Effect of aqueous comonomer solubility on the surfactant-free emulsion copolymerization of methyl methacrylate

Surfactant-free emulsion copolymerization was used to prepare methyl methacrylate-hydroxyethyl methacrylate (MMA-HEA) and methyl methacrylate-hydroxypropyl methacrylate (MMA-HPMA) latex particles. Also, glycidyl methacrylate (GMA) was grafted onto the surface of the preformed MMA-HPMA latex particles by seeded surfactant-free emulsion copolymerization. The copolymerization reactions were conducted at 75 °C using a water-soluble initiator, potassium persulfate (KPS). The morphologies of copolymer latex particles were observed using Scanning electron microscopy (SEM). The influence of different reactions parameters (the MMA saturation concentration (Sr), the KPS concentration and the aqueous solubility of the comonomers (HEA or HPMA)) on the particles average diameter and particles size dispersity was investigated. The experimental results showed that the increase of initiator concentration induces in all investigated cases the increase of particles average diameter, while the presence of HEA or HPMA as comonomers in the copolymerization reaction of MMA (1,000% Sr) lead to a decrease of particles average diameter. At small KPS concentration the latex is monodisperse, the increase of the initiator concentration leading to the formation of polydisperse latex. In the case of grafting reaction of GMA onto the monodisperse preformed MMA-HEA latex particles, although the average diameter of the final particles doubles the latex remains quasi-monodisperse.     

Counterion Effect of Cationic Surfactants Upon the Interaction with Poly(methacrylic acid)

This work investigates decylammonium salts, with inorganic (chloride and thiocyanate) and organic (acetate and butyrate) counterions, in interaction with poly(methacrylic acid) (PMA). The study is conducted by means of surface tension, relative viscosity and pH measurements. The role of the methyl group in PMA appears by comparison with analogous mixtures of poly(acrylic acid) (PAA). In aqueous solution, a non-cooperative interaction between the surfactant and the hydrophobic microdomains (HMD) of PMA starts first. With surfactant addition, micellar aggregates bound onto the polymer chain appear at a concentration T ₁, which is higher than for the analogous PAA systems, but lower than the respective CMC. T ₁ is lower for chloride than for thiocyanate and lower for acetate than for butyrate. Depending on the counterion, the HMD conceal or expose carboxyl groups, with influence upon the interaction strength and the bulk and surface behavior. Stronger interactions and maxima of surface tension and relative viscosity appear for the systems with organic counterions. An estimation of the interaction strength shows weaker surfactant interactions with PMA than with PAA, and that acetate induces the strongest interaction while thiocyanate the weakest.     

Optimization of synthesis parameters in interfacial polycondensation using design of experiments

The reaction of phenylphosphonic dichloride with 4,4′-cyclohexylidenebisphenol by a gas–liquid interfacial polycondensation was investigated. The design of experiments (DoE) method is used for determination of the best reaction conditions. The correlation of simultaneous influence of the parameters (reaction time, reaction temperature, alkaline medium, reagents molar ratio) on yield and inherent viscosity was studied.     

Semi-batch reactive crystallisation of mono-ammonium phosphate: An experimental study

NH₄H₂PO₄, mono-ammonium phosphate (MAP) and (NH₄)₂HPO₄, di-ammonium phosphate (DAP) have become leading phosphate fertiliser products worldwide. Ammonium phosphates are produced by reactions of ammonia and phosphoric acid resulting in the formation of the mono-basic, di-basic, or tri-basic salts. Inefficiencies in the MAP/DAP production process are due to the lack of a fundamental understanding of the crystallisation–reaction mechanisms. A semi-batch reactive crystalliser equipped with a cooling jacket, a dual feed system and a turbine type agitator has been used in this study. Effects of N/P ratio, seed crystals, feeding system, feed flow rate, initial supersaturation, feeding time and mixing intensity to the real-time supersaturation, crystal yield, crystal shape (aspect ratio) and final crystal size distribution (CSD) were studied in order to understand the kinetics. This study aims to provide new insights into the MAP/DAP reaction–crystallisation mechanisms.     

Influence of octyl substituted octakis(dimethylsiloxy)octasilsesquioxane on the morphology and thermal and mechanical properties of low density polyethylene

Low density polyethylene (LDPE) was melt blended with octyl substituted octakis(dimethylsiloxy)octasilsesquioxane (AS8) prepared in high yield by hydrosilylation of octene with octakis(hydrodimethylsiloxy)octasilsesquioxane. Two procedures were used to incorporate AS8 into LDPE at nanolevel and their efficiency was investigated by X‐ray diffraction (XRD), scanning electron microscopy, atomic force microscopy (AFM), differential scanning calorimetry, thermogravimetry and mechanical characterization. A slight increase of crystallite mean dimensions was observed by XRD in both types of LDPE‐AS8 composites compared with neat LDPE. Better AS8 dispersion was observed by AFM in the composite prepared by the first procedure and the increase of both tensile strength and elongation at break in this composite confirmed the nanolevel dispersion and interface improvement in this case. AS8 influence in the final stages of polyethylene fracture was illustrated by AFM of elongated tensile specimens and a new mechanism of AS8 action was suggested. An interesting behavior consisting of simultaneous improvement of elastic modulus, strength and ductility was detected in the low range of polyhedral oligomeric silsesquioxane concentration in LDPE (0.5 wt%). © 2013 Society of Chemical Industry     

The synthesis,activation and characterization of charcoal powder for the removal of methylene blue and cadmium from wastewater

Charcoal prepared from biomass, wastes of the local forest (tree branches), activated with NaOH solution and with Degussa P25 (TiO₂) was used as adsorbent and photocatalyst for the removal of cadmium cations and methylene blue from wastewater. These materials were characterized by using atomic force microscopy for roughness surface. The energy dispersive X-ray (EDX) spectroscopy and X-ray diffraction (XRD) analysis indicate the existence of nano TiO₂ on the charcoal surface. Additionally, the FT-IR spectroscopy measurements indicate that the alkali treatment develops hydroxyl groups on charcoal surface which could adsorb methylene blue, heavy metals and other pollutants via the synergistic effect. The activities of the charcoal (BC), activated charcoal (BCA) and BCA/TiO₂ mixture (BCA-D) depend on the contact time, adsorbent dosage and pH. The adsorption kinetic data were tested using pseudo-first-order, pseudo-second-order and intraparticle diffusion models. The kinetic studies showed that the adsorption is followed by the pseudo-second-order reaction with regard to the intraparticle diffusion rate kinetics.     

Noise in Refrigerating Tunnel Junctions and in Microbolometers

Microrefrigerators based on normal metal–insulator–superconductor (NIS) junctions represent a very attractive alternative to cool the microbolometers and calorimeters for astrophysical observations in space-borne experiments. The performance in such measurements requires a good knowledge of the noise sources in the detectors. In this paper we present detailed calculations of the thermal fluctuations and of the noise equivalent power due to the heat transfer through the NIS junctions or the thermal contact between different subsystems of the detector. The influence of the input optical power—which, in the cases that interest us, is the cosmic background radiation—will also be evaluated. Analytical approximations valid at low temperatures are given.     

Risk assessment for pipelines with active defects based on artificial intelligence methods

The paper provides another insight into the pipeline risk assessment for in-service pressure piping containing defects. Beside of the traditional analytical approximation methods or sampling-based methods safety index and failure probability of pressure piping containing defects will be obtained based on a novel type of support vector machine developed in a minimax manner. The safety index or failure probability is carried out based on a binary classification approach. The procedure named classification reliability procedure, involving a link between artificial intelligence and reliability methods was developed as a user-friendly computer program in MATLAB language. To reveal the capacity of the proposed procedure two comparative numerical examples replicating a previous related work and predicting the failure probabilities of pressured pipeline with defects were presented.     

Conformational Changes in the BSA-LT4 Complex Induced by the Presence of Vitamins: Spectroscopic Approach and Molecular Docking

Levothyroxine (LT4) is known for its use in various conditions including hypothyroidism. LT4 interaction with serum albumin may be influenced by the presence of vitamins. For this reason, we investigated the effect of vitamin C, vitamin B12, and folic acid on the complex of Bovine Serum Albumin with LT4 (BSA-LT4). UV-Vis spectroscopy was used to monitor the influence of vitamins on the BSA-LT4 complex. Fluorescence spectroscopy revealed a static quenching mechanism of the fluorescence of BSA-LT4 complex by the vitamin C and folic acid and a combined mechanism for vitamin B12. The interaction of vitamin C and folic acid with BSA-LT4 was moderate, while the binding of vitamin B12 was much stronger, extending the storage time of LT4 in blood plasma. Synchronous fluorescence found that the vitamins were closer to the vicinity of Trp than to Tyr and the effect was more pronounced for the binding of vitamin B12. The thermal stability of the BSA-LT4 complex was more evident, but no influence on the stability of BSA-LT4 complex was obtained for vitamin C. Molecular docking studies showed that vitamin C and folic acid bound the same site of the protein, while vitamin B12 bonded to a different site.