Experimental study and modelling of an azo colourant dynamic adsorption onto functional cross-linked chitosan/ceramic particles in a fixed bed column

The use of azo dyes in industrial activities generates a large volume of contaminated wastewater; these pollutants in water bodies affect aquatic biota and human health. A functional biocomposite sorbent material was synthesized using cross-linked chitosan with oxalic acid that forms a coating on alumina ceramic particles (AOCh). The removal of Reactive Red 195, a reactive azo dye, using a fixed-bed adsorption column filled with this material was tested. AOCh was physico-chemically characterized by Fourier transform infrared spectroscopy–total attenuated reflection (FTIR-ATR), scanning electron microscopy–energy dispersion spectrometry X-ray (SEM-EDS), X-ray diffraction (XDR), thermo-gravimetric analysis (TGA), and Z-potential. The dynamic adsorption performance was analyzed from experimental breakthrough curves obtained in fixed-bed columns by modifying different operating conditions (bed depth, volumetric flow rate, and dye inlet concentration). Equilibrium adsorption isotherms were determined under dynamic conditions and compared with batch results. The maximum adsorption capacity of the dynamic equilibrium isotherm obtained from the continuous assays was 331 mg/g; this value was the highest in comparison to other tested materials reported in the literature. Different dynamic adsorption models were applied to fit experimental data, including Thomas, Bohart–Admas, Yoon–Nelson, logistic general model, bed depth surface time (BDST), and modified dose response (Yan) models. A critical analysis of these equations was presented, showing the equivalences and the relationship among the coefficients. The Yan model achieved the highest level of agreement between the experimental and predicted values of the breakthrough curves. The use of this model enables scaling-up the industrial process for dye removal. The present work proposed a novel biosorbent material and contributes to the analysis of industrial dye removal under dynamic conditions.     

Refractive index and lattice parameter prediction for garnets (A3B2C3X12)

The validity of prediction methods for garnet lattice parameters was tested, and a modified model with best fit to a lattice parameter database with over 1000 garnet compositions was developed. The lattice parameter predictions were used in Shannon and Fischer's model to predict garnet refractive indices. The predictions were compared to refractive index measurements reported for 143 garnet compositions. After calibration of electron overlap factors used in the model, the average prediction error was 1.13%. Sources of error in the models are discussed, as well as applications of the predictive methods.     

Corrosion behavior of Monofrax K-3 refractory in borosilicate-based model low activity waste glass melts

Owing to its good chemical and thermal durabilities at high temperatures, Monofrax K-3 refractory is widely used in nuclear waste vitrification as a lining material in melting vessels. However, the corrosion of K-3 refractory during the vitrification of nuclear waste is a serious problem because it affects the melter's safety, performance, and lifetime. Therefore, in the present study, we have focused on unearthing the impact of glass network formers, such as SiO₂, B₂O₃, and Al₂O₃, in a model nuclear waste glass composition on the corrosion of Monofrax K-3 refractory. The corrosion tests have been performed per ASTM C621 at 1150°C for 5 days. The dimensional measurements on corroded K-3 refractory suggest that Al₂O₃ and SiO₂ tend to reduce the refractory corrosion (neck loss), with the effect of Al₂O₃ being significant. A corroded region on the K-3 refractory at the melt–refractory interface is observed. The corrosion occurs via a coupling of the melt infiltration induced by a capillary effect and the dissolution of Al, Mg, and Fe components from K-3 into the melt through chemical reactions. A Cr-rich layer is retained on the glass contact surface of the corroded K-3 refractory.     

Mixed modifier effect in Na2O·K2O·CaO aluminosilicate glasses: Pairwise and ternary interactions

The mixed modifier effect (MME) is one of the most challenging puzzles in the field of oxide glasses, as there exists no universal quantitative theoretical model for accurately describing and predicting the nonlinear deviation of property values. In this paper, pairwise and ternary interactions are examined experimentally to understand the MME in a series of aluminosilicate glasses. By keeping the glass network former concentration constant and adjusting the molar ratios of three network modifiers (Na₂O, K₂O, and CaO), the MMEs in glass transition temperature (T_g), Vickers hardness (H_v), and activation energy (E_a) for aqueous dissolution for each modifier cation are investigated. We examine whether a pairwise interaction model is sufficient, or if ternary interactions also need to be included to predict the MME in these aluminosilicate glass systems. This work reveals that the pairwise model can be used to predict the MME for T_g in complex multiple-modifier glass systems using only two-body interaction factors. However, ternary mixed-modifier interactions are present in other properties such as H_v and E_a.     

Interlaboratory study on lipid oxidation during accelerated storage trials with rapeseed and sunflower oil analyzed by conjugated dienes as primary oxidation products

Accelerated storage tests are frequently used to assess the oxidative stability of foods and related systems due to its reproducibility. Various methods and experimental conditions are used to measure lipid oxidation. Differences between laboratories make it necessary to determine the repeatability and reproducibility of oxidation tests performed under the same conditions. The objective of the present interlaboratory study was to evaluate the outcome of a storage test for two different bulk oils, sunflower oil (SFO) and rapeseed oil (RSO), during a period of 9 weeks at 20°C, 30°C, 40°C, and 60°C. Sixteen laboratories were provided with bottled oils and conducted the storage tests according to a detailed protocol. Lipid oxidation was monitored by the formation of conjugated dienes (CD) and the activation energy (E_a) was determined for comparative purposes and statistically evaluated. An increase in CD formation was observed for both oils when the storage temperature was increased in all laboratories. The E_a,1 ranged from 47.9 to 73.3 kJ mol⁻¹ in RSO and from 27.8 to 62.6 kJ mol⁻¹ in SFO, with average values of 58.2 and 46.8 kJ mol⁻¹, respectively. The reproducibility coefficients were 10.9% and 18.2% for RSO and SFO, respectively. Practical applications: In order to compare results on oxidative stability of foods derived from different studies, the reproducibility of storage tests and methods employed to evaluate the oxidation level should be considered. This study provides fundamental data on the reproducibility of lipid oxidation under accelerated storage conditions and defines important parameters to be considered for the conduction of experiments.     

New ultra high molecular weight acrylic processing aids for rigid PVC foaming

Foaming of rigid polyvinyl chloride (PVC) is studied as a function of high molecular weight acrylic processing aids. The industrial process to evaluate quality of foam is discussed in detail. The role of acrylic processing aids to improve melt strength and hence foaming of PVC is explained. It is demonstrated that increase in molecular weight of acrylic processing aids increases its effectiveness. It is found that ultra-high molecular weight processing aids is 25%–30% more efficient than relatively lower, but still high, molecular weight acrylic processing aids. The higher molecular weight processing aids provided comparable foaming performance at lower loading levels. Foaming reduced the density of PVC compounds to 0.32–0.34 g/cm³. More than 1000% expansion is achieved in the melt extrusion process using a chemical blowing agent. Fusion characteristics are also studied. Fusion times for initial fusion peaks are in the range of 42–44 s while the fusion times of the second fusion peaks are in the range of 74–94 s. The higher molecular weight processing aids maintained fusion characteristics of PVC compounds, warranting no significant changes in commercial process.     

Prediction of the Crevice Corrosion Incubation Period of Passive Metals at Elevated Temperatures: Part I — Mathematical Model

Previous researchers have numerically modelled the crevice corrosion of particular classes of metals and alloys. Applicable to passive metals immersed in an appropriate electrolyte, a new crevice corrosion model simulates the general passive crevice corrosion problem. Rapid approach of chemical equilibrium is assumed. Equilibrium constants and transport properties are adjusted for elevated temperature via the correspondence principle (Criss and Cobble, 1964) and the Nernst‐Einstein equation, respectively. The corrosion rate is adjusted for thermal and acidity effects via an Arrhenius expression and a Freundlich isotherm, respectively. Presented in a sequel publication, the predictions compare favourably with experimental results.     

Formation of hydrophilic starch coatings on polyethylene films

Thin starch coatings were deposited onto polyethylene (PE) film surfaces when PE films were immersed in 1% jet cooked starch solutions and the hot solutions were allowed to cool. Normal cornstarch, waxy cornstarch, high amylose cornstarch, and solvent‐extracted normal cornstarch (to remove native lipid) were used in these experiments. Amounts of adsorbed starch varied from about 0.03–0.05 mg per cm² of PE, and these starch coatings imparted hydrophilic properties to film surfaces, as evidenced by contact angle measurements. Although starch could be removed by gently rubbing water‐wet PE surfaces, air‐dried coatings were more firmly attached, and did not separate from the PE surface when films were bent or flexed. SEM images of starch‐coated film surfaces showed that starch was deposited as particles less than 1 μm in diameter, and also as aggregates of these submicron particles. Despite the fact that some starch samples contained only very small amounts of amylose and native lipid, surface‐deposited starch in all experiments contained 90–100% amylose; and exhibited the same V_h X‐ray diffraction pattern, indicative of helical inclusion complex formation. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1781–1788, 2002; DOI 10.1002/app.10589     

Preparation and characterisation of a poly(acrylamidoglycolic acid-co-acrylamide) hydrogel for selective binding of Cu and application to diffusive gradients in thin films measurements

A poly(acrylamidoglycolic acid-co-acrylamide) [poly(AAGA-co-AAm)] hydrogel was prepared by copolymerising 2-acrylamidoglycolic acid (AAGA) with acrylamide (AAm). The copolymer hydrogel composition and structure was characterised by FTIR spectroscopy and elemental microanalysis and found to contain 3.5 AAGA monomer units for each AAm monomer unit. This was similar to the monomer ratios used in the synthesis. The metal ion binding properties of the hydrogel were characterised for a range of metal ions (Cu²⁺, Cd²⁺, K⁺, Na⁺, Mg²⁺ and Ca²⁺) under varying conditions of pH, ionic strength, metal concentration and time. The hydrogel was shown to bind Cu²⁺ and Cd²⁺ strongly under non-competitive binding conditions, with binding capacities of 5.3 and 5.1 μmol cm⁻², respectively. The binding capacity of each metal decreased, under competitive binding conditions (with a range of metal ions present at 17.8 μN), to 1.3 and 0.17 μmol cm⁻², respectively, indicating stronger selectivity for Cu²⁺. The metal ions were readily recovered (>94%) by eluting with 2 M nitric acid solution for 24 h. The binding capacities for Cu²⁺ and Cd²⁺ were also found to decrease with increasing ionic strength and at pH values <5. The copolymer was found to have an equilibrium swelling ratio (q_w) of over 500 at a maxima of pH 5.4 and at low ionic strengths. Finally, the copolymer hydrogel was tested as a binding phase with the diffusive gradients in thin films technique. A linear mass vs. time relationship was observed for Cu²⁺ in synthetic Windermere water with a recovery of approximately 100%.     

Chemical doping of single-wall carbon nanotubes

Single-wall carbon nanotubes can be doped, or intercalated, with electron donors or acceptors, similar to graphite and some conjugated polymers. The resulting materials show many of the same features: enhanced electrical conductivity, conduction electron paramagnetism, partial or complete reversibility, and cyclability. Reactions may be carried out in vapor or liquid phase, or electrochemically. Structural information is sketchy at best, due to the limited quality of currently available materials and solvent-related effects. Recent developments in coagulation-based fiber extrusion and partially aligned materials offer new opportunities for novel material modifications by chemical doping.