Thermal decomposition behavior of γ‐irradiated poly(vinyl acetate)/poly(methyl methacrylate) miscible blends

Miscible polymer blends based on various ratios of poly(vinyl acetate) (PVAc) and poly(methyl methacrylate) (PMMA) were prepared in film form by the solution casting technique using benzene as a common solvent. The thermal decomposition behavior of these blends and their individual homopolymers before and after γ‐irradiation at various doses (50–250 kGy) was investigated. The thermogravimetric analysis technique was utilized to determine the temperatures at which the maximum value of the rate of reaction (T_max) occurs and the kinetic parameters of the thermal decomposition. The rate of reaction curves of the individual homopolymers or their blends before or after γ‐ irradiation displayed similar trends in which the T_max corresponding to all polymers was found to exist in the same position but with different values. These findings and the visual observations of the blend solutions and the transparency of the films gave support to the complete miscibility of these blends. Three transitions were observed along the reaction rate versus temperature curves; the first was around 100–200°C with no defined T_max, which may arise from the evaporation of the solvent. The second T_max was in the 340–380°C range, which depended on the polymer blend and the γ‐irradiation condition. A third transition was seen in the rate of reaction curves only for pure PVAc and its blends with PMMA with ratios up to 50%, regardless of γ‐ irradiation. We concluded that γ‐irradiation improved the thermal stability of PVAc/PMMA blends, even though the PMMA polymer was degradable by γ irradiation. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1773–1780, 2006     

Electrosynthèse des ions peroxodiphosphate sous potentiel constant ou pulsé

Electrosynthesis of peroxodiphosphate ions (P2O84–) was performed in 2m K3PO4, 1m K2HPO4 medium, using a platinum anode. The results showed that under conditions of potentiostatic polarization at constant potential, the reaction rate reaches a maximum value of 125mAcm–2 and a faradaic yield of 30%. From about 1.9V, the reaction kinetics are increasingly inhibited as the potential shifts positively. Rapid scanning potential voltammetry was used to characterize the oxidation state of the electrode surface. This method shows that the growth of (PtO) and (PtO2 or PtO3) oxides depend on the applied potential. It also establishes a correlation between the inhibition of P2O84– ion electrosynthesis and the oxide coating surface. When 2×10–3m KSCN is added to the solution, some oxygen evolution sites are selectively blocked and oxide occurs at more positive potential values. Consequently, the rate of peroxodiphosphate ion formation and the faradaic efficiency are increased to 380mAcm–2 and 75%, respectively. Under pulsed potential conditions it was possible to reach 1200mAcm–2 for P2O84– ion electrosynthesis with a faradaic yield of 82%.     

Study of Hydrodynamics,Mixing and Gas‐Liquid Mass Transfer in a Split‐Rectangular Airlift Reactor

Global hydrodynamic characteristics, liquid mixing and gas‐liquid mass transfer for a 63 L split‐rectangular airlift reactor were studied. Correlations for gas holdup and overall liquid circulation velocity were derived for the air‐water system as a function of the specific power input; these were compared to data and correlations for reactor volumes between 4.7 L and 4600 L. A partial recirculation of small bubbles in the riser was observed when U_gr > 0.03 m/s, which was attributed to the use of a single‐orifice nozzle as the gas phase distributor. The dimensionless mixing time and the overall axial dispersion coefficient were nearly constant for the range of gas flow rates studied. However, values of K_L/d_B were greater than those reported in previous studies and this is caused by the partial recirculation of the gas phase in the riser. While scale effects remain slight, the use of a gas distributor favouring this partial recirculation seems adequate for mass transfer in split‐rectangular airlift reactors.     

Modification of leather properties by grafting. I. Effect of monomer chain on the physico‐mechanical properties of grafted leather

Although leather has a number of desirable properties such as thermal stability and fire retardancey, in addition to high toughness, it has a few drawbacks such as weight, high water absorption, poor soil and rot resistance, and nonuniformity. If these defects are overcome, leather's usefulness would be further enhanced and its competitive position with respect to synthetics would increase. This study reports the physical and mechanical properties of buffalo leather after chemical graft copolymerization with ethyl acrylate, butyl acrylate, and 2‐ethyl hexyl acrylate using benzoyl peroxide as an initiator. The optimum conditions for grafting (e.g., monomer and initiator concentrations, temperature and time of grafting, and solvent leather ratio) were extensively investigated. The study achieved outstanding properties for buffalo leather in reduction of water uptake after grafting, especially on using 2‐ethyl hexyl acrylate and butyl acrylate monomers. FT‐IR and solid ¹³C‐NMR for leather before and after grafting confirmed the grafting process.© 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1478–1483, 2003     

Functional properties of a protein product from Caryodendron orinocense (Barinas nut)

The functional properties of Caryodendron orinocense protein product were investigated and compared with those of soybean (Glycina maxima). The product protein content was 24.47 g/100 g (Nx6.25). Solubility increased at both sides of the isoelectric point (pH 4.0) and with increased NaCl concentration up to 0.5M. Compared with soybean flour (50% protein), the protein product exhibited higher water and oil absorption, but lower emulsifying activity, emulsion stability, foaming capacity, and foam stability, the last one increase at higher pH. Emulsifying activity, foaming capacity, and foam stability were ionic strength dependent. C. orinocense protein product increased its emulsifying activity steadily from 0.05M to 0.75M NaCl, while it remained almost constant for soybean flour. Foaming capacity increased drastically at pH 10. The minimum time and concentration to form a gel was 20% in 4 min and 10% in 8 min for the Caryodendron protein product and soybean flour, respectively. The bulk density was 0.5056+/-0.0041 g/mL.     

Grafting poly(t‐butyl acrylate) to poly(allylamine) by inverse microemulsion radical polymerization: From comb‐polymer to amphiphilic shell crosslinked polymer nanocapsule

An interfacial grafting radical polymerization method for amphiphilic comb copolymer and shell crosslinked polymer nanocapsules was reported. Macropolyradicals on a water soluble long chain polyamine were generated with hydrogen peroxide in the water phase and subsequent grafting radical polymerization of a vinylic monomer at the water/oil interface proceeded at 65°C. In the presence of a crosslinker, the resulting graft copolymer formed a defined core‐shell structure with hydrophilic aqueous core functionalized by the polyamine and a hydrophobic crosslinked polymer shell. The structure of the core‐shell material was characterized by NMR, FTIR, DSC, TGA, SEM, TEM, and the mechanism of the graft polymerization is proposed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1905–1911, 2007     

Inhibition effect of some polymers on the corrosion of cadmium in a hydrochloric acid solution

The effects of poly(vinyl alcohol) (PVA), poly(acrylic acid) (PAA), sodium polyacrylate (NaPA), poly(ethylene glycol) (PEG), pectin (P), and carboxymethyl cellulose (CMC) on the corrosion of cadmium in a 0.5M hydrochloric acid (HCl) solution were studied with both electrochemical impedance spectroscopy and Tafel plot techniques. Measurements were carried out at cathodic, open‐circuit, and anodic potentials. All the investigated polymers had inhibitory effects on both the cathodic (except for NaPA, P, and CMC) and anodic processes, with a predominant anodic inhibiting action. However, NaPA, P, and CMC exhibited a slight cathodic inhibiting action only at higher polymer concentrations. This behavior may be attributed to the very weak adsorbability of the polymers on the cathodic sites. Because PVA and PEG had hydroxy groups, there could be bridging between the polymer and the surface, resulting in an inhibiting effect in the HCl solution. However, PVA had much greater adsorbability on the surface than PEG at the anodic potential. The adsorption of most of the polymers obeyed a Temkin adsorption isotherm, and this indicated indicating that the main process of inhibition was adsorption. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 866–871, 2003     

Lignin‐based polycondensation resins for wood adhesives

Lignin‐based wood adhesives are obtained that satisfy the requirements of relevant international standards for the manufacture of exterior‐grade wood particleboard. Formulations based on low molecular mass lignin and presenting an increase in the relative proportion of reactive points yield better results than the higher molecular mass lignin used in the past. These lignins allow a higher proportion of hydroxymethylation during preparation of methylolated lignins. These lignin‐based adhesives also yield acceptable results at particleboard pressing times that are sufficiently low to be of industrial significance. Lignin‐based wood adhesives, in which a nonvolatile nontoxic aldehyde (glyoxal) is substituted for formaldehyde in their preparation, are prepared and tested for application to wood panels such as particleboard. The adhesives yield good internal bond strength results for the panels, which are good enough to comfortably pass relevant international standard specifications for exterior‐grade panels. The adhesives also show sufficient reactivity to yield panels in press times comparable to that of formaldehyde‐based commercial adhesives. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1690–1699, 2007     

In vitro effects of urease inhibitors on rate of urea hydrolysis in soils

We studied the effect of urease inhibitors on the urea hydrolysis in some Sundanese soils belonging to the orders of Vertisol and Entisol. The hydrolysis showed a lag period of about 3 days and its rate (Y) per unit time (t) could be described by a two constants exponential equation of the general form Y = K₁t^K ₂. Statistical analysis showed that the intercept K₁ (rate of urea hydrolysis) was significantly affected by soil type rather than treatment. It seems that K₁ is associated with the soils' initial urease activity as it closely correlates with the Michaelis constant (km).The gradient, K₂, being significantly affected by soil type as well as treatment is probably associated with the induced urease activity with time and it, therefore, varied with variations in soils and treatments. Of the so-called urease inhibitors used in this study Ca(OH)₂, p-benzoquinone (PBQ) and orthophosphoric acid (OP) only PBQ reduced urea hydrolysis while the other chemicals have effects possibly related to modifying the soil pH. Inhibitor treated soils had substantial amounts of unacounted for N which was believed to be present, presumably, in the form of carbamate.Contribution from the Department of Biochemistry and Soil Science, Faculty of Agriculture, Shambat, Sudan.     

Modification of sandy soil using water‐borne polymer

A new polymeric system has been applied for structural modification of (noncompactable) sandy soils. The system is based on a water‐borne styrene acrylic polymeric formulation (emulsion) containing varying amounts of solid polymer. The present work deals with system optimization and measurements designed to examine the effects of polymer content on hydraulic conductivity and compressive strength. Samples were prepared from prescribed amounts of polymer, water, and sand by using two different preparations methods (mixing and spraying). Measurements of hydraulic conductivity for both sets of samples were conducted in a flexible membrane test apparatus. For the first set of samples, the permeability coefficient of the sand was noted to be reduced 10‐fold (from 10^?5 to 10^?6 m s^?1) upon the incorporation of about 2% polymer. In the second set (samples prepared with the spraying method), the hydraulic conductivity was further reduced to 7.2 × 10^?7 at a polymer concentration of about 2%. Stress–strain measurements made on dry cylindrical specimens disclosed remarkable enhancement in the mechanical behavior of the system. For both types of preparation methods, the compressive strength and modulus of elasticity increased linearly with the polymer concentration in the sample. Scanning electron microscopic examination revealed that the dramatic reduction in the permeability and the improved mechanical properties are attributed to the polymer coverage of the sand particles and the development of interconnecting ties between them. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2484–2491, 2003