Determination of the influence of the polymer structure and particle size on the film formation process of polymers by atomic force microscopy

The particle size and morphology of a synthetic polymer latex were shown to influence the film formation behavior. Theoretical models predict that small particles coalesce more easily than large colloids do.The influence of particle size and morphology of differently structured lattices on the film-formation process was investigated by atomic force microscopy (AFM). Sequences of AFM images were acquired over a certain temperature range or at room temperature as a function of time. From the resulting images the average particle diameter of the latex particles in the surface layer was determined as a function of the time or temperature. The resulting curves could be compared to observe differences in the film formation kinetics of the different lattices. These AFM studies confirmed that the film formation behavior is influenced by the particle size and particle morphology, but that the core/shell ratio of core-shell particles has no significant influence on the film formation kinetics.     

环糊精对聚合物乳胶粒子性能影响的研究

以苯乙烯（St）和甲基丙烯酸丁酯（BMA）为单体,采用核壳乳液聚合的方法,制备了苯丙乳胶粒子。研究了不同含量β-环糊精(β-CD)对聚合体系反应过程及苯丙乳胶粒子性能的影响。动态光散射(DLS)数据显示,制备的乳胶粒子粒径小且分布窄,分布均匀,具有单分散性;接触角表明,乳胶膜的亲水性增强,表面能较改性前有所增加;原子力显微镜(AFM)和透射电子显微镜(TEM)表明,改性后乳胶粒子为核壳结构,粒径分布均匀,大小均一;当β-CD含量为5 %时,制得的苯丙乳液聚合物综合性能最佳。     

Particle sizing of flocculated latex particles by physisorption of nitrogen

Physisorption of nitrogen at one specific pressure is used to determine the specific surface area of a flocculated polystyrene latex by applying BET theory. Assuming that a flocculated sample of Polymer latex is composed of distinct spherical latex particles (i.e., there is no coagulation of particles), the volume–surface-average diameter can be calculated. The resulting diameters are compared to sizes obtained using a disc centrifuge sedimentometer, which fractionizes the particles by sedimentation. The diameters from both techniques were in good agreement, showing that physisorption of nitrogen, which is a simple technique, can be used to determine sizes of flocculated latex particles. This agreement also shows that the flocculation of the polystyrene latex produced separate nonporous spherical particles. When flocculation of a latex is done above its glass transition temperature, coagulation will occur. While other particle sizing techniques can produce particle size distributions, the physisorption of nitrogen only gives the volume–surface-average diameter. However, one advantage of the physisorption of nitrogen is that it covers a broad range of particle sizes compared to most other techniques. © 1994 John Wiley & Sons, Inc.     

PMMA/PAN核-壳粒子制备工艺研究

加入适量的引发剂,通过无皂乳液聚合,以聚甲基丙烯酸甲酯( PMMA)核体为种子乳液,制备了PMMA/PAN核-壳乳液.实验中分别对引发剂量、丙稀腈( AN)滴加量对PMMA/PAN壳层厚度及其粒径和粒径分布的影响进行了较详细的研究,确定了种子乳液聚合法制备PMMA/PAN核-壳结构聚合物粒子的实验方法及条件.通过激光粒度仪、扫描电镜和透射电镜对核-壳粒子的形态结构进行了表征,证明了PMMA/PAN复合粒子的核-壳结构.     

A quantitative treatment of particle size distributions in emulsion polymerization

A quantitative analysis is presented for predicting the particle size distributions obtained in emulsion polymerization. The results obtained are compared with experimental data in terms of the particle-size-distribution curves as well as the statistical parameters of the distributions. Comparisons are made for changes in initiator level, surfactant level, water:monomer ratio, and temperature. The manner in which these variables change the distributions and the reasons for these changes are identified. The distribution of radicals among particles of different sizes is seen to be significant. Large particles are expected to contain a greater number of radicals per particle than the smaller ones in the same latex. The effects of such a radical distribution upon the properties of the latex are discussed.     

Preparation and characterization of imidazole‐functionalized microspheres

The preparation of imidazole‐functionalized latex microspheres by a two‐stage emulsion copolymerization process and their characterization are reported on. Emulsifier‐free emulsion copolymerization of styrene (St) and 1‐vinyl imidazole (VIMZ) exhibited bimodal particle size distributions caused by secondary homogeneous nucleation process. However, secondary nucleation can be avoided by using cetyltrimethylammonium bromide (CTAB) as a stabilizer at a concentration below its cmc (critical micelle concentration). This would result in the formation of monodisperse latex particles. The final particle size diameter depended on the concentration of CTAB as well as the amount of VIMZ. To control the amount of the functional imidazole groups on the latex particle surfaces, independent of the latex diameters, without secondary nucleation of particles, the seeded emulsion copolymerization of styrene and VIMZ was explored as a second‐stage polymerization at different concentrations and ratios of monomers in the presence of the previously prepared monodisperse poly(styrene‐co‐1‐vinyl imidazole) seed latex particles. The concentration of imidazole functional groups on the surface of the latex particles could also be varied through the rearrangement of hydrophilic imidazole groups by varying the second‐stage monomer addition process such as the utilization of monomer‐swollen seed particles or a shot addition of monomers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 120:5753–5762, 2006     

Simultaneous Elemental Composition and Size Distributions of Submicron Particles in Real Time Using Laser Atomization Ionization Mass Spectrometry

Composition and size of individual submicron particles have been measured using a laser atomization ionization mass spectrometry technique, the Particle Blaster. Individual particles are quantitatively converted to atomic cations, providing information on both their complete elemental composition and particle size. Measured average atomic ratios for 100 nm particles of sodium chloride is 1.12 +- 0.36 (Cl:Na), for 50 nm particles of silica is 1.93 +- 0.52 (O:Si), and for 64 nm polystyrene latex spheres (PSL) is 1.13 +- 0.19 (H:C), in excellent agreement with the empirical formulae. Calculated particle sizes agree well with electrostatic classifier or TEM measurements in the size range of 17-900 nm diameter for particles of sodium chloride, silicon, and PSL. Size distributions are also obtain able, giving narrower distributions than are measured with an electrostatic classifier, for particles of alumina, silica, sodium chloride, and PSL spheres. Comparison with TEM data shows comparable primary particle sizes, but numerous particle aggregates are detected by the Particle Blaster which are unreported by the TEM measurements.     

Probing polymer interdiffusion in carboxylated latices with force modulation atomic force microscopy

Interdiffusion of polymer chains between latex particles is a prerequisite for the development of good mechanical strength and homogeneity in a latex film. This process may be retarded in carboxylated latices if the particles are surrounded by a hard cell wall consisting of ionic groups on the particle surface. The presence of an ionic cell wall can be indirectly detected by atomic force microscopy (AFM) because surfactant migration to the film/air interface is retarded compared with a non-ionic case. In this paper we have used force modulation atomic force microscopy to directly probe the relative polymer density across the film surface during annealing thereby qualitatively monitoring the interdiffusion process. The applicability of this method to study polymer interdiffusion will be discussed.     

Polymeric particles prepared with fluorinated surfmer

Fluoro-containing particles have been obtained by miniemulsion polymerization of styrene and n-butyl methacrylate in presence of fluorinated monomer mono-fluoroalkyl maleate (MFM) which acts as a surfmer providing efficient stability to obtained dispersion and functionalization of particle surface with fluoro-groups. Increase of the MFM concentration in reaction mixture reduces the particle size and dispersions with narrower particle size distribution can be obtained. Blends of fluorinated latexes with styrene-butadiene copolymer latex were examined with regard to formation of low free energy surfaces. It has been shown that blends containing MFM-functionalized polymeric particles possess more hydrophobic surfaces then similar latex films, where particles prepared by polymerization of expensive fluorinated monomer have been applied.     

2‐Hydroxyethylmethacrylate carrying uniform porous particles: preparation and electron microscopy

Uniform macroporous particles carrying hydroxyl groups have been obtained in the size range 3–11.5 µm by seeded polymerization. For this purpose, uniform polystyrene particles in the size range 1.9–6.2 µm were used as seeds. The seed particles were successively swollen by dibutyl phthalate (DBP) and a monomer mixture comprising styrene, 2‐hydroxyethylmethacrylate (HEMA) and a crosslinker. Two different crosslinkers, divinylbenzene (DVB) and ethylene glycol dimethacrylate (EGDMA), were tested. Size distribution properties together with bulk and surface structures of the particles have been characterized by both scanning and transmission electron microscopy. While EGDMA provides uniform particles with a non‐porous surface, DVB produces uniform particles having a highly porous surface and interior. The comparison of FTIR and FTIR‐DRS spectra shows that the HEMA concentration is higher on the particle surface than within the particle interior. Seed latex size and monomer/seed latex ratios are identified as the most important variables affecting the final particles. Different seed latexes have been tried; the result is that highly macroporous particles with a sponge‐like pore structure both on the surface and in the particle interior have been obtained by use of the seed latex with the largest particles and the lowest molecular weight. An increase in the HEMA feed concentration leads to final particles with a non‐porous surface and a crater‐like porosity in the particle interior. The average pore size significantly decreases with increasing DBP/seed latex and monomer/seed latex ratios. © 2001 Society of Chemical Industry     

Characterization and properties of gradient polyacrylate latex particles by gradient emulsion polymerization

In this study, gradient acrylate latex particles were synthesized by gradient copolymerization. n-Butyl acrylate (BA) and methyl methacrylate (MMA) were used as co-monomers, dodecyl diphenyl ether sodium disulfonate as the emulsifier, and potassium persulfate as the initiator. The technique involved the continuous addition of one monomer mixture into a stirred tank containing another monomer mixture. Their microstructure and properties were analyzed by nuclear magnetic resonance (NMR), gel permeation chromatography (GPC), differential scanning calorimetry (DSC), atomic force microscopy (AFM), transmission electron microscopy (TEM), and particle size analysis. ¹H-NMR spectra show a gradual change in the chemical composition with the growth of molecular chains. The gradient polymer latexes, the instantaneous copolymer composition of which varies as the polymerization proceeds, are obtained. GPC analyses show that the aggregated molecular chain in the BA-centered latex particle experiences a process from dominant BA to MMA with changes in the monomer's feed composition during the polymerization. Particle size and TEM analyses show that the increasing latex size agrees well with the gradient growth pattern. DSC analyses show that the gradient latex particles exhibit only one broadened and ambiguous glass transition region. AFM analyses indicate no obvious microphase segregation occurs in the gradient latex particles, further verifying that the gradient microstructure is obtained.     

Controlled coagulation of emulsion polymers

Coagulation of latex particles is most often carried out in the diffusion limited aggregation (DLA) regime where the time for coagulation to take place is on the millisecond timescale. This process produces aggregates of low density, irregular shape, and a broad particle size distributions. When the coagulation is carried out in the reaction limited aggregation (RLA) regime, a coagulation time of about 1–120 sec, the system can be controlled by mixing to yield dense, spheroidal aggregates with a very narrow particle size distribution. The important variables in the RLA process for butyl acrylate/methyl methacrylate (BA/MMA) latexes were found to be mixing intensity, latex copolymer composition, and coagulation temperature. Dried aggregates formed in the RLA process were found to have excellent powder flow properties and low dustiness.     

Processing of polymer latex emulsion: Batch coagulation

A small-scale batch experiment has been developed to establish processing conditions for latex coagulation in an extruder environment—characterized by the prevailing flow field, temperature, and pressure. Our experiments have shown that the most effective processing means to control the particle size distribution and also the particle morphology is the coagulation temperature. The changes in hydrodynamics, introduced by variations in the channel depth and rotor speed, affect the average particle size to a lesser degree. The morphology of the coagulated particles and their size distribution have been found to play an important role in the latex dewatering process. By coagulating well above the glass transition temperature(s) of the polymer, an order of magnitude drop in the specific surface area of the coagulated particles has been observed.     

Aerosol measurement by laser doppler spectroscopy—I. Theory and experimental results for aerosols homogeneous

The basic theory, experimental techniques and results are presented describing a technique for sizing aerosol particles in situ using laser Doppler spectroscopy. Unlike conventional light scattering procedures which use average intensity information, this technique utilizes the Doppler shifted frequency of the scattered light produced by the Brownian motion of the aerosol particles to determine particle diffusion coefficients and size. Experiments were carried out using monodisperse dibutylpthalate aerosols and monodisperse polystyrene latex spheres, in concentrations ranging from 10³ to 10⁶ particles per cubic centimeter. Measured particle sizes were within 10 per cent of the size predicted by conventional light scattering methods for the DBP particles and the reported sizes of the PSL particles. Based on these results it is concluded that laser Doppler spectroscopy can be utilized to accurately measure aerosol particle size in situ.     

Theory of density separation of particulate systems

The theory of density separation of particulate systems is reviewed. It is shown that true density separation is obtainable only in special cases. In practical systems, grades and throughputs of concentrates depend on volume fractions occupied by particles, physical properties of components which comprise the slurry, and also on particle size and density distributions.Particles pertaining to finer size distributions, and to the ‘near density’ range, are in particular sensitive to motion of larger particles, with respect to the magnitude and direction of their velocity.In this context, relations between size and density distributions are defined, specific examples illustrated, and practical applications discussed.     

The preparation of uniform polystyrene latices by true emulsion polymerization

Conventional emulsion polymerization of styrene produces some polydispersion in particle sizes in the latex. By carrying out a one-stage polymerization of finely emulsified monomer droplets of styrene formed in a mixture of methanol and water, it is possible to prepare stable latices of polystyrene in which the particles are perfectly uniform in size. The polymer has a relatively low molecular weight, but it is more stable to fragmentation by surfactant solutions than polystyrene prepared by conventional emulsion polymerization, the molecular weight of which is greater. The surface charge density of the particles is higher than that of particles produced by emulsion polymerization, and this probably accounts for the stability of the dispersion during polymerization and of the latex.     

Monodisperse ellipsoidal polystyrene latex particles: Preparation and characterisation

An improved version of a novel method first employed by Nagy & Keller for the preparation of monodisperse ellipsoidal polystyrene latex particles is described. The method involves embedding monodisperse spherical polystyrene latex particles as starting material in a deformable polymer matrix such as poly(vinyl alcohol) and deforming these mechanically to various predetermined macroscopic draw ratios to give ellipsoids of various axial ratios. Ellipsoids with lengths ranging from about 350 to 12250nm were prepared. Stable aqueous dispersions of these were recovered and characterised with respect to particle size and axial ratio distributions and surface morphology using electron microscopy. Axial ratios ranging from 2.0 to 5.65 were obtained for the resulting ellipsoids. Various factors influencing the monodispersity of the resulting ellipsoids in the preparation method are discussed.     

Preparation and properties of alkoxysilane/butyl acrylate/methyl methacrylate copolymer latices

The incorporation of alkoxysilanes into latex systems is of major interest in the field of colloidal science. Two kinds of vinyl‐containing alkoxysilanes, methacyloxypropyltrimethoxyl silane and vinyltriethoxysilane, were copolymerized with butyl acrylate and methyl methacrylate by seeded emulsion polymerization, and copolymer latices were obtained. The morphologies of the latex particles were characterized with transmission electron microscopy. Dynamic light scattering showed that the particle size increased and the particle size distributions of all the copolymer latex particles were alike with increasing amounts of organosilane. The effects of the organosilane content on the morphology of the particles, the rheology, and the swelling properties were also investigated. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Separation of Cells and Cell-Sized Particles by Continuous SPLITT Fractionation Using Hydrodynamic Lift Forces

Abstract

The use of hydrodynamic lift forces for the separation of particles according to size by continuous SPLITT fractionation is explored. The mechanism for particle separation in the transport mode of SPLITT fractionation is first explained. This is followed by a discussion of the hydrodynamic lift forces that act upon particles entrained in fluid flow between the parallel bounding walls of the SPLITT cell. The effect of the bounding walls on particle motion both parallel and perpendicular to the direction of flow is explained. Computer simulations of particle trajectories are presented that predict extremely high size selectivity for the method. A parallel experimental study was carried out using both polystyrene latex particles and red blood cells. The experimental selectivity was found to be smaller than that predicted theoretically. This discrepancy is attributable to nonidealities in the construction of the SPLITT cell. Nonetheless, the results are promising. Suspensions of polystyrene particle standards (from 2 to 50 μm in diameter) demonstrate that fast and relatively clean size separations are possible provided particles differ sufficiently in size and flow conditions are properly optimized. It is also shown that the system has the potential to quickly and gently separate blood cells from plasma.     

Monte Carlo modeling of fluidized bed coating and layering processes

A stochastic modeling approach based on a Monte Carlo method for fluidized bed layering and coating is presented. In this method, the process is described by droplet deposition on the particle surface, droplet drying and the formation of a solid layer due to drying. The model is able to provide information about the coating coverage (fraction of the particle surface covered with coating), the particle‐size distribution, and the layer thickness distribution of single particles. Analytical solutions for simplified test cases are used to validate the model theoretically. The simulation results are compared with experimental data on particle‐size distributions and layer thickness distributions of single particles coated in a lab‐scale fluidized bed. Good agreement between the simulation results and the measured data is observed. © 2016 American Institute of Chemical Engineers AIChE J, 62: 2670–2680, 2016