A novel method for making ultra-fine metal fibers and particles

A novel method based on plastic processing and equipment for preparing ultra-fine metal fibers and particles is reported. With this new method, metal fibers and particles can both be produced on the same equipment and the surfaces of the fibers and particles can be protected from oxidation by the polymers or solvents during the preparation process. Metal-alloy powders with lower melt point were filled into polymer by an extruder, followed by a die-drawing process at a temperature lower than the melt temperature of the metal alloy. Metal fibers or particles were obtained after the polymer matrix was washed away. Metal alloy fibers can be obtained when a polymer that strongly interacts with metal alloy, such as a special polyvinyl alcohol with a low alcoholysis degree, is used as the polymer matrix. Metal-alloy particles can be obtained when a polymer with weak interaction with metal alloy, such as polyethylene (PE), is used as the polymer matrix. Based on the principle of this new method, it is possible to produce finer or even nano-sized metal fibers and particles with higher melting points.     

Functions of polymers in composite electrodes of lithium ion batteries

The different functions of polymer binders on the processing of the electrode, the electrical (electronic and ionic) and mechanical properties of the electrode, and as a consequence on the electrochemical performance are discussed. The role of the polymer binder on the solid–electrolyte interface (SEI) layer and the cyclability of the graphite- and silicon-based negative electrodes is also addressed. All these properties critically depend on the very thin layer formed by the polymer at the surface of the active and conductive particles. That is where research efforts have to focus on, now, for further optimization of electrodes through tailoring of the binder combination.     

New method for post-processing crosslinking reaction

A new processing method to process functionalized polymer materials that are able to crosslink has been developed. The crosslinking reaction occurs after the melt processing stage at moderate temperature and without the addition of external reagents. Maleic anhydride-ethylene copolymer was processed with 1,4-butanediol in the presence of para-toluene sulfonic acid as catalyst. To prevent the reaction in the melt, it was chosen to trap the 1,4-butanediol onto vector particles. The extent of the crosslinking reaction during the mixing at 110 °C has been studied for three different particles taken as vector particles. It was found that Orgasol^® polyamide particles are efficient to inhibit the crosslinking reaction in the mixer. The reaction then takes place at 40 °C and after 100 h the cured samples appeared to be highly and homogeneously crosslinked with a gel content above 90%.     

Separation of cationic polymer particles and characterization of avidin-immobilized particles by capillary electrophoresis

Cationic polymer microparticles have received much attention especially in the field of biotechnology, such that their analysis and separation have become important. So far, the separation of cationic polymer particles with different size using CE has not been achieved and the cationic particles migrated as if they are negatively charged, probably due to electrostatic interaction between capillary wall and cationic polymer particles. In this paper, the separation of cationic polymer microparticles by CE was investigated in detail. The separation of cationic particles with different size was achieved in CE by taking into account the interaction between sample particles and the inner surface of capillaries. By employing a poly(vinyl alcohol)-coated capillary, a better size separation of amine-modified latex particles was obtained compared to a Polybrene-coated capillary. It was elucidated that the composition, concentration, and pH of the background solution were also important factors in the separation of colloidal particles to avoid the surface adsorption and the characteristic aggregation of polymer particles. Furthermore, the CE analysis was applied to the characterization of cationic protein-immobilized particles.     

Synthesis and characterization of monodisperse porous polymer particles

Monodisperse porous polymer particles in the size range of 10 μm in diameter were prepared via seeded emulsion polymerization. Linear polymer (polystyrene seed) or a mixture of linear polymer and solvent or nonsolvent were used as inert diluents. The pore diameters of these porous polymer particles were on the order of 1000 Å with pore volumes up to 0.9 mL/g and specific surface areas up to 200 m²/g. The physical features of the porous polymer particles depended on the diluent type and the crosslinker content, as well as the molecular weight of polymer seed particles. By varying the molecular weight of the linear polymer, monodisperse porous polymer particles with different pore size distribution could be synthesized. Polymer seed with a low degree of crosslinking instead of linear polymer could also be used to prepare monodisperse porous polymer particles with smaller pore volume and pore size.     

Influence of added particles on the phase behavior of polymer solutions. Analysis by mean-field lattice theory

The influence of added colloidal particles on the phase stability of polymer solutions is investigated theoretically. The polymer has an affinity to the particle surface. A mean-field lattice theory based on the Flory-Huggins theory is used to calculate the phase behavior in solutions containing a single polymer component and particles. The particles are described in two different ways. The first approach considers the surface free energy associated with added solid particles and the mixing entropy of the particles. In the second approach, the particles are simply modeled as large polymers. Both ways of describing the added particles show that the added particles decrease the stability of the polymer solution when the polymer-particle attraction is strong. A higher particle concentration enhances the effect. Experiments where polystyrene latex particles are added at different concentrations to aqueous dispersions of ethyl(hydroxyethyl)cellulose (EHEC) support the theoretical findings.     

TEM-cross section investigations of plasma polymer silver composite films

Plasma polymer silver composite films were investigated by means of cross section transmission electron microscopy (XTEM). The silver is encapsulated in the form of small particles in a nearly homogeneous plasma polymer matrix. The shape and the size of the particles vary with the polymerization power density. At lower polymerization power density the silver particles appear almost spherical and a three-dimensional particle distribution can be found in the polymer matrix. However the shape of particles at higher power density is more elliptic and the particle distribution is two-dimensional. The different kinds of encapsulation can be interpreted as being due to the different densities and porosities of the plasma polymer matrix.     

Thermodynamic analysis of the morphology of monomer-adsorbed,cross-linked polymer particles prepared by the dynamic swelling method and seeded polymerization

Thermodynamic simulation of the morphology of monomer-adsorbed, cross-linked polymer particles prepared by the dynamic swelling method which the authors proposed was conducted to clarify its thermodynamic stability from the viewpoint of the total interfacial free energy. By comparing it with experimental results reported in previous articles, it was found that the morphology was controlled thermodynamically. Snowman-shaped composite polymer particles having different morphologies were prepared by seeded polymerization of the monomer-adsorbed, cross-linked polymer particles, in which the polymer particles had different cross-linking densities.     

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.     

Asymmetric Polymer Particles with Anisotropic Curvatures by Annealing Polystyrene Microspheres on Poly(vinyl alcohol) Films

Anisotropic polymer particles such as Janus particles have attracted significant attention in recent years because of their unique properties and unusual self‐assembly behavior. Most anisotropic polymer particles synthesized so far, however, only have different chemical regions compartmentalized on the particles. It remains a great challenge to fabricate anisotropic polymer particles with different shapes within a single particle. A novel approach is developed to prepare anisotropic polymer particles that contain two hemispheres with different curvatures by annealing polystyrene microspheres on poly(vinyl alcohol) films. During the annealing process, the polymer microspheres gradually sink into the polymer films and transform to asymmetric polymer particles, driven by the surface and interfacial tensions of the polymers. Selective removal techniques are also used to confirm the morphologies of the asymmetric particles.

     

Swelling-based method for preparing stable, functionalized polymer colloids

We describe a swelling-based method to prepare sterically stabilized polymer colloids with different functional groups or biomolecules attached to their surface. It should be applicable to a variety of polymeric colloids, including magnetic particles, fluorescent particles, polystyrene particles, PMMA particles, and so forth. The resulting particles are more stable in the presence of monovalent and divalent salt than existing functionalized colloids, even in the absence of any surfactant or protein blocker. While we use a PEG polymer brush here, the method should enable the use of a variety of polymer chemistries and molecular weights.     

Preparation of micron-sized composite polymer particles containing hydrophilic 2-hydroxyethyl methacrylate and their biomedical applications

Micron-sized polystyrene or PS particles were first prepared by dispersion polymerization. Then a series of polystyrene/poly(styrene-2-hydroxyethyl methacrylate) or PS/P(S-HEMA) composite polymer particles was prepared by seeded copolymerization using different amounts of 2-hydroxyethyl methacrylate (HEMA) at the constant core/shell ratio of 1/0.5. The produced PS seed and composite polymer particles were characterized by transmission electron microscopy. Adsorption behaviors of some biologically active macromolecules were studied under similar conditions. In each case the magnitude of adsorption on composite polymer particles decreased with the increase in HEMA content in the recipe, which means that the hydrophobic interaction between the surface of the particles and biomolecules decreased. The specific activities of trypsin aqueous solution and adsorbed trypsin on PS seed and composite polymer particles prepared with different HEMA contents were also measured and compared. The activity of adsorbed trypsin on composite polymer particles improved significantly with the incorporation of hydrophilic HEMA.     

Prototype of Low Thermal Expansion Materials: Fabrication of Mesoporous Silica/Polymer Composites with Densely Filled Polymer inside Mesopore Space

A prototype of novel low thermal expansion materials using mesoporous silica particles is demonstrated. Mesoporous silica/polymer composites with densely filled polymer inside the mesopore space are fabricated by mechanically mixing both organically modified mesoporous silica and epoxy polymer. The mesopores are easily penetrated by polymers as a result of the capillary force during the mechanical composite processing. Furthermore, we propose a new model of polymer mobility restriction using mesoporous silica with a large pore space. The robust inorganic frameworks covering the polymer effectively restrict the polymer mobility against thermal energy. As a result, the degree of total thermal expansion of the composites is drastically decreased. From the mass‐normalized thermal mechanical analysis (TMA) charts of various composites with different amounts of mesoporous silica particles, it is observed that the coefficient of thermal expansion (CTE) values gradually increase with an increase of the polymer amount outside the mesopores. It is proven that the CTE values in the range over the glass‐transition temperatures (T_g) are perfectly proportional to the outside polymer amounts. Importantly, the Y‐intercept of the relation equation obtained by a least‐square method is the CTE value and is almost zero. This means that thermal expansion does not occur if no polymers are outside the mesopores. Through such a quantative discussion, we clarify that only the outside polymer affects the thermal expansion of the composites, that is, the embedded polymers inside the mesopores do not expand at all during the thermal treatment.     

Thermal conductivity of polymers filled with dispersed particles: A model

A method for calculating the thermal conductivity coefficient in polymers filled with dispersed particles is proposed. This model is based on estimation of the mean width of a polymer layer between the particles that are randomly distributed in space. This model makes it possible to allow for the effect of particle dimensions, interaction between components, and their characteristics in the course of processing via extrusion.     

Electrohydrodynamic atomization for biodegradable polymeric particle production

Electrohydrodynamic atomization (EHDA) has many applications such as electrospray ionization in mass spectroscopy, electrospray deposition of thin films, pharmaceutical productions, and polymeric particle fabrications for drug encapsulation. In the present study, EHDA was employed to produce biodegradable polymeric micro- and nanoparticles. The effects of processing parameters such as polymer concentration, flow rate, surfactants, organic salt, and setup configurations on the size and morphology of polymeric particles were investigated systematically. By changing the various processing parameters, controllable particle shape and size can be achieved. PLGA nanoparticles with size of around 250 nm can be obtained by using organic salts to increase the conductivity of the spraying solution even at a relatively high flow rate. A higher flow rate has the advantage of producing a stable cone spray and can be easily reproduced. Solid and porous particles can be fabricated using different experimental setups to control the organic solvent evaporation rate. Also, paclitaxel, a model antineoplastic drug, was encapsulated in polymeric particles which can be employed for controlled release applications. In short, EHDA is a promising technique to fabricate polymeric micro- or nanoparticles which can be used in drug delivery systems.     

An Unexpected Molecular Imprinting Effect for a Polyaromatic Hydrocarbon,Anthracene, Using Uniform Size Ethylene Dimethacrylate Particles

A non-covalent type of molecular imprinting effect toward a polyaromatic hydrocarbon (PAH), viz. anthracene, was studied utilizing uniformly sized ethylene dimethacrylate (EDMA) polymer particles without functional host monomers. Although polymerization at 0°C initiated by a redox initiation system was expected to afford larger molecular imprinting effect due to stronger and more effective intermolecular interaction between the template and surface functional groups of the polymer, almost no imprinting effect was observed, while a much higher polymerization temperature of 70°C unexpectedly afforded a larger molecular imprinting effect for the template anthracene. In order to determine the unexpected imprinting effects observed, uniformly sized, macroporous un-imprinting EDMA polymer particles (base particles) were prepared by various polymerization techniques at different polymerization temperature as well as with different initiation systems. The careful studies proved that each kind of base polymer particle showed different molecular recognition ability, especially toward anthracene, which is depends upon the physical properties of each kind of base polymer particle. On the basis of these facts, we would propose that the potential molecular recognition ability of the un-imprinted base polymer particles is another important factor for realization of effective molecular imprinting alongside the factors reported previously.     

Permanent antistatic phthalocyanine/epoxy nanocomposites - Influence of crosslinking agent, solvent and processing temperature

Cross-linked epoxy matrices containing small amounts of semi-conductive phthalocyanine (Phthalcon) nanoparticles were prepared using different crosslinking agents and processing temperatures. A starting mixture containing an optimum dispersion of these nanoparticles and with an almost equal and large Hamaker constant was always used. Nevertheless large differences in the relation between the volume conductivity σ_v and the particle concentration φ were found and this relation appeared to be sensitive to small changes in processing temperature and the application of a post-cure. Also the amine crosslinker chosen and the initial amount of solvent (catalyst) in the starting dispersion had a major effect. It was shown that these changes influence strongly the formation of and the final conductive fractal particle network morphology through the polymer matrix. During processing a local relaxation of the initially formed fractal particle network into another fractal particle network was often observed, which introduced or enlarged the amount of isolating material between the particles of the conductive network and changed the fractality and structure of the conductive backbone of the particle network. This local relaxation lowered the σ_v at each phthalcon concentration and enlarged φ_c by several orders of magnitude. The occurrence of local relaxation is dependent on the rate of viscosity change during the crosslinking of the polymer matrix components, the way the fractal conductive particle network is formed during processing (universal or non-universal) and the amount of solvent present. Local relaxation may even occur after the gel point of the polymer matrix. A severe post-cure may be needed to stop this local relaxation. To our knowledge local relaxation of a (fractal) nanoparticle network in a polymer matrix during processing is a new phenomenon, not reported before for polymer composites containing (conductive) nanoparticles.     

Core–shell particles with conductive polymer cores

Heterocoagulation of large cationic polypyrrole particles with small anionic polyacrylate beads followed by heat processing of the heterocoagulate units proved to be an efficient method in the preparation of core-shell particles with conductive cores and dielectric shells. Specific conditions required for producing monodispersed composite particles with uniform shells were examined in the stages of the synthesis of polypyrrole particles with controlled size, in "one-step" heterocoagulation of oppositely charged polypyrrole microbeads with small polyacrylic particles, and during shell formation by spreading of the acrylic polymer on the surface of polypyrrole cores.     

Composite polymer particles prepared with different amounts of acrylic acid and their usefulness as carriers for biomolecules

Modification of surface properties of polymer particles suitable for biomedical application has been done by incorporating acrylic acid (AA) as a hydrophilic component. First, submicron-sized poly(methyl methacrylate) seed particles were prepared by soap-free emulsion polymerization. Then, seeded emulsion copolymerizations were carried out with varying proportions of AA and methyl methacrylate (MMA). MMA was used as a comonomer to prevent the dissolution of AA from the polymer particles. The adsorption behaviors of different biomolecules indicate that the surface of the composite polymer particles is sufficiently hydrophilic, particularly at higher AA content. Specific activities of adsorbed trypsin on the composite polymer particles were also comparatively high compared to free trypsin, which suggests that the adsorbed trypsin undergoes only slight conformational change owing to the interaction with the surface of particles.     

Controllable porous polymer particles generated by electrospraying

In this paper, an electrospraying technique was applied to prepare polycaprolactone (PCL) polymer particles with a different microstructure. The PCL particles can be controlled to have a porous microstructure by tailoring the evaporation of solvents during the electrospraying process. The effect of various concentrations on the morphology and microstructure of PCL particles was investigated. The experiment has demonstrated the versatile capability of the electrohydrodynamic atomization process for preparing polymer PCL porous particles and fibers. The thermally induced and evaporation-induced phase separations are proposed as the main mechanisms for the porous microstructure formation. The results demonstrate that the electrospraying method is a simple, innovative and cost-effective method for preparing polymer particles with controllable microstructures.