The final bleaching of eucalypt kraft pulps with hydrogen peroxide: relationship with industrial ECF bleaching history and cellulose degradation

BACKGROUND: The process of chemical pulp bleaching is based for the most part in chlorine dioxide within elemental chlorine free (ECF) technologies. The use of greener alternatives such as bleaching with hydrogen peroxide (P stage) is not widely used owing to selectivity concerns related to transition metal‐catalyzed decomposition reactions. Even at the final stage where peroxide is recognized to boost brightness and improve the brightness stability of the bleached pulp, cellulose degradation often overcomes these advantages. This paper presents the results of studies intended to optimize final peroxide bleaching performance considering two standard ECF industrial bleaching sequences: the conventional DED and the ECF‐light OQ(PO)D (stages name: D—chlorine dioxide; E—alkaline extraction; O—oxygen; Q—chelation, (PO)—hydrogen peroxide pressurized with oxygen). RESULTS: The addition of sodium diethylenetriaminepentaacetate (DTPA) was the most effective option in terms of DED pulp bleachability and selectivity with hydrogen peroxide, as well as in terms of brightness reversion. As regards the OQ(PO)D pulp, a blend of DTPA and magnesium was the most beneficial in those properties. CONCLUSIONS: The choice of the best hydrogen peroxide stabilizer, among the different tested combinations of magnesium and chelants (EDTA and DTPA) studied, in terms of pulp bleachability, bleaching selectivity and brightness reversion is dependent on the impact of the previous bleaching stages on metallic nature and content. The pulp Mg/(Fe + Cu) ratio was highlighted as a process parameter controlling cellulose degradation in peroxide bleaching. Copyright © 2010 Society of Chemical Industry     

Comparative study of homogeneous and heterogeneous styrene polymerizations with Ni(acac)2/MAO catalytic system

Styrene polymerization was carried out with Ni(acac)₂/MAO and Ni(acac)₂/SiO₂/MAO. The influence of reaction parameters (Al/Ni mole ratio, catalyst concentration, temperature and time polymerization) on styrene polymerization was evaluated. It was observed that both catalytic systems were affected by reaction parameters and that the heterogeneous catalyst presented higher activity than the homogeneous one. Polystyrenes with different molecular weight, stereoregularity and polydispersity were obtained. These results suggest that different active catalyst species could have been present. In addition, two types of methylaluminoxane (MAO) with different molecular weights were also evaluated as cocatalyst. As a result, the catalyst activity and stereospecificity were strongly affected by the MAO type.     

Physicochemical Study of Glycerol Hydrogenolysis Over a Ni–Cu/Al2O3 Catalyst Using Formic Acid as the Hydrogen Source

Glycerol hydrogenolysis to propanediols requires the use of hydrogen as reactant. One interesting option is to directly generate this hydrogen in active sites of the support using hydrogen donors, such as formic acid. The effect that the reacting pressure has on glycerol conversion and product selectivity over a Ni–Cu/Al₂O₃ catalyst was studied. The negative effect of decreasing the pressure was much more significant when the source of hydrogen was dissolved molecular hydrogen than when it was formic acid. X-ray photoelectron spectroscopy and temperature programmed reduction measurements were performed to understand the effect of Ni–Cu/Al₂O₃ reduction procedure on the catalytic activity. Semi-batch reactor studies with the Ni–Cu/Al₂O₃ catalyst were carried out with continuous addition of the hydrogen donor to obtain kinetic data. Langmuir–Hinshelwood type models were developed to describe the direct conversion of glycerol into propanediol, and propanediol further hydrogenolysis to 1-propanol. The model included the competitive adsorption between both glycols. These models were used to obtain valuable data for the optimization of the process.     

Degradation kinetics of epoxidized soybean oil composites filled with sisal fiber

Epoxidized soybean oil (ESO) composites were cured with methyl tetrahydrophthalic anhydride (MTHPA) and 2,4,6-tris(dimethylaminomethyl)phenol (DEH 35) as a catalyst, sisal fibers were added at 10% and 30% of percent per weight. Composites curing was monitored using Fourier transform infrared spectroscopy, whereas the thermal stability and the degradation kinetics were investigated using thermogravimetry (TG). ESO/MTHPA/DEH35/S10 and ESO/MTHPA/DEH35/S30 composites displayed curing temperatures approximately 100°C lower related to ESO/MTHPA/DEH35, as well as higher degree of conversion. Sisal addition improved the thermal stability, shifting the weight loss shifting the weight loss onset to higher temperature (from 82 to 120°C). Thermal degradation energy $$ was determined using Friedman, Kissinger-Akahira-Sunose and Ozawa-Flynn-Wall models. Sisal significantly increased $$, especially in the intermediate phase (α = 0.2 and 0.8). The degradation kinetics was investigated by TG, and the degradation mechanisms modeled using Kamal-Sourour, Sestack-Berggren, and 1st order (F1), showed excellent fit, with R² > 0.99. Acquired results demonstrate that sisal fiber addition benefited the curing process and increased the thermal stability of ESO composites.     

Novel copolymer for SiO2 nanoparticles dispersion

High performance polymers exhibiting multifunctional characteristics can be achieved by the introduction of inorganic nanoparticles like SiO₂ into the functional polymers. In the present work a copolymer epoxy poly(dimethylacrylamide) was synthesized to disperse the SiO₂ nanoparticles. The aim of the work is to develop a new method/process/material for the dispersion of nanoparticles and evaluating the performance of these composites. FT‐IR studies of the polymer adsorbed SiO₂ nanoparticles confirmed that the polymer molecules chain was anchored on the surface of the SiO₂ nanoparticles. The improved interfacial interaction between the particles and polymer enhanced the thermal properties of the composites. The results also show the newly synthesized polymer disperse the nanoparticles well as evidenced by SEM analysis, the uniformly dispersed SiO₂ nanoparticles in the polymer matrix and the particles almost remained in their original shape and size even after incorporation in to the polymer matrix. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Resistance variation of conductive ink applied by the screen printing technique on different substrates

This research study focuses on the application of conductive ink by the screen printing technique to evaluate the potential of creating printed electrodes and to investigate the effect of washing upon electrical resistance and flexibility. Two conductive inks were applied by a conventional screen printing method on four different textile substrates, 100% cotton, 50%/50% cotton/polyester, 100% polyester and 100% polyamide. The inks were also applied on a multifibre fabric. Atmospheric plasma treatment was applied to improve the adhesion to the samples, and the resistance values were compared with those of non‐treated samples. The values were measured before and after cleaning and washing tests, which were performed to simulate domestic treatment for garments to predict the behaviour of the inks after normal usage of the fabrics. Comfort properties like stiffness of the fabrics were also evaluated after five and 10 washing cycles. It was observed that PE 825 ink forms a thicker film on the fabric surface, contributing to the loss of flexibility of the textile. However, PE 825 ink also produced the best results in terms of durability and lower values of resistance. Polyamide fabrics lost their conductive property after five washing cycles due to weak bonding between the ink and the fibres, whereas cotton fibres provided the best results.     

Synthesis of Isopropyl Palmitate by Lipase Immobilized on a Magnetized Polymer Matrix

Penicillium camemberti lipase immobilized on a magnetized poly(styrene-co-divinylbenzene) was used as a biocatalyst for isopropyl palmitate synthesis. The reaction conditions were determined by 2² factorial central composite design. A mathematical model based on a simplified kinetic approach was developed to describe the system and validated with the experimental data. An assay carried out in a stirred-tank reactor confirmed the proposed model. The ester was purified and the properties such as density and water content were similar to those found in commercially available isopropyl palmitate.     

Kinetics of Soybean Oil Hydrolysis on Niobium Catalysts

The catalytic hydrolysis of soybean oil was used as an alternative for the production of monoglycerides (MG) and diglycerides (DG). The reactions were conducted in a stainless-steel tubular reactor in the temperature range of 240–290 °C, on niobium phosphate (NBP) and niobium oxide (NBO) as catalysts. In the hydrolysis reactions at 270 °C, the maximum selectivities of the products of interest were obtained at 22 % MG and 48 % DG for the reaction with NBP, and 7 % MG and 33 % DG with NBO, for 59 % and 36 % of triglyceride conversion in 10 min, respectively. The proposed kinetic model presented a good fit of the theoretical model with the experimental data, showing that the previous hypotheses considered for the mechanism development are suitable for describing the kinetics of soybean oil hydrolysis.     

Inhibition of the FGF/FGFR System Induces Apoptosis in Lung Cancer Cells via c-Myc Downregulation and Oxidative Stress

Lung cancer represents an extremely diffused neoplastic disorder with different histological/molecular features. Among the different lung tumors, non-small-cell lung cancer (NSCLC) is the most represented histotype, characterized by various molecular markers, including the expression/overexpression of the fibroblast growth factor receptor-1 (FGFR1). Thus, FGF/FGFR blockade by tyrosine kinase inhibitors (TKi) or FGF-ligand inhibitors may represent a promising therapeutic approach in lung cancers. In this study we demonstrate the potential therapeutic benefit of targeting the FGF/FGFR system in FGF-dependent lung tumor cells using FGF trapping (NSC12) or TKi (erdafitinib) approaches. The results show that inhibition of FGF/FGFR by NSC12 or erdafitinib induces apoptosis in FGF-dependent human squamous cell carcinoma NCI-H1581 and NCI-H520 cells. Induction of oxidative stress is the main mechanism responsible for the therapeutic/pro-apoptotic effect exerted by both NSC12 and erdafitinib, with apoptosis being abolished by antioxidant treatments. Finally, reduction of c-Myc protein levels appears to strictly determine the onset of oxidative stress and the therapeutic response to FGF/FGFR inhibition, indicating c-Myc as a key downstream effector of FGF/FGFR signaling in FGF-dependent lung cancers.