Future directions in physiochemical modeling of the thermodynamics of polyelectrolyte coacervates

We review theories of polyelectrolyte (PE) coacervation, which is the spontaneous association of oppositely charged units of PEs and phase separation into a polymer-dense phase in aqueous solution. The simplest theories can be divided into “physics-based” and “chemistry-based” approaches. In the former, PEs are treated as charged, long-chain, molecules, defined by charge level, chain length, and chain flexibility, but otherwise lacking chemical identity, with electrostatic interactions driving coacervation. The “chemistry-based” approaches focus on the local interactions between the species for which chemical identity is critical, and describe coacervation as the result of competitive local binding interactions of monomers and salts. In this article, we show how these approaches complement each other by presenting recent approaches that take both physical and chemical effects into account. Finally, we suggest future directions toward producing theories that are made quantitatively predictive by accounting for both long range electrostatic and local chemically specific interactions.     

Synthesis of Co3O4 @ Organo/Polymeric Bentonite Structures as Environmental Photocatalysts and Antibacterial Agents for Enhanced Removal of Methyl Parathion and Pathogenic Bacteria

Two green nanocomposites of Co₃O₄ decorated CTAB/bentonite (Co@CT/BE) and chitosan/bentonite (Co@CH/BE) were synthesized as enhanced and environmental photocatalysts and antibacterial agents. As photocatalysts, the products were applied in the effective oxidation of toxic methyl parathion pesticide (MP) in wastewater under a visible light source. The application of Co@CH/BE (0.02 g) resulted in the complete oxidation of MP (50 mg/L) after 40 min and complete mineralization after 60 min. while the complete oxidation and mineralization of MP (50 mg/L) by Co@CT/BE was recognized after 75 min and 100 min, respectively. The Co@CH/BE composite is of higher activity than Co@CT/BE and can cause complete oxidation for MP at high concentrations up to 100 mg/L after 75 min. The oxidation pathway was illustrated considering the existence of the hydroxyl radicals as the active oxidizing species and the identified secondary organic compounds during the oxidation tests. The detected intermediate converted into end products of CO₂ and inorganic anions of SO₄^?2, NO₃^?, and PO₄^?3 at the final stages of the oxidation processes. As antibacterial agents, the two composites exhibit considerable inhabitation zones of about 20 mm against both the Gram-positive Staphylococcus aureus and Gram-negative bacterium Vibrio Sp. The synthetic Co@CH/BE showed the best antibacterial properties with 200 μg/mL as minimum inhibitory against Staphylococcus aureus.

     

The effect of substrate surface integrity on the surface properties of TiCrN coating applied via the CAE-PVD method

This study aims to investigate how the predeposition machining processes such as magnetic grinding, turning machining, and wire electrical discharge machining can influence the surface properties including electrochemical and tribological behavior of TiCrN nanostructured coating applied on Mo40 steel substrate. A physical vapor deposition technique using cathodic arc evaporation was used to apply the coating. The crystallographic phases and the microstructure of the coating were studied by X-ray diffraction and scanning electron microscope, respectively. Rockwell-C, electrochemical impedance spectroscopy and potentiodynamic polarization, and pin-on-disk wear tests were employed to evaluate the adhesion strength, corrosion behavior, and tribological property of specimens, respectively. The electrochemical results after 24 h of exposure to 3.5 wt% NaCl solution showed that TiCrN coating pretreated with a turning process with polarization resistance of about 3525.32 Ω.cm² had the best corrosion resistance among all specimens. This was because of the improvement of the smoothness, surface quality, and adhesion after the turning process. On the other, the friction coefficient of the grounded sample is less than that of other ones. This is probably due to its higher adhesion strength and higher surface smoothness.     

Rolling element bearings absolute life prediction using modal analysis

In this paper, the authors introduce an experimental procedure for predicting the fatigue life of each individual rolling element bearing separately using vibration modal analysis. The experimental procedure was developed based on a statistical analysis. A statistical analysis was performed to find an empirical model that correlates the dynamic load capacity of rolling bearings to their dynamic characteristics (Natural frequencies and damping). These dynamic characteristics are obtained from the frequency response function of each individual bearing that results from vibration modal analysis. A modified formula to the already known Lundberg-Palmgren life formula is proposed for rolling element bearings. Given the modified formula, one can predict the fatigue life of each individual rolling element bearing based on its dynamic characteristics. The paper compares the results from the modified formula with those from Lundberg-Palmgren formula. The modified formula provides an accurate prediction for the fatigue life of each individual bearing based on its dynamic characteristics. The experimental validation of the modified formula is considered for future work. Therefore, it can be used in various applications of rolling element bearings in machinery systems.     

Some Studies on Starch Carbamate

Starch carbamate was prepared by reacting maize starch with urea using solid state technique. The different factors affecting this reaction were studied. These factors include urea concentration, type of starch, reaction and duration. The carbamate extent and carbamation reaction efficiency (%) were traced by estimating the nitrogen content of the reaction product. Solubility, viscosity and total ester content of starch carbamate samples were estimated. The carbamate extent increases by increasing urea concentration as well as reaction temperature and duration. Increasing the reaction temperature and duration has the same effect on carbamation reaction efficiency (%), while increasing urea concentration do the reverse. The solubility (%) of starch carbamate samples depends on urea concentration, reaction temperature and duration as well as the type of starch used. The maximum solubility obtained was 63% and 43% for starch carbamate derived from pregelled and native starch, respectively. Tentative mechanism for the reaction between starch and urea has been proposed.     

CFD simulation of transverse vibration effects on radial temperature profile and thermal entrance length in laminar flow

Radial heat transfer in laminar pipe flow is characterized by a wide temperature distribution over the pipe cross‐section. We use a validated Computational Fluid Dynamics (CFD) model to show that the superimposition of a transverse vibration on the steady laminar flow of a Newtonian fluid moving in a pipe with an isothermal wall, generates considerable chaotic flow and radial mixing which result in a large enhancement in wall heat transfer as well as a considerably more uniform radial temperature field. Transverse vibration also causes the temperature profile to develop very rapidly in the axial direction reducing the thermal entrance length by a large factor. These effects are dependent on vibration amplitude and frequency, and fluid viscosity. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

New kinetic models for the crystallization of anatase nanoparticles from amorphous titania (TiO2)

In this article, amorphous Titania (TiO₂) nanoparticles were crystallized both in a solution environment and by a dry heat treatment using new kinetic models with the capabilities of more accurately predicting the polymorphic transformation behavior of TiO₂. In these models, both the nucleation and growth processes were simultaneously taken into account. The results were indicative of the Surface Nucleation (SN) of anatase occurring in a hydrothermal treatment process through the phase transformation. Also, both the surface and interface nucleation processes were found to play significant roles in the phase transformation kinetics when dealing with dry heat treatments at low temperatures. The proposed models were advantageous to any other published models, in which the nucleation mechanisms had been incorporated with suitable growth expressions. In other words, no experimental data of a particle size were required to investigate the phase transformation kinetics of TiO₂ nanoparticles in the models presented in this article.     

Synthesis,Characterization and Catalytic Activities of Palladium(II) Nitroaryl Complexes

Two palladium(II) nitroaryl complexes trans-[bromo(p-nitrophenyl)bis(triphenylphosphine)palladium(II)] 1 and trans-[bromo(2,4-dinitrophenyl)bis(triphenylphosphine)palladium(II)] 2 have been synthesized. The complexes were characterized by FTIR and NMR (¹H, ¹³C and ³¹P) spectroscopy and elemental analysis. The molecular structure of complex 2, as confirmed by X-ray crystallography, reveals that the Pd atom and its neighboring groups (two PPh₃, Br and phenylene group) lie in a slightly distorted square plane. In the UV–Vis spectra of the complexes 1 and 2, the palladium to aryl charge transfer bands were observed. The emission peaks from the singlet excited states (S₁ → S₀) were observed in the photoluminescence spectra of the complexes. The thermal stability of the complexes has been studied by thermal gravimetric analysis (TGA). TGA data showed that both complexes are thermally stable up to 200 °C, and complex 1 is more stable than 2. The catalytic efficiency of the new palladium(II) complexes was studied as demonstrated using the Sonogashira coupling reactions with good yields. The experimental results suggest that the Sonogashira coupling reactions can be performed at moderate temperature (50 °C) using these new palladium(II) complexes as catalysts.     

Processing of High‐Density Magnesia Spinel Electro‐Conducting Ceramic Composite and its Oxidation at 1400°C

Dense conductive ceramic composites of MgAl₂O₄ and MoSi₂ were processed using combustion synthesis under‐load methodology. The starting reactants were blends of MoO₃, SiO₂, MgO, and Al powders. The study revealed that to obtain dense composite with homogeneous microstructure, 30 wt. % of MoSi₂, 18.5 μm Al average particle size, and 175 MPa load are required. The produced dense composite was found to have a low apparent porosity (<1.0 vol. %), moderate density 4.61 g/cm³, and low electrical resistivity 0.3 Ωcm. The dense composite exhibited excellent thermodynamic stability between its phases at 1400°C in open atmosphere.     

Correction to: Synthesis of Co3O4 @ Organo/Polymeric Bentonite Structures as Environmental Photocatalysts and Antibacterial Agents for Enhanced Removal of Methyl Parathion and Pathogenic Bacteria

Journal of Inorganic and Organometallic Polymers and Materials -