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.     

The effect of clay on the morphology of multiphase latex particles

The effect of montmorrilonite clay (MMT) platelets on the morphology of polystyrene/poly(methyl methacrylate) (PMMA) composite latex particles prepared via PMMA-seeded (semi-) batch emulsion polymerization of styrene was studied. It was found that the particle morphology obtained greatly depended on the ability of the clay platelets to diffuse through the polymer particle. Indeed, when the reactions were strictly under kinetic control, i.e., where the clay platelets were unable to diffuse during polymerization, anisotropic core-shell-like morphologies with split core were observed. A better mobility of the clay platelets could more or less restrict the diffusion of the second-stage polymers within the host polymer, leading to original kinetically controlled morphologies. In the case of a full migration of the clay platelets to the particle surface, the penetration of the second-stage polymer species in the seed latex was found to be more limited, enhancing the formation of secondary particles.     

聚合物纳米微粒静电组装行为及其表征

使用2,2′-偶氮二异丁基脒二盐酸盐自由基引发剂,改变甲基丙烯酰氧乙基十六烷基二甲基溴化铵阳离子功能单体的量与苯乙烯进行乳液聚合获得不同粒径的阳离子乳胶粒,使用十二烷基硫酸钠为乳化剂和过硫酸钾为引发剂制备阴离子聚合物乳胶粒.采用基于静电相互作用的异凝聚法将以上2种带有相反电荷的乳胶粒组装,获得了表面粗糙程度不同的复合微粒.对异凝聚过程中复合液透光率和微粒大小及分布进行跟踪测试,并用透射电子显微镜表征了阳离子微粒、阴离子微粒以及复合微粒的形态和大小.结果表明,在一定范围内可以通过控制阴离子乳胶粒与阳离子乳胶粒的复合比例改变单个复合微粒表面阳离子小微粒的数目.     

Morphology and properties of waterborne adhesives made from hybrid polyacrylic/montmorillonite clay colloidal dispersions showing improved tack and shear resistance

The morphology and adhesive properties of waterborne films from n-butyl acrylate/methyl methacrylate/montmorillonite clay hybrid polymer latexes which were synthesized by miniemulsion polymerization in the presence of a reactive organoclay ((2-methacryloylethyl) hexadecyldimethylammonium modified montmorillonite, CMA16) were investigated. It was found by cryo-TEM analysis that the hybrid dispersions were a mixture of colloidal particles composed of a small fraction of free montmorillonite clay platelets, polymer latex particles, polymer particles to which one or more clay platelets where adhered onto its surface and a fraction of colloidal material consisted of a clay platelet with a polymer lob adhered to either side, in other words hybrid particles with a dumbbell-like morphology. The films made from these waterborne hybrid dispersions presented a homogeneous dispersion of the clay platelets and exfoliated morphology. The shear adhesion failure temperature (SAFT) and shear resistance of the hybrid latex films synthesized with CMA16 were better than those prepared with a commercial clay (Cloisite 30B), but presented a liquid-like probe-tack performance. When allyl methacrylate (AMA) was added in the formulation, SAFT and shear resistance improved, but the film had a very low energy of adhesion due to the excessively crosslinked matrix. In order to reduce crosslink density and thus improve the adhesion energy, small amounts of chain transfer agent, in this case n-dodecyl mercaptan (n-DDM), were used in the miniemulsion polymerization process. Adhesive films made from these waterborne hybrid dispersions showed excellent SAFT and shear resistance, and good energy of adhesion.      

Non-affine structural evolution of soft colloidal crystalline latex films under stretching as observed via synchrotron X-ray scattering

A polymer dispersion consisting of soft latex spheres with a diameter of 135 nm was used to produce a crystalline film with face-centered cubic (fcc) packing of the spheres. Different from conventional small-molecule and hard-sphere colloidal crystals, the crystalline latex film in the present case is soft (i.e., easily deformable). The structural evolution of this soft colloidal latex film under stretching was investigated by in-situ synchrotron ultra-small-angle X-ray scattering. The film exhibits polycrystalline scattering behavior corresponding to fcc structure. Stretching results not only in a large deformation of the crystallographic structure but also in considerable nonaffine deformation at high draw ratios. The unexpected nonaffine deformation was attributed to slippage between rows of particles and crystalline grain boundaries. The crystalline structure remains intact even at high deformation, suggesting that directional anisotropic colloidal crystallites can be easily produced.     

Synthesis of highly monodisperse particles composed of a magnetic core and fluorescent shell

Highly monodisperse particles composed of a magnetic silica core and fluorescent polymer shell were synthesized with a combined technique of heterocoagulation and soap-free emulsion polymerization. Prior to heterocoagulation, monodisperse, submicrometer-sized silica particles were prepared with the Stober method, and magnetic nanoparticles were prepared with a modified Massart method in which a cationic silane coupling agent of N-trimethoxysilylpropyl- N, N, N-trimethylammonium chloride was added just after coprecipitation of Fe (2+) and Fe (3+). The silica particles with negative surface potential were heterocoagulated with the magnetic nanoparticles with positive surface potential. The magnetic silica particles obtained with the heterocoagulation were treated with sodium silicate to modify their surfaces with silica. In the formation of a fluorescent polymer shell onto the silica-coated magnetic silica cores, an amphoteric initiator of 2,2'-azobis[ N-(2-carboxyethyl)-2-2-methylpropionamidine] (VA-057) was used to control the colloidal stability of the magnetic cores during the polymer coating. The polymerization of St in the presence of a hydrophobic fluorophore of pyrene could coat the cores with fluorescent polymer shells, resulting in monodisperse particles with a magnetic silica core and fluorescent polymer shell. Measurements of zeta potential for the composite particles in different pH values indicated that the composite particles had an amphoteric property originating from VA-057 initiator.     

Design and Preparation of Highly Filled Water‐Borne Polymer–Gibbsite Nanocomposites

Highly filled, high solids content, water‐borne polymer–Gibbsite nanocomposites are prepared with Gibbsite contents as high as 35 wt%. The polymer–Gibbsite nanocomposites are synthesised via conventional starved feed emulsion polymerization using negatively charged butyl acrylate‐co‐acrylic acid oligomers, which functioned as electrosteric stabilizers for the initial platelets and the subsequently formed latex particles. A simple mathematical model describing the amount of cooligomer required for the colloidal stability of the initial Gibbsite platelets and the subsequently formed particles was derived. This model was used to determine the reaction conditions required for obtaining colloidally stable nanocomposites with a targeted filler content. Cryogenic transmission electron microscopy characterization of the resulting nanocomposites with filler contents up to 20 wt% revealed fully encapsulated Gibbsite platelets and a mixed morphology of “muffin‐like” and encapsulated particles was obtained at higher filler contents.     

Composite natural rubber–polychloroprene latex particles produced by the heterocoagulation technique

Composite natural rubber (NR) based latex particles were prepared using the heterocoagulation technique. A nonionic surfactant (Tween 80) whose molecules bear poly(ethylene oxide) (PEO) was adsorbed on polychloroprene (CR) latex particles and allowed to form complexes between PEO and indigenous surfactant (protein–lipid) on the NR particle surface. The heterocoagulated NR/CR–Tween particles produced were characterised by particle size, zeta-potential and glass-transition temperature measurements and the data indicated the presence of CR–Tween on the outer layer of the composite polymer particles. The results agreed well with the better oil resistance of films cast from heterocoagulated latex when compared with that of the NR film. Received: 22 August 2000 Accepted: 8 January 2001     

Preparation of core–shell composite polymer particles by a novel heterocoagulation based on hydrophobic interaction

Submicron-sized cationic polystyrene shell particles with active ester groups were effectively self-assembled on hydrophobic surfaces of cross-linked polystyrene (PST) particles, uncharged core particles with ca. 8.5-µm diameter in aqueous systems. The hydrophobic interactions between the shell particles and core particles play a key role in heterocoagulation. The resulting heterocoagulates were highly physically stable in water, and the morphology was controlled by several factors including the solid content of latex, self-assembling time, and electrolyte concentration. Composite polymer particles with a core–shell structure were successfully obtained from the heterocoagulates by heat treatment for 3 h at a temperature above the glass transition temperature (T_g) of the cationic polymer shell particles.     

Lyotropic smectic B phase formed in suspensions of charged colloidal platelets

Here, we present the first observation of a smectic B (Sm(B)) phase in a system of charged colloidal gibbsite platelets suspended in dimethyl sulfoxide (DMSO). The use of DMSO, a polar aprotic solvent, leads to a long range of the electrostatic Coulomb repulsion between platelets. We believe this to be responsible for the formation of the layered liquid crystalline phase consisting of hexagonally ordered particles, that is, the Sm(B) phase. We support our finding by high-resolution X-ray scattering experiments, which additionally indicate a high degree of ordering in the Sm(B) phase.     

Heteroaggregation in binary mixtures of oppositely charged colloidal particles

Heteroaggregation (or heterocoagulation) rate constants have been measured in mixtures of well-characterized colloidal particles of opposite charge with multiangle static and dynamic light scattering. This technique permits routine measurements of absolute heteroaggregation rate constants, also in the presence of homoaggregation. Particularly with multiangle dynamic light scattering, one is able to estimate absolute heteroaggregation rate constants accurately in the fast aggregation regime for the first time. Heteroaggregation rate constants have also been measured over a wide range of parameters, for example, ionic strength and different surface charge densities. Amidine latex particles, sulfate latex particles, and silica particles have been used for these experiments, and they were well characterized with respect to their charging and homoaggregation behavior. It was shown that heteroaggregation rate constants of oppositely charged particles increase slowly with decreasing ionic strength, and provided the surface charge is sufficiently large, the rate constant is largely independent of the surface charge. These trends can be well described with DLVO theory without adjustable parameters.     

Synthesis of PVAc/SiO2 latices stabilized by silica nanoparticles

This paper presents a method for the preparation of raspberry-like organic-inorganic composite spheres with poly(vinyl acetate) (PVAc) as core and nanosilica particles as shell. A small amount of anionic reactive surfactant, 3-allyloxy-2-hydroxy-1-propanesulfonic acid sodium salt (HAPS), was used as co-stabilizer and nanosilica particles were adsorbed onto the growing latex core in aqueous medium via the formation of hydrogen bonds between nanosilica particles and PVAc particles. TEM indicated that the hydrogen bonds between nanosilica particles and PVAc were strong enough for the formation of long-stable composite spheres with raspberry-like morphology. Influences of some synthetic parameters, for instance, type of silica sol, initial silica amount, and different kinds of low-molecular-weight surfactant, on the morphology of the composite spheres and properties of the latex films were studied in detail. A possible formation mechanism of the composite spheres was also proposed.     

Colloidal stability of dextran-modified latex particles toward adsorption of concanavalin A

The colloidal stability of the dextran-modified poly(methyl methacrylate) (PMMA) latex particles toward adsorption of a carbohydrate-binding protein, concanavalin A (Con A), is primarily controlled by the charge neutralization mechanism. Formation of a crosslinked network structure via the specific affinity interactions between the dimeric Con A molecules and the dextran molecules anchored onto different latex particles may also have an impact on the coagulation kinetics. Judging from the data of coagulation kinetics, the colloidal stability of the latex particles toward added Con A in the decreasing order is: latex particles without dextran modification>latex particles with a dextran content of 2.15%>latex particles with a dex-tran content of 1.24% based on total polymer weight (PMMA+grafted dextran). The coagulation mechanisms involved in the adsorption of Con A onto the latex particles have been proposed to explain these experimental data. Charge neutralization of the negatively charged latex particles by adsorption of the positively charged Con A is the predominant destabilization mechanism. The ratio of the number of dextran active sites to that of Con A molecules plays an important role in the formation of the crosslinked network structure. The electrolytes in water cause a reduction in the electrostatic repulsion force among the interactive latex particles, but this ionic strength effect is not significant in comparison with charge neutralization. Received: 22 October 1997 Accepted: 24 December 1997     

Correlative studies on the fabrication of poly(styrene-methyl-methacrylate-acrylic acid) colloidal crystal films

This research describes a one-step procedure for monodispersed poly(styrene-methyl-methacrylate-acrylic acid colloidal spheres [P(St-MMA-AA)] via soap-seeded emulsion polymerization. The effects ofreaction conditions such as temperature, stirring speed, initiation concentration, e.t.c. were examined. The results obtained showed that the spheres average particle diameter decreased with increase in initiator concentration, the reaction temperature and stirring speed and increased with an increase in monomer concentrations. The particles show stable mechanical properties within the transition and heating temperatures of 111.9?°C and 388?°C respectively. Zeta-potential values ranging from ?31.8?mV to ?36.5?mV which is indicative of stable dispersion of colloidal particles were obtained for all the prepared latexes. The assembled colloidal latex had periodic structures with mainly hexagonal three-dimensional structures with multi-facet arrangements. The latex also shows spherical shape of monodispersed core-shell particles.     

Monitoring the transformation of colloidal crystals by styrene vapor using atomic force microscopy

The stages of transformation of a colloidal crystalline film of latex spheres to a new periodic structure were imaged by atomic force microscopy. Colloidal crystalline films were prepared with 320 nm diameter poly(styrene-co-2-hydroxyethyl methacrylate) (PSt/HEMA) spheres. The hexagonally ordered surfaces of the colloidal crystalline films were transformed with styrene vapor at room temperature to a new morphology having holes in the surface and the same periodicity as the original films. The surfaces of colloidal crystals and the transformed films have a raspberry-like texture superposed on the 320 nm hexagonal periodicity. Both height images and phase images reveal that the latex spheres shrink and the transformation proceeds by an order-disorder-order sequence. The final structure is an interconnected colloidal array with smaller polystyrene particles dispersed in a continuous PSt/HEMA matrix.     

The use of surface tension to predict the formation of 2D arrays of latex spheres formed via the Langmuir-Blodgett-like technique

Highly ordered hexagonal arrays of latex spheres on highly ordered pyrolytic graphite (HOPG) have been prepared from a Langmuir-Blodgett-like (LB-like) technique using both polymers and surfactants as spreading agents. The role of spreading agent concentration in forming a well-ordered, stable monolayer at the air-liquid interface was studied by means of atomic force microscopy, scanning electron microscopy, optical microscopy, and surface tension measurements for three different systems: a nonionic surfactant, octylphenoxy poly(ethyleneoxy)ethanol (Igepal CO 630); an anionic surfactant, sodium dodecyl sulfate; and a low-molecular-weight, water-soluble polymer, polyacrylamide. For both the anionic surfactant and the water soluble polymer, a correlation was found between a unique feature in surface tension measurements of the latex-spreading agent mixture and the concentrations at which hexagonal arrays of latex spheres form on the surface of HOPG. For the nonionic surfactant, no ordered structures were found on HOPG for any surfactant concentration, consistent with no appearance of the unique feature in surface tension measurements. These results show that a tensiometer can be used to determine the conditions under which well-ordered latex films have the possibility of forming on a substrate using the LB-like technique; however, other factors, such as pulling speed and surface chemistry, play a role as well.     

Metal Nanoparticle/Polymer Hybrid Particles: The Catalytic Activity of Metal Nanoparticles Formed on the Surface of Polymer Particles by UV-Irradiation

Summary: Polymer particles decorated with metal nanoparticles were prepared by UV-irradiation of polystyrene latex particles incorporating polymethylphenylsilane (PS/PMPS) and P[S-co-NIPAM]/PMPS particles (NIPAM: N-isopropyl acrylamide) in the presence of metal salts. The metal nanoparticle/polymer hybrid particles were used as a catalyst for the reduction of 4-nitrophenol with NaBH₄. The Pd- and Ag-P(S-co-NIPAM)/PMPS hybrid particles had larger metal nanoparticles and the lower catalytic activity than those of Pd- and Ag-PS/PMPS, respectively. The surface functional group of the polymer particles affected the formation of the metal nanoparticles and their catalytic activity.     

Effect of an anionic monomer on the pickering emulsion polymerization stabilized by titania hydrosol

Polystyrene (PS) nanocomposite particles with high titania content are prepared by Pickering emulsion polymerization. A self‐made titania hydrosol modified by an anionic monomer sodium styrene sulfonate (NaSS) is used as a stabilizer and photocatalyst. The stability of the emulsion system is greatly improved by the electrostatic interaction between negatively charged NaSS and positively charged titania nanoparticles. The nanocomposite spheres with the diameter of around 120 nm are highly charged, indicating titania‐rich surfaces of latex particles. It is also proven by the field‐emission transmission electron microscope and field‐emission scanning electron microscope images. The well‐defined core‐shell structure of the obtained PS/titania composite particles is confirmed by the formation of fragile hollow titania nanospheres after thermogravimetric analysis tests. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5728–5736, 2009     

Facile fabrication of mechanochromic-responsive colloidal crystal films

This paper presents a simple approach to fabricate a reversible mechanochromic-responsive crystal film based on the room-temperature film-formation of monodisperse polymer latex by the aid of nanosilica particles. In this approach, when the "soft" colloidal polymer spheres were blended with colloidal silica particles and then cast on a substrate, followed by drying at room temperature for self-assembly, an elastic crystal film was directly obtained. This crystal film has not only reversible and repeatable mechanochromic-responsive property, but also tunable color and peak position covering almost entire visible spectral region, depending upon the sizes of polymer spheres and strains. This optical response is attributed to the variation of lattice spacing during deformation.     

Structural morphology developments in the interfacial phase of heterocoagulated composite particles: dynamic mechanical measurements

The dynamic mechanical properties of polymeric composites composed of poly (methyl methacrylate) continuous-phase and various inclusion types of heterocoagulated composite particles were investigated in order to relate them to the morphology of shell region of composite particles. Using the heterocoagulation process, large particles were encapsulated with various types of small particles: (1) conventional linear-type polymer particles; (2) crosslinked polymer particles; and (3) reactive polymer particles capable of forming crosslinked structure, whereby the interfacial properties of the composite become modified. These composite particles were subsequently annealed to form continuous shell regions and then mixed with matrix particles. It is shown that chain diffusion movement of the small particles having different chain characteristics influences the network formation at the interfacial shell region. The ability of maintaining interfacial domain structure depends on the degree of network formation.