Efficient transport and selective extraction of Cr(VI) from waste pickling solution of the stainless steel-cold rolled plate process using Aliquat 336 via HFSLM

The selective extraction of Cr(VI) from waste pickling solution of the stainless steel-cold rolled plate process by hydrophobic hollow fiber supported liquid membrane (HFSLM) was investigated. The effects of various parameters— types of organic extractants, i.e., metyl trioctylammonium chloride (Aliquat 336), tri-n-octylamine (TOA), tri-n-butyl phosphate (TBP) and the mixture of Aliquat 336 and TBP, concentration of the selected extractant, types of stripping solutions (NaCl and NaOH), pH and concentration of the selected stripping solution, and the operating temperature—were studied. The feed and stripping solutions flowed countercurrently. The results showed that the coexisting contamination in spent pickling solution of Fe(II) and Ni(II) ions had no significant effect on Cr(VI) extraction. Among the extractants used in this study, Aliquat 336 was a specific carrier to attain the highest percentage of Cr(VI) extraction. About 70% extraction was achieved by using 0.11 M Aliquat 336 and 0.5 M NaCl at pH 7. The percentage of stripping slightly increased when the concentration of NaCl increased. In addition, it was found that the operating temperature of 20, 30, 40, and 50 °C had almost no influence on the percentages of extraction and stripping of Cr(VI). The calculated diffusion energy of Cr(VI) extraction was 15.14 kJ/mol.     

Half metallic ferroamgnetism,and transport properties of vacancy ordered double perovskites Rb2(Os/Ir)X6 (X = Cl,Br) for spintronic applications

The defected double perovskites, being non-toxic, stable, and capable to exhibit both spin-up (↑) and spin-down (↓) polarizations, are attractive for spintronic devices. In the present article, the role of 5d-electrons of Os and Ir to control the magnetic characteristics of Rb₂(Os/Ir)Cl/Br₆ is addressed. The structural and magnetic characteristics are investigated using PBEsol-mBJ functional, while thermoelectric behaviors are studied using BoltzTrap code. The computed tolerance factors (0.95/0.98, 0.94/0.96) and formation energies (?2.0/-1.65eV, ?1.70/-1.10eV) confirm the structural and thermodynamic stabilities, respectively. The examination of band structures and density of states have revealed half-metallic ferromagnetic nature, which is further discussed in terms of double exchange model, exchange constants and exchange energies. The presented calculations indicate that underlying hybridization process, exchange energy, and crystal field energy induce ferromagnetism due to electron spin. Furthermore, thermal, and electrical conductivities, power factor, and Seebeck coefficients are computed and discussed to understand the thermoelectric applications.     

Preparation and characterization of partially substituted LiMyMn2−yO4 (M=Ni, Co, Fe) spinel cathodes for Li-ion batteries

The electrochemical and thermal behaviors of the spinels-LiMn₂O₄, LiCo_1/6Mn_11/6O₄, LiFe_1/6Mn_11/6O₄, and LiNi_1/6Mn_11/6O₄ were studied using electrochemical and thermochemical techniques. The electrochemical techniques included cyclic voltammetry, charge-discharge cycling of 2016 coin cells and diffusion coefficient measurements using Galvanostatic Intermittent Titration Technique. Better capacity retention was observed for the substituted spinels (0.11% loss per cycle for LiCo_1/6Mn_11/6O₄; 0.3% loss per cycle for LiFe_1/6Mn_11/6O₄; and 0.2% loss per cycle for LiNi_1/6Mn_11/6O₄) than for the lithium manganese dioxide spinel (1.6% loss per cycle for first ten cycles, 0.9% loss per cycle for 33 cycles) during 33 cycles. The Differential Scanning Calorimetry results showed that the cobalt substituted spinel has better thermal stability than the lithium manganese oxide and other substituted spinels.     

Design of a new yttrium silicate Environmental Barrier Coating (EBC) based on the relationship between microstructure,transport properties and protection efficiency

Yttrium mono- and di-silicates are excellent candidate materials for Environmental Barrier Coatings (EBC), to protect Ceramic-Matrix Composites (CMC). A large distribution of microstructures can be generated by varying the duration of sintering, the particle size distribution of the precursor and/or the deposition method. In the present work, investigations of the corrosion resistance of yttrium silicate coatings with various microstructures in the high temperature range, under different oxidizing environments are reported. An original experimental methodology has allowed quantifying the influence of the microstructure (especially grain size and grain boundary surface area) on properties such as ionic conductivity, resistance to oxygen diffusion, volatilization rate and surface recession, and showing that they directly affect their protection efficiency against oxidation. Based on these results, guidelines for the design of an optimized yttrium silicate EBC featuring microstructural and compositional variations are proposed.     

Mass transport process for the adsorption of Cr(VI) onto water‐insoluble cationic starch synthetic polymers in aqueous systems

Dynamic adsorption behaviors between Cr(VI) ion and water‐insoluble amphoteric starches was investigated. It was found that the HCrO ion predominates over the initial pH ∼ 2–4, the CrO ion predominates over the initial pH ∼ 10–12, and both ions coexist over the initial pH ∼ 6–8. The sorption process occurs in two stages: the external mass transport process occurs in the early stage and the intraparticle diffusion process occurs in the long‐term stage. The diffusion coefficient of the early stage (D₁) is larger than that of the long‐term stage (D₂) for the initial pH 4 and pH 10. The diffusion rate of HCrO ion is faster than that of CrO ion for both processes. The D₁ and D₂ values are ∼ 1.38 × 10⁻⁷–10.1 × 10⁻⁷ and ∼ 0.41 × 10⁻⁷–1.60 × 10⁻⁷ cm² s⁻¹, respectively. The ion diffusion rate in both processes is concentration dependent and decreases with increasing initial concentration. The diffusion rate of HCrO ion is more concentration dependent than that of CrO ion for the external mass transport process. In the intraparticle diffusion process, the concentration dependence of the diffusion rate of HCrO and CrO ions is about the same. The external mass transport and intraparticle diffusion processes are endothermic and exothermic, respectively, for the initial pH 4 and pH 10. The k_d values of the external mass transport and intraparticle diffusion processes are ∼ 15.20–30.45 and ∼ −3.53 to −12.67 kJ mol⁻¹, respectively. The diffusion rate of HCrO ion is more temperature dependent than that of CrO ion for both processes. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2409–2418, 1999     

A novel technique based on the ratio of potentio-charge capacity to galvano-charge capacity (RPG) for determination of the diffusion coefficient of intercalary species within insertion-host materials: theories and experiments

The diffusion process of intercalary species within insertion-host materials is the key step during the whole electrode reaction. Here a novel method based on the ratio (q) of the potentio-charge capacity to the galvano-charge capacity (RPG) was developed to determine the diffusion coefficient of intercalary species for porous electrode by the spherical diffusion model. By the RPG method, the Li⁺ diffusion coefficients within graphite were determined from the galvano-potentio-charge curves. The values of diffusion coefficient measured at different galvano-charge current or at different cutoff voltage suggested that the RPG method has a good reliability for determination of the diffusion coefficient.     

Comments of the paper ‘Capacity intermittent titration technique (CITT). A novel technique for determination of Li solid diffusion coefficient of LiMn2O4’ [X.-C. Tang, X.-W. Song, P.-Z. Shen, D.-Z. Jia, Electrochim. Acta 50 (2005) 5581-5587]

The article by Tang et al., which was published recently [Electrochim. Acta, Electrochim. Acta 50 (2005) 5581-5587], proposed a novel technique for the determination of diffusion coefficients of intercalated species in host materials. The capacity intermittent titration technique (CITT) is an extension of the ratio of potentiostatic-to-galvanostatic charge (RPG) technique developed initially by the same authors. By the CITT, the Li⁺ solid-state diffusion coefficient within LiMn₂O₄ was determined by these authors at different voltages and different galvanostatic-charge currents. In these comments, the ratio of potentiostatic-to-galvanostatic charge is reexamined by taking finite charge-transfer kinetics at the interface and Ohmic drop into consideration. The measurement error of diffusion coefficients evaluated by CITT while using the approximation of infinitely fast charge-transfer kinetics is predicted quantitatively.     

Cure kinetics modeling and process optimization of the vialux 81 epoxy photodielectric dry film (PDDF) material for microvia applications

The cure kinetics of a photodielectric dry film (PDDF) material called ViaLux 81 has been studied, with the aim of understanding and optimizing its curing schedule for the fabrication of sequentially built‐up (SBU) high‐density‐interconnect printed wiring boards (HDI‐PWB). Initial dynamic differential scanning calorimetry (DSC) scans on the material revealed a two‐stage curing mechanism due to the long lifetime of the photoinitiator catalyst, which could not be separated at lower heating rates. On the other hand, the heat flow exotherm from isothermal DSC experiments showed a rapid reaction rate at the beginning with only a single peak. Therefore, to capture the complexity of the process, the faster multiple heating rate DSC experiments are used to predict the degree‐of‐cure (DOC) evolution. Two approaches have been developed based on the dynamic DSC data: (1) a “model‐free” approach, which only requires information about the cure‐dependence of the activation energy; and (2) a practical scheme to deconvolute the two curing peaks. Excellent agreement is observed for the heating rate experiments, but the methods are inadequate for predicting the DOC evolution under isothermal conditions. Therefore, a modified autocatalytic model with temperature‐dependent kinetic parameters has been developed based on the isothermal DSC data. This model predicts the DOC evolution for isothermal curing profiles very well. However, some discrepancy is evident in predicting the DOC evolution for heating rate experiments, due to the underestimation of the activation energy. With appropriate corrections, excellent predictive capability is illustrated for complex cure schedules with combined heating rate and isothermal segments. In addition, a cure process optimization strategy has been suggested, and the fabrication of fine features and microvias is demonstrated. © 2002 John Wiley & Sons, Inc. J Appl Polym Sci 84: 691–700, 2002; DOI 10.1002/app.2345     

Integration of immersed membrane ultrafiltration with the reuse of PAC and alum sludge (RPAS) process for drinking water treatment

Effects of PAC and alum sludge generated from water treatment process on the effluent quality and fouling of immersed UF membrane were systematically investigated with representative source of natural water and the efficiency of coagulation, PAC adsorption and RPAS to treat natural surface water prior to UF were compared. It was found that the average turbidity removal by RPAS could reach up to 80.2%, and the turbidity removal of immersed membrane UF was independent of the influent, which could be kept at 99%. Particulates were reduced after being pre-treated by different processes, and particles with sizes ranging from 0.5 to 3.5 μm and larger than 13.5 μm were effectively removed by RPAS. UF coupled with RPAS pre-treatment got the best removal for DOM compared to other processes with average DOC and UV₂₅₄ removal 54.1% and 47.2% due to the high removal in the influent of UF. The residual alum content in the effluent of RPAS with UF was less than coagulation and bacteria were almost all removed by membrane. The membrane-fouling was mitigated by pre-treatment processes at different degrees, TMP of UF coupled with RPAS process was relatively stable in 15 d of run, the adsorption of PAC and large number of Al(OH)₃ complexes and precipitates for the foulant molecules might be an important mechanism.     

Isolation and Characterization of New Microsatellite Markers for the Invasive Softshell Clam, Mya arenaria (L.) (Bivalvia: Myidae)

The invasive softshell clam (Mya arenaria Linnaeus, 1758) is native to the northwestern region of the Atlantic Ocean. This species has been introduced in the northeast Pacific and along the European coasts, due to intense naval transports and aquaculture, and it is now present in all the European seas. In this paper we describe seven new microsatellite loci for Mya arenaria. The isolated loci are polymorphic with a number of alleles per locus between 6 and 14. The observed and expected heterozygosities ranged from 0.417 to 0.951, and from 0.643 to 0.895, with an average of 0.716 and 0.775, respectively. These microsatellite markers should be useful in analyzing this species' genetic diversity, which could explain various processes of its invasion history.     

Modification and magnetization of MOF (HKUST-1) for the removal of Sr2+ from aqueous solutions. Equilibrium,kinetic and thermodynamic modeling studies

In this research, metal-organic framework MOF(HKUST-1) was synthesized, magnetized and modified by hexacyanoferrate in order to prepare an efficient adsorbent for the removal of Sr²⁺ from aqueous solutions. The synthesized adsorbent was characterized by X-ray diffraction (XRD), energy dispersive X-ray spectroscopy, thermal methods (TG-DTG[Themogravimetry- Derivative Theromogravimetry]), Fourier transform infrared (FTIR) spectroscopy, Brunauer–Emmett–Teller (BET) surface area and scanning electron microscopy (SEM). The non-magnetized (MOF/KNiFC[potassium nickel hexacyanoferrate]) and magnetized (MOF/Fe₃O₄/KNiFC) adsorbents were then employed for the removal of Sr²⁺ from aqueous solutions. The adsorption capacity of 110 and 90 mg.g^?1 was obtained, respectively, for MOF/KNiFC and MOF/Fe₃O₄/KNiFC. The adsorption process was kinetically fast and the equilibration was established within 45 min. The magnetic capability of the adsorbent examined by the vibrating sample magnetometer (VSM) technique indicated that the used adsorbent was capable of separating from the solution by applying an external magnetic field. The adsorbent showed good selectivity toward Sr²⁺ in the presence of Cs⁺, Na⁺, Mg²⁺, Ca²⁺ and Ba²⁺. The regenerated adsorbent retained more than 90% of its initial capacity. Different isotherm models including Langmuir, Freundlich, Tempkin, Sips and Redlich–Peterson were employed to examine the applicability of the isotherms to the experimental data. It was concluded that the data was best fitted to the Langmuir isotherm model. The thermodynamic parameters showed that the process was endothermic.     

Metal ion binding capability of the water‐soluble poly(vinyl phosphonic acid) for mono‐, di‐, and trivalent cations

A water‐soluble polymer containing phosphonic acid groups was investigated as a polychelatogen by using the liquid‐phase polymer‐based retention technique (LPR) under different experimental conditions. The maximum retention capacity of this polymer was determined at different pHs and polymer–metal ion ratios. The metal ions investigated were Ag(I), Cu(II), Co(II), Ni(II), and Cr(III). The maximum retention capacity values of the divalent metal ions were very similar and higher than those for the trivalent cations, indicating that the polymer–metal ion interaction was basically through electrostatic type. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2917–2922, 2004     

An extension of the group contribution method for estimating thermodynamic and transport properties part II. Polyatomic gases (F2, Cl2, CS2, H2S, NO and N2O)

Earlier work on the group contribution method applied to the Kihara potential is extended to polyatomic gases for the calculation of second virial coefficients, viscosities and diffusivities of dilute gases with a single set of gas group parameters. Functional group parameters are evaluated from the simultaneous regression of second virial coefficient and viscosity data of pure gases. Parameters for gas groups (F₂, Cl₂, CS₂, H₂S, NO, nd N₂O) are found to provide good predictions of second virial cross coefficients, mixture viscosities and binary diffusion coefficients of gas-gas mixtures. Application of the model shows that second virial coefficient data can be represented with good results comparable to the values by means of the corresponding states model. The reliability of the present model in viscosity predictions is proved by comparison with the Lucas method. Predictions of binary diffusion coefficients are in excellent agreement with experimental data and compare well with values obtained by means of the Fuller method.     

A simple and clean process for the synthesis of M(C17H35COO)2 (M = Zn, Pb)

This paper presents a cleaner production process for producing metal stearates particles using solid-state reaction at low temperatures. Zinc stearate and lead stearate were synthesized using PbO, ZnO and stearate acid as the reactants. The products were characterized by XRD, TG, DSC and FTIR techniques. The results showed this process yielded the products in excellent yield. Compared with precipitation or saponifying process, metal stearates prepared in this way appear of shorter process, lower cost, and no production of polluted water and higher yields.     

Porcine Small Intestinal Submucosa (SIS) as a Suitable Scaffold for the Creation of a Tissue-Engineered Urinary Conduit: Decellularization,Biomechanical and Biocompatibility Characterization Using New Approaches

Bladder cancer (BC) is among the most common malignancies in the world and a relevant cause of cancer mortality. BC is one of the most frequent causes for bladder removal through radical cystectomy, the gold-standard treatment for localized muscle-invasive and some cases of high-risk, non-muscle-invasive bladder cancer. In order to restore urinary functionality, an autologous intestinal segment has to be used to create a urinary diversion. However, several complications are associated with bowel-tract removal, affecting patients’ quality of life. The present study project aims to develop a bio-engineered material to simplify this surgical procedure, avoiding related surgical complications and improving patients’ quality of life. The main novelty of such a therapeutic approach is the decellularization of a porcine small intestinal submucosa (SIS) conduit to replace the autologous intestinal segment currently used as urinary diversion after radical cystectomy, while avoiding an immune rejection. Here, we performed a preliminary evaluation of this acellular product by developing a novel decellularization process based on an environmentally friendly, mild detergent, i.e., Tergitol, to replace the recently declared toxic Triton X-100. Treatment efficacy was evaluated through histology, DNA, hydroxyproline and elastin quantification, mechanical and insufflation tests, two-photon microscopy, FTIR analysis, and cytocompatibility tests. The optimized decellularization protocol is effective in removing cells, including DNA content, from the porcine SIS, while preserving the integrity of the extracellular matrix despite an increase in stiffness. An effective sterilization protocol was found, and cytocompatibility of treated SIS was demonstrated from day 1 to day 7, during which human fibroblasts were able to increase in number and strongly organize along tissue fibres. Taken together, this in vitro study suggests that SIS is a suitable candidate for use in urinary diversions in place of autologous intestinal segments, considering the optimal results of decellularization and cell proliferation. Further efforts should be undertaken in order to improve SIS conduit patency and impermeability to realize a future viable substitute.     

Experimental, kinetic and 2-D reactor modeling for simulation of the production of hydrogen by the catalytic reforming of concentrated crude ethanol (CRCCE) over a Ni-based commercial catalyst in a packed-bed tubular reactor

Mechanistic kinetic models were formulated based on Langmuir-Hinshelwood-Hougen-Watson and Eley-Rideal approaches to describe the kinetics of hydrogen production by the catalytic reforming of concentrated crude ethanol over a Ni-based commercial catalyst at atmospheric pressure, temperature range of 673-863 K, ratio of weight of catalyst to the molar rate of crude ethanol 3472-34722 kg cat s/kmol crude in a stainless steel packed bed tubular microreactor. One of the models yielded an excellent degree of correlation, and was selected for the simulation of the reforming process which used a pseudo-homogeneous numerical model consisting of coupled material and energy balance equations with reaction. The model was solved using finite elements method without neglecting the axial dispersion term. The crude ethanol conversion predicted by the model was in good agreement with the experimental data (AAD%=4.28). Also, the predicted concentration and temperature profiles for the process in the radial direction indicate that the assumption of plug flow isothermal behavior is justified within certain reactor configurations. However, the axial dispersion term still contributed to the results, and thus, cannot be neglected.     

Tuning of Bi3+-related excitation and emission positions through crystal field modulation in the perovskite-structured La2(Znx, Mg1-x)TiO6 (0 ≤ x ≤ 1):Bi3+ solid solution for white LEDs

In the past year, emission-tunable crystals based on the rare-earth (RE) ions as luminescent center have been frequently reported for use in UV and blue converted white LEDs, but so far tuning the non-RE Bi³⁺ related emissions through the crystal field modulation is still not discovered in the perovskite crystals. In this work, we design and report a type of Bi³⁺ doped La₂(Zn_x,Mg_1-x)TiO₆ (0 ≤ x ≤ 1) perovskite solid solutions, which enable showing the tunable Bi³⁺ excitation and emission positions. The XRD results show that gradual substitution of smaller Mg²⁺ ions with larger Zn²⁺ ions can lead to the blue-shifting of X-ray diffraction (XRD) position, revealing the expansion of cell lattice. Together with structural analysis, our refined XRD and time-resolved spectral results reveal that there is only one type of La site available for Bi³⁺ substitution. With this regular crystal lattice change, the crystal field strength around Bi³⁺ ions is found to vary regularly, allowing to realization of the excitation and emission spectral tuning, i.e., the Bi³⁺ excitation and emission positions as the Mg ions are replaced by the Zn ions can tune from 348?nm to 392?nm and from 405?nm to 433?nm, respectively. This Bi³⁺ spectral tuning peak after calculated by the dielectric chemical bond theory features a linear relationship with the crystal field strength and, thus, is ascribed to the crystal field modulation. On basis of the La₂(Zn_0.4,Mg_0.6)TiO₆ blue, SrGa₂S₄:Eu²⁺ green and Y₂O₃:Eu³⁺ red phosphors, a UV converted warm white LED device with desirable color rendering index (CRI) of 78, correlated color temperature (CCT) of 3650 K and good luminous efficacy of 118.13?lm/W, is fabricated. This work provides new insights into using the crystal-field modulation to discover more Bi³⁺ emission-tunable crystals for white LEDs in the future.