Kinetics of sorption of poly(ethylene glycols) of various molecular masses by globular carbon

The kinetics of adsorption of poly(ethylene glycols) with molecular masses in the range 300–15000 from aqueous solutions by globular carbon with different radii of curvature of particles is studied. The kinetic adsorption coefficients of poly(ethylene glycols) are calculated. The dependences of the kinetic absorption coefficient on adsorbent dispersion and molecular mass of poly(ethylene glycol) are discussed.     

Mathematical Modeling of Aluminum Diboride Combustion in an Air Flow

A mathematical model and the results of calculating the ignition and combustion of energetic condensed systems based on mono- and polydispersed aluminum diboride particles in air flows in constant-cross-section channels are reported. The kinetic characteristics of the transformations that separate aluminum diboride particles formed by gasification of energetic condensed systems undergo in a high-temperature oxidizing medium were determined using the dependences of the ignition induction period and combustion time on the air temperature and diameter and initial temperature of the particles. These dependences, in turn, were calculated using the model of parallel chemical reactions. The range of combustion conditions corresponding to the initial air temperatures from 300 to 2000 K and Mach numbers in the channel from 0.1 to 1.5 was considered. The influence of the aluminum diboride particle size and of the rate and initial temperature of the air flow on the combustion efficiency was demonstrated. The relationships between the combustion completeness factor of aluminum diboride particles at various initial parameters of the air flow and gasification products of energetic condensed systems at various fuel mixture equivalence ratios, corresponding to the diffusion and kinetic combustion, were determined. The conditions of the transition between the diffusion and kinetic control modes were found.

     

Hydroxypropyl cellulose (HPC)-stabilized dispersion polymerization of styrene in polar solvents: Effect of reaction parameters

Dispersion polymerization of styrene in polar solvents in the presence of hydroxypropyl cellulose (HPC) produces latex particles from ca. 1 to 26 μm depending on reaction parameters. Increasing the initiator concentration or temperature decreases the molecular weight, but increases the particle size and breadth of the size distribution. The decrease in molecular weight with increasing R_i, caused by larger initiator concentration or higher temperature, is expected based of fundamental kinetic relationships. The inverse correlation between size and rate of initiation is rationalized by polarity (stabilizing ability) of the grafted HPC-polystyrene formed in situ. High polar HPC-g-PS, which contains shorter graft polystyrene chain, stabilizes particles less effectively and this leads to larger particles. The primary influence of initial styrene concentration is a solvent effect: larger particles are obtained at high styrene concentration due to high solubility of polystyrene during the initial part of the reaction. The influence of the molecular weight of HPC is to change the polarity of the HPC-g-PS stabilizer. Comparison of particle growth of three critical polymerization systems suggests that the favorable continuous-phase solubility parameter for dispersion polymerization of styrene is around 11.6 (cal/mL)^1/2. Too high or too low polarity generates particles with broad size distribution because large particles are formed during the initial stage and nucleation continues as the polymerization proceeds. © 1992 John Wiley & Sons, Inc.     

AFM study of the behavior of polystyrene and glass particles during the electrodeposition of copper

In this paper, the behavior of polystyrene and glass particles on a copper electrode during the electrodeposition of copper was studied using an atomic force microscope (AFM). Polystyrene or glass particles glued to the tip of the AFM cantilever were kept in contact with the surface of the electrode. The surface forces between the polystyrene or glass particle and the copper electrode were measured before, during, and after electrodeposition. These experiments revealed that glass particles do not make contact with the electrode, probably due to the repulsive hydration force. Polystyrene particles, on the other hand, make contact with the electrode, due to the attractive hydrophobic force. The AFM experiments were correlated with sedimentation co-deposition experiments of polystyrene and glass particles with copper. It was found that 80% of the polystyrene particles added to the plating solution incorporated with copper, while only 0.25% of the glass particles co-deposited under the same conditions.     

Kinetics of the reduction of molecular oxygen from water by ultrafine copper in an ion-exchange matrix

The rate of the reduction of molecular oxygen from water with a low-capacity copper-containing electron-ion exchanger at various initial ionic forms, grain radii, and sizes of metal particles dispersed into pores. The applicability of the mixed-diffusion and diffusional-kinetic models incorporating a first-order irreversible reaction to describing the system under study was examined. The kinetic parameters of the system were determined within the framework of these models. It was found that the limiting stage of the process in the stationary mode is the internal diffusion of oxygen molecules to the redox sorbent particle. The increase in the rate of the absorption of oxygen by samples containing copper of higher dispersity was observed at the initial stage of the process and was likely associated with an increase in the surface area of the reactive interface.     

Photochromic transformations of 6-nitrospiropyran in matrices of linear and branched polymers

Photochromic transformations of 6-nitrospiropyran in matrices of linear polystyrene and poly(methyl methacrylate) and branched polymethacrylates of various composition and structure were studied by absorption spectroscopy. In the case of linear polymers the kinetics of bleaching of the colored merocyanine form of 6-nitrospiropyran is determined by polarity and molecular mobility of the polymer matrix. The kinetic regularities of merocyanine transformations into the initial spiropyran in the branched polymer matrices are apparently caused by specific features of their architecture, differences in the degree of branching, and the properties associated with molecular mobility. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 191–198, February, 2007.     

Structure and infrared emissivity of polyimide/mesoporous silica composite films

Polyimide/mesoporous silica composite films were prepared by direct mixing of polyamic acid solution and silylated mesoporous silica particles, or by condensation polymerization of dianhydride and diamine with silylated mesoporous silica particles in N,N-dimethylacetamide, followed with thermal imidization. Structure and glass transition temperatures of the composite films were measured with FTIR, SEM, EDX, XPS and DMTA. The results show that the silylated mesoporous silica particles in the composites tend to form the aggregation with a strip shape due to phase separation. The composite films exhibit higher glass transition temperature as comparing with that of pure polyimide. It is found that the composite films present lower infrared emissivity value than the pure polyimide and the magnitude of infrared emissivity value is related to the content of silylated mesoporous silica in the composite films. Inhibiting actions of silylated mesoporous silica on infrared emission of the composite films may be owing to presence of nanometer-scale pores in silylated mesoporous silica.     

Photochemical and thermal isomerization in polymer matrices: Azo compounds in polystyrene

Photochemical and thermal geometrical isomerizations of monoazo compounds have been studied in polystyrene–n-butylbenzene compositions. Cis–trans isomer ratios established by light absorption were found to depend on matrix viscosity. Where the compositions were above their respective glass temperatures, all thermal isomerizations conformed to first-order kinetics. Where compositions were below their respective glass temperatures, the initial isomerization rates were abnormally fast, decaying to normal first-order processes after substantial amounts of reaction had taken place. These effects have been interpreted in terms of the vitreous properties of polystyrene.     

The relationship between micro- and mesoporous substructures upon removal of colloidal silica from porous glasses subjected to alkaline treatment

The effect of alkaline treatment of two basal liquation sodium borosilicate porous glasses on their micro- and mesoporous substructures has been studied. The morphology of pores has been investigated and the structural characteristics of micro- and mesoporosity have been determined by the equilibrium and kinetic adsorption-desorption methods at low, moderate, and high relative pressures. It has been established that the alkaline treatment leads to a substantial increase in the volume of mesopores and a noticeable decrease in the volume of micropores, which correlates with a reduction in the specific surface area of the mesopores. After the alkaline treatment, the trimodal distribution and the average diameter (0.5–0.6 nm) of micropores remain unchanged and ultramicropores do not arise in the range of 0.27–0.37 nm. It has been concluded that micropores represent only the regions of interglobular contacts of secondary silica in liquation channels with sizes of 1–2 diameters of an adsorbate molecule. The alkaline treatment is accompanied by the structuring and dissolution of silica globules in liquation channels; as a result, wide-porous glass samples with monomodal interglobular pores are obtained, while new micropores are not formed via the etching of channel walls in the glass matrix. Correlation dependences between the coordination number, porosity, and diameters of pores and globules of colloidal silica have been proposed for a large set of standard globular packings. It has been shown that, as the boron content in a porous glass rises, secondary silica globules in liquation channels grow, while their packing becomes looser.     

扫描探针显微技术研究聚苯乙烯单链颗粒的力学响应

首先通过极稀溶液滴膜的方法得到了聚苯乙烯的单链颗粒 .之后 ,采用稍浓溶液得到了既有单链聚苯乙烯颗粒又有多链 (上千根 )聚苯乙烯颗粒的样品 .力调制技术显示单链聚苯乙烯颗粒比多链聚苯乙烯颗粒软 ;另一方面 ,对多链聚苯乙烯颗粒和聚苯乙烯本体的纳米压印实验结果表明二者的模量是近似的 .因此 ,可以得出单链聚苯乙烯颗粒比本体聚苯乙烯软 ,这说明存在于聚苯乙烯单链颗粒中的分子链内的缠结点密度不如存在于本体中的分子链间的缠结点密度大     

Preparation and characterization of three-dimensionally ordered mesoporous titania microparticles as anode material for lithium ion battery

Three-dimensionally (3D) ordered mesoporous titania (anatase) microparticles without substrate were prepared by using polystyrene (PS) colloidal crystal as a template and characterized by transmission electron microscopy, X-ray diffraction, thermogravimetry and electrochemical measurement. As anode materials for lithium ion battery, they present eximious kinetic performance and good capacity retention due to their special architecture with mesoporous channels and thin walls, which are beneficial to the diffusion of lithium ions. Besides, mixing 3D ordered mesoporous titania microparticles with conductive additive can reduce the resistance of the anode, favor the mobility of the electrons, and decrease the polarization.     

Electrode Reactions of Catechol at Tyrosinase‐Immobilized Latex Suspensions

Tyrosinase was immobilized on polystyrene latex particles in order to control amounts of the enzyme. The tyrosinase‐coated latex particles were composed of the core polystyrene and four successive coating layers: polystyrene sulfonate, polyallylamine, tyrosinase and polyallylamine again, built up by the layer‐by‐layer technique. They showed catalytic currents for the enzymatic oxidation of catechol to o‐quinone. The enzyme activity per particle was evaluated as 2.3×10^?7 units from UV absorption of o‐quinone. The relation between the catalytic current and the concentration of catechol leads to a Michaelis‐Menten type kinetic equation. The layer‐by‐layer method was found to have a deactivating effect on enzyme catalysis. In spite of this, the catechol oxidation current was larger than the current from free tyrosinase at a common value of enzyme units per volume. This is ascribed to strong adsorption of the latex particles on the electrode, leading to the enhancement of the local concentration of tyrosinase.     

Particle Network Self-Assembly of Similar Size Sub-Micron Calcium Alginate and Polystyrene Particles Atop Glass

Particle-mediated self-assembly, such as nanocomposites, microstructure formation in materials, and core-shell coating of biological particles, offers precise control over the properties of biological materials for applications in drug delivery, tissue engineering, and biosensing. The assembly of similar-sized calcium alginate (CAG) and polystyrene sub-micron particles is studied in an aqueous sodium nitrate solution as a model for particle-mediated self-assembly of biological and synthetic mixed particle species. The objective is to reinforce biological matrices by incorporating synthetic particles to form hybrid particulate networks with tailored properties. By varying the ionic strength of the suspension, the authors alter the energy barriers for particle attachment to each other and to a glass substrate that result from colloidal surface forces. The particles do not show monotonic adsorption trend to glass with ionic strength. Hence, apart from DLVO theory—van der Waals and electrostatic interactions—the authors further consider solvation and bridging interactions in the analysis of the particulate adsorption-coagulation system. CAG particles, which support lower energy barriers to attachment relative to their counterpart polystyrene particles, accumulate as dense aggregates on the glass substrate. Polystyrene particles adsorb simultaneously as detached particles. At high electrolyte concentrations, where electrostatic repulsion is largely screened, the mixture of particles covers most of the glass substrate; the CAG particles form a continuous network throughout the glass substrate with pockets of polystyrene particles. The particulate structure is correlated with the adjustable energy barriers for particle attachment in the suspension.     

Monodisperse micron-sized macroporous poly(styrene-co-divinylbenzene) particles by seeded polymerization

Macroporous poly(styrene-co-divinylbenzene) particles were produced in a micron-size range by two-stage swelling and continuous polymerization. The molecular weight of the polystyrene seed particles was controlled by incorporating a urethane acrylate. It was found that the porosity of the particles produced by the seeded polymerization was dependent on the molecular weight of the seed polymer. As the molecular weight of the polystyrene seed increased, the porous particles produced became macroporous. Interestingly, the high molecular weight of the polystyrene seed had a negligible influence on the change of porosity of the seeded polymerized particles. It is believed that the viscosity of the swollen droplet phase remained pretty high with the change in composition because the polystyrene seed copolymerized with urethane cacrylate had many side chains. Received: 16 December 1999 Accepted: 9 August 2000     

Influence of the molecular weight of polystyrene on its thermodynamic properties

The thermodynamic properties of a series of polystyrene samples with different molecular weights (M _w was varied from 2.5·10³ to 6.57·10⁴) were studied by precision adiabatic vacuum, high-accuracy dynamic, and combustion calorimetry: temperature dependences of the heat capacity in a wide temperature range, thermodynamic characteristics of glass transition and glassy state under standard pressure, and energy of combustion. The thermodynamic functions C ^○ _p (T), H ^○(T) - H ^○(0), S ^○(T) - S ^○(0), and G ^○(T) - H ^○(0) of polystyrene with different molecular weights, enthalpies of combustion Δ_c H ^○, thermodynamic parameters of formation from simple substances Δ_f H ^○, Δ_f S ^○, and Δ_f G ^○ at T = 298.15 K, and parameters of their synthesis from monomers were calculated from the experimental data. The temperature dependences of the heat capacity for a region of 0–380 K, glass transition temperatures, and thermodynamic characteristics of formation and synthesis of polystyrene depending on its molecular weight were examined.     

Contact Angle Measurement for Dispersed Microspheres Using Scanning Confocal Microscopy

Abstract

Scanning confocal microscopy was used for contact angle measurement of individual microspheres. The measurements were carried out by using different laser‐scanned layers of the particle floating on the air–water interface. The ratio of the diameter for the cross‐section of the protruded area of the particle at the air–water interface to the actual diameter of the particle is used for contact angle measurements. Two systems, i.e., glass and polystyrene microspheres with diameters of 3–10 and 6 µm, respectively, with water were used for this investigation (this size range of particles are most relevant to inhalation applications). Using the developed methodology, contact angles of 27° and 41° were measured (with water) for glass and polystyrene particles, respectively. The theoretical error in contact angle measurement for the developed methodology is determined to be generally about 1° with a maximum of 3° for contact angle of particles ranging from 2 to 24 µm in size; the experimental error was 4–6°. The contact angles of glass and polystyrene particles were compared to those obtained from pendant drop method and confirmed.     

Dual latex/surfactant templating of hollow spherical silica particles with ordered mesoporous shells

Hollow spherical silica particles with hexagonally ordered mesoporous shells are synthesized with the dual use of cetyltrimethylammonium bromide (CTAB) and unmodified polystyrene latex microspheres as templates in concentrated aqueous ammonia. In most of the hollow mesoporous particles, cylindrical pores run parallel to the hollow core due to interactions of CTAB/silica aggregates with the latices. Effects on the product structure of the CTAB:latex ratio, the amount of aqueous ammonia, and the latex size are studied. Hollow particles with hexagonally patterned mesoporous shells are obtained at moderate CTAB:latex ratios. Too little CTAB causes silica shell growth without surfactant templating, and too much induces nucleation of new mesoporous silica particles without latex cores. The concentration of ammonia must be large to induce co-assembly of CTAB, silica, and latex into dispersed particles. The results are consistent with the formation of particles by addition of CTAB/silica aggregates to the surface of latex microspheres. When the size and number density of the latex microspheres are changed, the size of the hollow core and the shell thickness can be controlled. However, if the microspheres are too small (50 nm in this case), agglomerated particles with many hollow voids are obtained, most likely due to colloidal instability.     

Atom transfer radical polymerization from nanoparticles: a tool for the preparation of well-defined hybrid nanostructures and for understanding the chemistry of controlled/"living" radical polymerizations from surfaces

Structurally well-defined polymer--nanoparticle hybrids were prepared by modifying the surface of silica nanoparticles with initiators for atom transfer radical polymerization and by using these initiator-modified nanoparticles as macroinitiators. Well-defined polymer chains were grown from the nanoparticle surfaces to yield individual particles composed of a silica core and a well-defined, densely grafted outer polystyrene or poly(methyl methacrylate) layer. In both cases, linear kinetic plots, linear plots of molecular weight (M(n)) versus conversion, increases in hydrodynamic diameter with increasing conversion, and narrow molecular weight distributions (M(w)/M(n)) for the grafted polymer samples were observed. Polymerizations of styrene from smaller (75-nm-diameter) silica nanoparticles exhibited good molecular weight control, while polymerizations of methyl methacrylate (MMA) from the same nanoparticles exhibited good molecular weight control only when a small amount of free initiator was added to the polymerization solution. The difference in polymerization behavior for styrene and MMA was ascribed to the facts that styrene undergoes thermal self-initiation while MMA does not and that termination processes involving freely diffusing chains are faster than those involving surface-bound chains. The polymerizations of both styrene and MMA from larger (300-nm-diameter) silica nanoparticles did not exhibit molecular weight control. This lack of control was ascribed to the very high initial monomer-to-initiator ratio in these polymerizations. Molecular weight control was induced by the addition of a small amount of free initiator to the polymerization but was not induced when 5--15 mol % of deactivator (Cu(II) complex) was added.     

Controlling the thermomechanical properties of polymer nanocomposites by tailoring the polymer–particle interface

We show that the thermomechanical properties of polymer nanocomposites are critically affected by polymer-particle wetting behavior. Silica nanoparticles grafted with dense polystyrene brushes of degree of polymerization 1050 are blended with polystyrene melts to form nanocomposites. It was found that low molecular weight (MW) polystyrene melts with lengths <880 wet these particles. Concurrently, the glass transition temperature (T_g) of the nanocomposite increases. At higher MW, the matrix does not wet the particles and the T_g decreases. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2944–2950, 2006