glass transition temperature. The films were prepared by sintering pyrene-labeled poly(methyl methacrylate) latex particles. During the annealing processes, the transparency of the film changed considerably. Direct fluorescence emission from excited pyrene was monitored as a function of annealing temperature to detect these changes. Scanning electron microscopy in conjunction with Monte Carlo simulations of photon diffusion in latex film were used to interpret the fluorescence results. Healing temperature and time were measured at the point where the fluorescence emission intensity becomes maximum. This was associated with the longest optical path of a photon in latex film during healing of particle(SINGLEBOND)particle boundaries. Healing activation energy was measured and found to be 10 kcal/mol. © 1996 John Wiley & Sons, Inc.     

Adsorption of sterically stabilized latex particles at liquid surfaces: effects of steric stabilizer surface coverage, particle size, and chain length on particle wettability

A series of five near-monodisperse sterically stabilized polystyrene (PS) latexes were synthesized using three well-defined poly(glycerol monomethacrylate) (PGMA) macromonomers with mean degrees of polymerization (DP) of 30, 50, or 70. The surface coverage and grafting density of the PGMA chains on the particle surface were determined using XPS and (1)H NMR spectroscopy, respectively. The wettability of individual latex particles adsorbed at the air-water and n-dodecane-water interfaces was studied using both the gel trapping technique and the film calliper method. The particle equilibrium contact angle at both interfaces is relatively insensitive to the mean DP of the PGMA stabilizer chains. For a fixed stabilizer DP of 30, particle contact angles were only weakly dependent on the particle size. The results are consistent with a model of compact hydrated layers of PGMA stabilizer chains at the particle surface over a wide range of grafting densities. Our approach could be utilized for studying the adsorption behavior of a broader range of sterically stabilized inorganic and polymeric particles of practical importance.     

Hollow‐particle latexes: Preparation and properties

Hollow‐particle latexes were prepared according to the following stages: (1) the preparation of the methyl methacrylate–methacrylic acid (MAA)–ethylene glycol dimethacrylate copolymer ( I ) latex, (2) the preparation of a shell ( II ) based on polystyrene or styrene–acrylonitrile–divinyl benzene copolymer polymerized onto copolymer ( I ) particles, and (3) the neutralization of the core ( I ) carboxyl groups with a base (NH₄OH or NaOH) at temperatures close to the glass‐transition temperature of the polymer ( II ). The neutralization resulted in the expansion of the particles and formed water‐filled hollow particles. The microspheres had an overall diameter of 460–650 nm and a hollow diameter of 300–450 nm. Rheological studies and particle size measurements by transmission electron microscopy and dynamic light scattering of the copolymer ( I ) latex indicate that the maximum particle swelling occurred at an approximately equimolar MAA/base ratio. It was found that even without the neutralization of the MAA units, a small hollow formation in the latex particles occurred during stage 2 because one volume of the copolymer ( I ) retained about 8 volume parts of water. It was also discovered that the final hollow‐particle geometry after neutralization depends on the shell copolymer thickness and type as well as on the conditions during stage 3, that is, the time, temperature, base type, and concentration. The opacifying ability of the synthesized hollow particles was investigated in latex coatings. The opacifying ability values were generally in agreement with the hollow‐particle geometry. The only exception was related to the copolymer ( I )/copolymer ( II ) ratio. The maximum hollow volume was obtained at this value equal to 1/8, whereas the highest opacifying ability was observed at 1/10. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1435–1449, 2001     

Calibration of Polarization-Sensitive and Dual-Angle Laser Light Scattering Methods Using Standard Latex Particles

A polarization-sensitive laser light scattering (PSLLS) method and a dual-angle laser light scattering (DALLS) method have been studied for in situ measurement of submicrometer hydrosol and aerosol particles. By using standard monodisperse polystyrene latex particles suspended in water and air as test particles, calibration of systems built based on the above methods have been performed. The effects of light scattered by agglomerated aerosol particles (multiplets) were corrected by considering the fraction of multiplets as determined with an aerosol measurement technique using a differential mobility analyzer. The change in the measured intensities of scattered light with particle diameter was then determined by calculations based on Mie theory. It was shown that the PSLLS system can determine particle diameters as small as approximately 60 nm for the test hydrosol particles and approximately 100 nm for test aerosol particles, respectively. The DALLS system can determine smaller diameters than the PSLLS system for test particles with no light absorption. The change in scattered light intensities with particle diameter was also investigated by theoretical calculations with various refractive indexes and scattering angles. The PSLLS and DALLS systems promise to become routine measurement tools for absorbing and nonabsorbing particles, respectively. Copyright 2001 Academic Press.