High solids TEMPO‐mediated radical semibatch emulsion polymerization of styrene

A bicomponent initiation system consisting of 2,2,6,6‐tetramethylpiperidine‐N‐oxyl (TEMPO) and the water soluble initiator potassium persulfate (KPS) was used to develop a robust and versatile semibatch emulsion polymerization process to obtain polystyrene (PS) latexes with solids contents of 5–40 wt %. A window of operating conditions was found that yielded high conversion (>95%) stable latexes and well controlled polymers, overcoming limitations found in previous attempts at developing similar processes using TEMPO. The critical parameters studied were surfactant concentration, monomer concentration in the nucleation step and the monomer feed rate in the semibatch step. Methyl acrylate (MA) was used in the nucleation step to improve the nitroxide efficiency (N_Eff). Latexes having molecular weight distribution (MWD) with dispersity (?) lower than 1.5, average particle size (D_p) from ≈32 to ≈500 nm, nitroxide efficiencies N_Eff up to ≈1.0 and monomer conversions >90% were obtained in less than 12 h with solids contents up to 40 wt %. These results constitute a significant advance over prior efforts in TEMPO‐mediated polymerization in aqueous dispersions. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 49–62     

Adsorption studies of iron(III) on chitin

Adsorption of ferric ions by chitin was studied by the batch equilibration method. The influence of particle size and dosage of the adsorbant, contact time, initial concentration of the adsorbate and temperature were experimentally verified. The effect of anions like chloride, nitrate and sulphate and also of cations like zinc, chromium and copper on the adsorption of iron(III) was determined. The time dependence of fraction of adsorption,Yt, at varying particle sizes and doses of chitin and the intraparticle diffusion rate constants,k _p , of the adsorption process were calculated. Thermodynamic and equilibrium parameters of the reaction were determined to understand the sorption behaviour of chitin. The results revealed that the adsorption of iron(III) by chitin is spontaneous, endothermic and favourable.     

Dynamics in simultaneous bio-electro-generative leaching for pyrite-MnO<Subscript>2</Subscript>

The principle for the electro-generative simultaneous leaching (EGSL) is applied to simultaneous leaching of pyrite-MnO₂ in this paper. A galvanic system for the bio-electro-generative simultaneous leaching (BEGSL) has been set up. The equation of electric quantity vs. time is used to study the effect of produced sulfur on electro-generative efficiency and quantity. It has been shown that the resistance decreased in the presence of Acidithiobacillus thiooxidans (A. thiooxidans) with the increase of electro-generative efficiency. The effects of temperature and grain size on rate of ferrous extraction from pyrite under the conditions of presence and absence of A. thiooxidans were studied, respectively. The changes in the extraction rate of Fe²⁺ as particle size in presence of A. thiooxidans were more evident than that in the absence, which indicated that the extraction in bio-electro-generative leaching was affected by particle size remarkably. Around the optimum culture temperature for A. thiooxidans, the bigger change in the conversion rate of Fe²⁺ was depending on temperature. The transferred charge in BEGSL including part of S⁰ to sulfate group in the presence of (A. thiooxidans) which is called as biologic electric quantity, and the ratio of biologic electric quantity reached to 58.10% in 72 h among the all-transferred charge. Supported by the major state basic research development program (No. 2004CB619204); the National Science Foundation of China (No. 50374077); the Education Department Foundation of Hunan Province (No. 07D069).     

Self-assembled ultra-thin coatings of octadecyltrichlorosilane (OTS) formed at the surface of iron oxide nanoparticles

In a series of experiments, we coated iron oxide nanoparticles, which were originally stabilized with lauric acid, with a polymer layer of Octadecyltrichlorosilane (OTS). Characterization of the different coated nanoparticles was accomplished by Static and Dynamic Light Scattering, acoustic spectroscopy, and Atomic Force Microscopy. In various experiments, we systematically investigated the effect of different parameters such as the OTS concentration and iron oxide content on the particle size of the coated nanoparticles. It was recognized that the size of the coated nanoparticles mainly depend on the concentration of OTS (C _OTS) measured with respect to the concentration of the iron oxide particles (C _mag.). Below a well-defined threshold value of C _OTS /C _mag, we did not observe any adsorption of OTS on the surface of iron oxide nanoparticles. The particle size of OTS-coated iron oxide nanoparticles increased rapidly at concentration ratios above the threshold concentration and reached a typical plateau value for long periods of time.     

Leaching of El-Missikat low-grade fluoritized uranium ore by sulfuric acid: mechanism and kinetic

A well-characterized low-grade fluoritized uranium samples from new occurrence in Gabal El-Missikat prospect, Eastern Desert, Egypt was subjected to sulfuric acid leaching. The effects of leaching parameters on uranium dissolution mechanism were investigated. The shrinking core model was used to model leaching reactions. The kinetics equations indicates that the reactions appear to be controlled by layer diffusion process. The activation energy for uranium dissolution was evaluated. Low activation energy value (2.54 kJ mol⁻¹) confirm the diffusion layer mechanism. The presence of fluoride ions in the solution increases the dissolution of uranium. The optimum process operating parameters were: sulfuric acid concentration: 1.5 M, solid–liquid ratio: 1:3, contact time 8 h; agitation speed rate 200 rpm; and ore particle size − 75 µm at temperature 60 °C, in the absence of an external oxidant. Under these experimental conditions, the extraction efficiency of uranium was about 91%.

     

Synthesis of amphiphilic diblock copolymers poly[2-(<Emphasis Type="Italic">N</Emphasis>, <Emphasis Type="Italic">N</Emphasis>-dimethylamino)ethyl methacrylate]-<Emphasis Type="Italic">b</Emphasis>-poly(stearyl methacrylate) and their self-assembly in mixed solvent

Amphiphilic diblock copolymers consisting of 2-(N, N-dimethylamino)ethyl methacrylate (DMAEMA, abbreviated as DMA) and stearyl methacrylate (SMA) with different degrees of polymerization and compositions were prepared by reversible addition–fragmentation chain transfer (RAFT) copolymerization. The composition and chemical structures of (co)polymers were confirmed by the measurements of ¹H NMR spectroscopy and gel permeation chromatography (GPC). The self-aggregating structures of amphiphilic diblock copolymers with the concentration of 0.1~0.3 wt.% in THF/water mixed solvent was investigated by transmission electron microscopy (TEM) and dynamic light scattering (DLS). It was found that both the morphologies and aggregating particle size resulted from the amphiphilic diblock copolymers depended on the variation of pH values, the lengths of the hydrophobic PSMA chains, and the weight ratio of THF/water mixed solvent.     

Adsorption dynamics and equilibrium studies of Zn (II) onto chitosan

Batch equilibration studies are conducted to determine the nature of adsorption of zinc (II) over chitosan. The factors affecting the adsorption process like particle size, contact time, dosage, pH, effects of chloride and nitrate are identified. The influence of temperature and co-ions on the adsorption process is verified. The fraction of adsorption,Y _t and the intraparticle diffusion rate constant,k _p are calculated at different environments and the results are discussed. The nature of adsorption of the zinc (II)-chitosan system is explained using Freundlich, Langmuir isotherms and thermodynamic parameters     

The effect of cosurfactants and the initiator concentration on the polymer to surfactant concentration in nanolatexes

The effect of cosurfactant and initiator concentration on the ab initio production of nanolatexes using low surfactant levels was investigated. While the use of cosurfactants (acrylic acid and pentanol) increased the amount of monomer that can be used in styrene‐SDS microemulsion formulations to 13 wt %, high surfactant concentrations are still required, resulting in polymer‐to‐surfactant ratios (Pol/Surf) <1. Latexes with particle size of 30 ± 5 nm were produced upon polymerization of these microemulsions. The Pol/Surf can be significantly increased by increasing the initiator concentration of emulsion polymerization recipes. Particle sizes are comparable with microemulsion latexes, however, less surfactant is required. The reduction in the particle size with higher initiator concentration is attributed to a higher efficiency of particle nucleation and to a higher nucleation rate relative to the rate of monomer transfer. Nanolatexes (particle size < 30 nm) were obtained with 19 wt % solids content and Pol/Surf of 3.6 in ab initio. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Superparamagnetic Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> Nanoparticles Decorated Multiwalled Carbon Nanotubes: Preparation via Cyclic Microwave Approach and Their Drug Release Behavior

Superparamagnetic Fe₃O₄ nanoparticles decorated multiwalled carbon nanotubes were synthesized by cyclic microwave method and the effect of different reaction parameters on the products were also investigated. The as synthesized products were characterized by XRD, TEM, SEM, EDS, FT-IR, VSM, and Uv–Vis spectroscopy. It was observed that precursors’ concentration ratio had great effect on the particle size and decorating quality. Also the effect of the other parameters including irradiation power and time on product size and uniformity of the product were also investigated. The best products with desired particle size distribution obtained when irradiation power and reaction time were 900 W and 6 min, respectively. Aspirin and acetaminophen were applied as a model drug and the drug release behavior of the composite was investigated. It was observed that the drug discharge was highly dependent to the pH and can be tuned by applying magnetic field.     

Rice Bran as an Excellent Sorbent for Heavy Metals from Aqueous Media, 1. Optimization of Conditions

In this two‐part report, the efficiency of rice bran in removal of heavy metals such as cadmium, lead, zinc, nickel, copper and iron(III) from aqueous solution is investigated. The different experimental conditions such as pH, temperature, volume of solution, bran amount, particle size, exchange time, stirring speed, etc. are studied, and the optimum conditions are selected in part 1 of this series of reports. The efficiency of bran in removal of heavy metals is presented with and without treatments. For treatment, heat or acid, alkali and salt solutions were used. The results obtained show that after treating with saturated sodium chloride solution, its efficiency for Ni²⁺ and Zn²⁺ improves. At pH 5, all studied cations have recoveries more than 93% (lead and cadmium 100%). The exchange speed is very high and has preference over the classical ion exchangers.     

Determination of impurities in magnesium niobate by slurry introduction axially viewed inductively coupled plasma optical emission spectrometry

A simple preparation scheme is described for the quantitative analysis of a magnesium niobate sample using slurry introduction axially viewed inductively coupled plasma optical emission spectrometry. Relationships between the stability of slurries and the conditions, such as particle size, pH, dispersant and amount of dispersant, were investigated experimentally. The MgNb₂O₆ slurry sample was prepared by adding the dispersant sodium polyacrylate and agitation in an ultrasonic bath to ensure good dispersion. Under optimization of pH and amount of dispersant, an analysis of minor and trace impurities (Ba, Ca, Cr, Cu, Fe, Mn, Ni, Pb) in magnesium niobate was accomplished. Applying a paired t test, we showed that the results were in agreement at a 95% confidence level with the reference values obtained by a fusion method for a magnesium niobate sample, which verified that the calibration curves could be established by aqueous standards. Analytical results demonstrate that the factors that affected the accuracy of determination for MgNb₂O₆ are mainly the particle size of the sample and the stability of slurry.     

Beneficiation of zinc from electric arc furnace dust using hydrometallurgical approach

Zinc bearing wastes such as electric arc furnace dust (EAFD) obtained from steel making constitute an important resource for zinc extraction. Inclusion of heavy metals such as Pb, Cd, Cu, Cr, Ni, etc., in these wastes makes them hazardous to use and/or dispose. In the present research work, leaching kinetics of EAFD with sulfuric acid has been investigated and various experimental parameters such as concentration of lixiviant, stirring rate, sample particle size, liquid/solid proportion, and temperature of the reaction have been optimized. It has been found that the dissolution rate of EAFD increases with rise in temperature, acidic strength, rate of stirring, liquid to solid proportion and with reduction in EAFD particle size. From the analysis of leaching kinetic data by means of graphical and statistical methods, it has been evaluated that the leaching kinetics of EAFD is dictated by surface diffusion reaction. Apparent energy of activation for the leaching reaction of EAFD with sulfuric acid is found to be 13.1 kJ mol^–1 within the temperature range of 308 to 358 K.     

Determination of manganese and zinc in powdered chocolate samples by slurry sampling using sequential multi-element flame atomic absorption spectrometry

In the present work, a slurry sampling flame atomic absorption spectrometric method to determine directly manganese and zinc in powdered chocolate samples is proposed. The optimization step was performed using univariate methodology involving the following factors: nature and concentration of the acid solution, sonication time, and particle size. The established conditions led to the use of a sample mass of 150 mg, 2.0 mol L^− 1 nitric acid solution, sonication time of 15 min, and a slurry volume of 50 mL. This method allows the determination of manganese and zinc with detection limit of 52 and 61 ng g^− 1, respectively, and a precision expressed as relative standard deviation (RSD) of 2.6% and 3.2% (both, n = 10) for contents of manganese and zinc of 52.4 and 100.0 μg g^− 1, respectively. The proposed method was applied for determination of manganese and zinc in five powdered chocolate samples. In these, the manganese content varied from 42.8 to 52.7 and from 88.6 to 102.4 μg g^− 1 of zinc. The analytical results were compared with the results obtained by analysis of these samples after digestion using open vessel and acid bomb digestion procedures and determination using FS-FAAS. The statistical comparison by t-test (95% confidence level) showed no significant difference between these results.     

Removal of zinc metal ion (Zn) from its aqueous solution by kaolin clay mineral: A kinetic and equilibrium study

A laboratory batch study has been performed to study the effect of various physic-chemical factors such as initial metal ion concentration, solution pH, and amount of adsorbent, contact time and temperature on the adsorption characteristics of zinc (Zn²⁺) metal ions onto kaolin. It has been found that the amount of adsorption of zinc metal ion increases with initial metal ion concentration, contact time, solution pH but decreases with the amount of adsorbent and temperature of the system. Kinetic experiments clearly indicate that adsorption of zinc metal ion (Zn²⁺) on kaolin is a two steps process: a very rapid adsorption of zinc metal ion to the external surface is followed by possible slow decreasing intra-particle diffusion in the interior of the adsorbent which has also been confirmed by intra-particle diffusion model. The equilibrium time is found to be in the order of 60 min. Overall the kinetic studies showed that the zinc adsorption process followed pseudo-second-order kinetics among pseudo-first-order and intra-particle diffusion model. The different kinetic parameters including rate constant are determined at different initial metal ion concentration, solution pH, amount of adsorbent and temperature respectively. The equilibrium adsorption results are analyzed by both Langmuir and Freundlich models to determine the mechanistic parameters associated with the adsorption process. The value of separation factor, R_L from Langmuir equation also gives an indication of favorable adsorption. Finally thermodynamic parameters are determined at three different temperatures and it has been found that the adsorption process is exothermic due to negative ΔH° accompanied by decrease in entropy change and Gibbs free energy change (ΔG°).     

Synthesis and properties of new chelating resin with a spacer containing alpha-nitroso-beta-naphthol as the functional group

A new chelating ion-exchange resin with a spacer CH₂-NH-C₆H₄- based on a microreticular chloromethylated styrene-divinylbenzene copolymer containing α-nitroso-β-naphthol as a functional group has been synthesized. The sorption characteristics for manganese(II), iron(III), cobalt(II), nickel(II), copper(II), and zinc(II) have been investigated over the pH range 1.0–7.0. The resin is highly stable in acidic and alkaline medium. Iron(III) and cobalt(II); copper(II) and iron(III) are separated very effectively in a column operation by stepwise elution.     

Reaction kinetics of malachite in ammonium carbamate solution

The dissolution of malachite particles in ammonium carbamate (AC) solutions was investigated in a batch reactor, using the parameters of temperature, AC concentration, particle size, and stirring speed. The shrinking core model was evaluated for the dissolution rate increased by decreasing particle size and increasing the temperature and AC concentration. No important effect was observed for variations in stirring speed. Dissolution curves were evaluated in order to test shrinking core models for fluid-solid systems. The dissolution rate was determined as being controlled by surface chemical reaction. The activation energy of the leaching process was determined as 46.04 kJ mol^?1.     

Mycelial pellet formation by Rhizopus oryzae ATCC 20344

Factors in a cultivation medium affecting fungal growth morphology and funmaric acid production by Rhizopus oryzae ATCC 20344 were investigated. These factors included the initial pH value and trace metals such as zinc, magnesium, iron, and manganese in the cultivation medium. It was found that a significant change in the growth morphology of R. oryzae ATCC 20344 occurs when the initial pH value is varied. A lower initial pH value in the cultivation medium was inhibitory to fungal growth, and fast growth in the cultivation medium at a higher initial pH value promoted, the formation of large pellets or filamentous forms. Trace metals in the cultivation media also had significant effects on pellet formation and fumaric acid fermentation.     

Kinetic study of the nitroxide‐mediated controlled free‐radical polymerization of n‐butyl acrylate in aqueous miniemulsions

The controlled free‐radical homopolymerization of n‐butyl acrylate was studied in aqueous miniemulsions at 112 and 125 °C with a low molar mass alkoxyamine unimolecular initiator and an acyclic β‐phosphonylated nitroxide mediator, N‐tert‐butyl‐N‐(1‐diethylphosphono‐2,2‐dimethylpropyl) nitroxide, also called SG1. The polymerizations led to stable latices with 20 wt % solids and were obtained with neither coagulation during synthesis nor destabilization over time. However, in contrast to latices obtained via classical free‐radical polymerization, the average particle size of the final latices was large, with broad particle size distributions. The initial [SG1]₀/[alkoxyamine]₀ molar ratio was shown to control the rate of polymerization. The fraction of SG1 released upon macroradical self‐termination was small with respect to the initial alkoxyamine concentration, indicating a very low fraction of dead chains. Average molar masses were controlled by the initial concentration of alkoxyamine and increased linearly with monomer conversion. The molar mass distribution was narrow, depending on the initial concentration of free nitroxide in the system. The initiator efficiency was lower than 1 at 112 °C but was very significantly improved when either a macroinitiator was used at 112 °C or the polymerization temperature was raised to 125 °C. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4410–4420, 2002     

Poly(PEGDMA‐MAA) copolymeric micro and nanoparticles for oral insulin delivery

Poly(ethylene glycol) dimethacrylate (PEGDMA) and methacrylic acid (MAA) based micro and nanoparticles were prepared and evaluated as a carrier for oral delivery of insulin. PEGDMA was synthesized by esterification reaction of the PEG4000 with MAA in the presence of an acid catalyst. Particles of different size were prepared by emulsion polymerization reaction using different concentration of sodium lauryl sulphate (SLS) as an emulsifying agent. Synthesized copolymeric particle were characterized by attenuated total reflectance‐Fourier transform infrared spectroscopy (ATR‐FTIR), scanning electron microscopy, and acid value. The mean particle diameter of the polymeric micro and nanoparticles at various physiologically relevant pH values was measured using dynamic light scattering. Insulin loading efficiency of the particles was found to be directly proportional to the particle size and inversely proportional to the acid value of the particles. In vitro insulin release studies from various insulin loaded particles were performed by simulating the gastrointestinal tract conditions using HPLC. At pH 2.5, the release of insulin from polymeric particles was observed in the range of 5–8% while a significant higher release (20–35%) was observed at pH 7.4 during first 15 min of in vitro release. Largest size copolymeric particles of 8.3 µm also showed the highest efficiency to reduce the blood glucose level in diabetic rabbits. Copyright © 2010 John Wiley & Sons, Ltd.     

Oxidative dehydrogenation of isobutane to isobutylene over supported transition metal oxide catalysts

Para-selectivity of ZSM-5 zeolites with similar bulk Si/Al ratio, but different particle size and surface Al concentration has been investigated in toluene disproportionation. Results showed that enhancedpara-selectivity is a consequence not only of the particle size but also of the external surface aluminium concentration in the particles.