ALKYD PAINT WASTE CHARACTERIZATION AND DISTILLATION

In the present study the characterization and distillation of alkyd paint waste have been carried out in order to establish the technical viability of organic solvents recovery and to decide upon the best environmental management for the waste stream from a paint spray-booth application in an automotive component factory. The paint is a black primer based on an alkyd resin with toluene and xylene as solvents, black carbon as pigment, fillers, and other minor components.

The paint, paint wastes, and distillation wastes have been characterized by determination of the physicochemical properties of the solid (solvents content and flash point) and determination of ecotoxicity (EC₅₀), total organic carbon (TOC), and metals concentration of the leachates. The highly volatile matter (HVM) content, determined by the weight loss at 200°C, has been used as a parameter to relate with the hazardous wastes regulations based on the characterization parameters EC₅₀, TOC, and flash point.

Distillation experiments have been performed in a simple batch mode with mixtures of paint waste, water, and additives in order to obtain high efficiencies in the recovery of volatile organic compounds and to obtain a final solid with nonhazardous behavior and good manageability qualities. A fractional factorial design (2^3-1) of experiments was carried out in order to study the influence of the distillation variables: water/paint waste ratio (2/1-3/1 (g/g)), temperature (110°-145°C), alkaline additives (Na(OH),CaO, Ca(OH)₂), and amount of other additives (wt.% of bentonite, cement, and Ca(OH)₂) on the solvent recovery, [% VOCs]_Recovery, on the residual volatile organic compounds, [% VOCs]_{Distillation Waste}, and on the total organic content (TOC) of the waste leachates. The present work shows the quantitative results of the alkyd paint waste distillation process under optimum conditions.     

Isomerization of n-hexane over mono- and bimetallic Pd–Pt catalysts supported on ZrO2–Al2O3–WOx prepared by sol–gel

The catalytic performance of mono- and bimetallic Pd (0.6, 1.0 wt.%)–Pt (0.3 wt.%) catalysts supported on ZrO₂ (70, 85 wt.%)–Al₂O₃ (15, 0 wt.%)–WO_x (15 wt.%) prepared by sol–gel was studied in the hydroisomerization of n-hexane. The catalysts were characterized by N₂ physisorption, XRD, TPR, XPS, Raman, NMR, and FT-IR of adsorbed pyridine. The preparation of ZrW and ZrAlW mixed oxides by sol–gel favored the high dispersion of WO_x and the stabilization of zirconia in the tetragonal phase. The Al incorporation avoided the formation of monoclinic-WO₃ bulk phase. The catalysts increased their S_BET for about 15% promoted by Al₂O₃ addition. Various oxidation states of WO_x species coexist on the surface of the catalysts after calcination. The structure of the highly dispersed surface WO_x species is constituted mainly of isolated monotungstate and two-dimensional mono-oxotungstate species in tetrahedral coordination. The activity of Pd/ZrW catalysts in the hydroisomerization of n-hexane is promoted both with the addition of Al to the ZrW mixed oxide and the addition of Pt to Pd/ZrAlW catalysts. The improvement in the activity of Pd/ZrAlW catalysts is ascribed to a moderated acid strength and acidity, which can be correlated to the coexistence of W⁶⁺ and reduced-state WO_x species (either W⁴⁺ or W⁰). The addition of Pt to the Pd/ZrAlW catalyst does not modify significantly its acidic character. Selectivity results showed that the catalyst produced 2MP, 3MP and the high octane 2,3-dimethylbutane (2,3-DMB) and 2,2-dimethylbutane (2,2-DMB) isomers.     

Composition effects of thermal barrier coating ceramics on their interaction with molten Ca–Mg–Al–silicate (CMAS) glass

Systematic studies have been performed to investigate the composition effects of ZrO₂-based thermal barrier coating (TBC) ceramics on their interactions with molten Ca–Mg–Al–silicate (CMAS) glass. Porous ceramic pellets (～15% porosity), instead of actual TBCs, are used in these model studies, where the penetration of molten CMAS into the pellets is investigated. This study involves a total of six compositions of ZrO₂-based ceramics: two containing low solute (Y³⁺ or Gd³⁺) concentration, three with high concentration of solute (Y³⁺, Gd³⁺ or Yb³⁺), and one containing a combined intermediate concentration of Y³⁺+Al³⁺+Ti⁴⁺ solutes. While both the type of the solute and its concentration in the ZrO₂-based TBC ceramics have been found to influence the extent of molten CMAS penetration into the pellets, the solute concentration has the most dramatic effect. In particular, molten CMAS penetration is almost completely suppressed in porous TBC ceramic pellets containing a high concentration of Y³⁺ solute (Y₂Zr₂O₇). Possible mechanisms governing these effects are presented, together with a discussion of guidelines for the chemical design of CMAS-resistant zirconate TBC ceramics. Generally, for a TBC ceramic to be highly effective against CMAS attack it must interact vigorously with the molten CMAS, which must result in the rapid crystallization of the refractory oxide phase(s) that form a sealing layer, arresting further penetration of the molten CMAS. The porous ceramic pellets approach used here could be developed into rapid-screening methodologies for the discovery of CMAS-resistant TBC ceramic compositions, and to study the effect of composition of CMAS glasses on their interactions with TBC ceramics of specific compositions.     

Melt extrusion and blow molding parts-per-million POSS interspersed the macromolecular network and simultaneously enhanced thermomechanical and barrier properties of polyolefin films

There has been the expectation that polymers filled with small concentrations of nanosized particles will exhibit superior thermomechanical properties. We demonstrate that dispersing parts-per-million (ppm) polyhedral oligomeric silsesquioxane (POSS) nanochemicals by melt extrusion with polyolefins increased the tensile Young's modulus, yield stress, and toughness of blow molded and extruded films without penalizing extensibility, which is common to polymers reinforced with nano/microparticles. Transmission electron microscopy showed that the key to mechanical reinforcement is the spatial distribution of POSS at ca. single nanocage thus enabling interspersion of the macromolecular network. The thermal stability, water contact angle, and oxygen transmission of the films were also enhanced enabling a single component food package capable to keep food without decay for two weeks. The physical properties are improved when the nanoparticle size <D> is about the size of the virtual tube diameter d_t, that is, <D>/d_t ≈ 1. The enhancement of physical properties by placing the nanoparticle in the free space of the molecular network is a new paradigm in engineering polymer nanocomposites and opens opportunities for recyclable single component packaging films and tunable lightweight engineering and biomimetic materials.     

Influence of the dispersion of Nanoclays on the cellular structure of foams based on polystyrene

In the present work blends of polystyrene (PS) with sepiolites have been produced using a melt extrusion process. The dispersion degree of the sepiolites in the PS has been analyzed by dynamic shear rheology and X-ray micro-computed tomography. Sepiolites treated with quaternary ammonium salts (O-QASEP) are better dispersed in the PS matrix than natural sepiolites (N-SEP) or sepiolites organo-modified with silane groups (O-SGSEP). A percolated network is obtained when using 6.0 wt% of O-QASEP, 8.0 wt% of N-SEP and 10.0 wt% of O-SGSEP. It has been shown that multiple extrusion processes have a negative effect on the polymer architecture. They produce a reduction in the length of the polymeric chains, and they do not lead to a better dispersion of the particles in the polymer matrix. Foams have been produced using a gas dissolution foaming process, where a strong effect of the dispersion degree on the cellular structure of the different foams was found. The effects on the cellular structure obtained by using different types of sepiolites, different contents of sepiolites and different extrusion conditions have been analyzed. The foams produced with the formulations containing O-QASEP present the lowest cell size and the most homogeneous cellular structures.     

Self-feed device behaviour evaluation designed for assessment of operability of coated electrodes

The objective of the present work is to evaluate the effectiveness of a self-feed device for coated electrodes. This device is able to eliminate disturbances from manual operation or the use of automatic control systems during the study of coated electrode behaviour. The conjugation of different methods such as short-circuit time statistical analysis and metallographic analysis (penetration, heat-affected zone, shape and mean distance between successive solidification fronts) together with the analysis of the electric arc and electrode melting parameters allows us to obtain relationships between arc behaviour, mass transfer processes and bead appearance. This permits the extraction of criteria to describe process stability and the behaviour of the feed device employed. An appropriate statistical methodology was obtained to process the ‘duration of the short-circuit’ parameter through an appropriate adjustment of empirical distributions to a log-normal model. The self-feed device for coated electrode welding allows the repeatable and reproducible execution of welding beads in the flat position, keeping the arc length based on physical and chemical characteristics of the electrode during welding trials using 125, 140 and 160 A.     

Aetiology and Pathogenesis of Cutaneous Melanoma: Current Concepts and Advances

Melanoma develops from malignant transformations of the pigment-producing melanocytes. If located in the basal layer of the skin epidermis, melanoma is referred to as cutaneous, which is more frequent. However, as melanocytes are be found in the eyes, ears, gastrointestinal tract, genitalia, urinary system, and meninges, cases of mucosal melanoma or other types (e.g., ocular) may occur. The incidence and morbidity of cutaneous melanoma (cM) are constantly increasing worldwide. Australia and New Zealand are world leaders in this regard with a morbidity rate of 54/100,000 and a mortality rate of 5.6/100,000 for 2015. The aim of this review is to consolidate and present the data related to the aetiology and pathogenesis of cutaneous melanoma, thus rendering them easier to understand. In this article we will discuss these problems and the possible impacts on treatment for this disease.     

Microstructural development during crystallization firing of a dental-grade nanostructured lithia-zirconia glass-ceramic

The microstructural development during crystallization firing of a commercially-available dental-grade nanostructured lithia-zirconia glass-ceramic (Vita Suprinity® PC) was unraveled using a wide battery of ex-situ and in-situ characterization techniques. It was found that the milling blocks are slightly crystallized glass-ceramics, with a complex chemical composition and consisting of partially de-polymerized glass plus lithium silicate (Li₂SiO₃) nanocrystals. It was also found that during crystallization firing the glassy matrix first reacts with part of the Li₂SiO₃ to form lithium disilicate (Li₂Si₂O₅) at ～810?820 °C, and then lithium orthophosphate (Li₃PO₄) precipitates from the glass. This results in glass-ceramics with abundant nanocrystals embedded in a sparse zirconosilicate glass matrix (containing many other cations subsumed) that, due to its high viscosity, inhibited crystal growth. Therefore, these dental glass-ceramics are not reinforced with zirconia (ZrO₂) crystals unless over-fired above ～890 °C and at the expense of its singular nanostructure. Finally, this study opens doors for optimizing the clinical performance of these dental glass-ceramics via microstructural tailoring.     

Hot corrosion behaviour of 7YSZ + Gd2O3 nano-composites in molten salts prepared by spark plasma sintering

This study compares the hot corrosion performance of yttria-stabilised zirconia (7YSZ), and 7YSZ?+?Gd₂O₃ composite samples in the presence of molten mixture of Na₂SO₄?+?V₂O₅ at 1150°C. For 7YSZ, the reaction between NaVO₃ and Y₂O₃ produces YVO₄ and leads the transformation of tetragonal ZrO₂ to monoclinic ZrO₂. A high-density in sintered 7YSZ?+?Gd₂O₃ samples, led minor amounts of monoclinic ZrO₂ and tetragonal GdVO₄ as the hot corrosion products with only traceable amounts of YVO₄, and a stable corroded layer was formed. Due to the synergic effect of doping of zirconia with Gd₂O₃, the 7YSZ?+?Gd₂O₃ sample has a much better hot corrosion crack resistance than 7YSZ.