Ethylene–vinyl acetate semi-batch emulsion copolymerization: Use of factorial experiments for improved process understanding

A good working knowledge of the mechanism and an appreciation of the effects the process variables have on the properties of interest are required for optimization and control of polymerization processes. Despite the importance of ethylene-vinyl acetate emulsion copolymers, limited kinetic information is available. Results from a series of factorial experiments are presented here which examine the emulsion polymerization of ethylene with vinyl acetate. Copolymers of up to 32 wt % ethylene have been produced at an ethylene pressure of 500 psig and a temperature of 20°C. The effects of the process variables on the rate of polymerization, copolymer composition, particle size and number, molecular weight averages, and gel content are discussed. The kinetic results obtained suggest process improvements for the production of homogeneous copolymer. Mechanistically, the locus of polymerization has been verified as the polymer particles and little water phase polymerization was observed. © 1993 John Wiley & Sons, Inc.     

Ethylene–vinyl acetate semi-batch emulsion copolymerization: Experimental design and preliminary screening experiments

Ethylene–vinyl acetate emulsion copolymers are useful materials for paint, adhesive, and coating applications. The kinetics of their production remain largely unstudied, probably due to the inherent difficulties associated with pressure polymerizations. Polymerizations at elevated pressures are in general more difficult to understand and control, and relatively more expensive since one has to consider the added cost of increased safety precautions. Reported here are the preliminary results of an extensive experimental investigation of the variables which govern the ethylene–vinyl acetate emulsion process. Two redox initiator systems have been identified as more suitable for the polymerization process. Two buffer systems, namely sodium acetate/acetic acid and potassium phosphate, have been used to effectively control pH. The addition of n-hexane has offered an effective method of enhancing the ethylene content in the copolymer produced. Several other important variables including agitation/mixing and emulsifier type and concentration have been identified and are discussed. These screening experimental observations have aided in the selection of suitable design levels for future, more focused experimentation to quantify the effects of reaction variables on the latex and copolymer properties of interest. A review of the existing literature on ethylene–vinyl acetate copolymer properties and processes is also included. © 1993 John Wiley & Sons, Inc.     

Protein Footprinting by Carbenes on a Fast Photochemical Oxidation of Proteins (FPOP) Platform

Protein footprinting combined with mass spectrometry provides a method to study protein structures and interactions. To improve further current protein footprinting methods, we adapted the fast photochemical oxidation of proteins (FPOP) platform to utilize carbenes as the footprinting reagent. A Nd-YAG laser provides 355 nm laser for carbene generation in situ from photoleucine as the carbene precursor in a flow system with calmodulin as the test protein. Reversed-phase liquid chromatography coupled with mass spectrometry is appropriate to analyze the modifications produced in this footprinting. By comparing the modification extent of apo and holo calmodulin on the peptide level, we can resolve different structural domains of the protein. Carbene footprinting in a flow system is promising.

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Highly Strained Heterocycles Constructed from Boron–Boron Multiple Bonds and Heavy Chalcogens

The reactions of a diborene with elemental selenium or tellurium are shown to afford a diboraselenirane or diboratellurirane, respectively. These reactions are reminiscent of the sequestration of subvalent oxygen and nitrogen in the formation of oxiranes and aziridines; however, such reactivity is not known between alkenes and the heavy chalcogens. Although carbon is too electronegative to affect the reduction of elements with lower relative electronegativity, the highly reducing nature of the B?B double bond enables reactions with Se⁰ and Te⁰. The capacity of multiple bonds between boron atoms to donate electron density is highlighted in reactions where diborynes behave as nucleophiles, attacking one of the two Te atoms of diaryltellurides, forming salts consisting of diboratellurenium cations and aryltelluride anions.     

Photoluminescence of the nanosized xerogel Zn<Subscript>2</Subscript>SiO<Subscript>4</Subscript>:Mn<Superscript>2+</Superscript> in pores of anodic alumina

The photoluminescence properties of a composite material prepared by the introduction of the nanosized phosphor Zn₂SiO₄:Mn²⁺ into porous anodic alumina have been investigated. Scanning electron microscopy studies have revealed that Zn₂SiO₄:Mn²⁺ particles are uniformly distributed in 70% of the volume of the pore channels. The samples exhibit an intense luminescence in the range of 2.3–3.0 eV, which corresponds to the emission of different types of F centers in alumina. After the formation of Zn₂SiO₄:Mn²⁺ nanoparticles in the pores, an intense photoluminescence band is observed at 2.4 eV due to the ⁴T₁–⁶A₁ electronic transition within the 3d shell of the Mn²⁺ activator ion. It has been found that the maximum of the photoluminescence of Zn₂SiO₄:Mn²⁺ xerogel nanoparticles located in the porous matrix is shifted to higher energies, and the luminescence decay time decreases significantly.     

Reduction of colloidal Ag2S to binary Ag2–XS/Ag nanoparticles under UV and visible irradiation

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The design of hybrid materials based on magnetic Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticles and luminescent CdS nanoparticles for cell visualization

Hybrid nanoparticles based on Fe₃O₄ and CdS combining magnetic and luminescence properties were synthesized. The possibility of visualization of various cells by 3-mercaptopropylsilane-modified CdS nanoparticles and hybrid nanoparticles based on them using a confocal microscope was demonstrated. The synthesized materials did not show a clear-cut cytotoxicity.     

Eine Druckflasche zur St?rkemehlbestimmung

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Optimal feedback control of the forced van der Pol system

A simple feedback control strategy for chaotic systems is investigated using the forced van der Pol system as an example. The strategy regards chaos control as an optimization problem, where the maximum magnitude Floquet multiplier of a target unstable periodic orbit (UPO) is used as a cost function that needs to be minimized. Thus, the method obtains the optimal control gain in terms of the stability of the target UPO. This strategy was recently proposed for the proportional feedback control (PFC) method. Here, it is extended to the highly popular delayed feedback control (DFC) method. Since the DFC method treats the system as a delay-differential equation whose phase space is infinite-dimensional, the characteristic multipliers are found through a truncation in the number of delayed states. Control of a target UPO is achieved for several values of the forcing amplitude. We compare the DFC and PFC methods in terms of stability of the controlled orbit, steady state error and control effort.