Nanoraspberry-like palladium/spongy nickel oxide for electrooxidation of five light fuels

The spongy nickel oxide (SNO) was synthesized the solution combustion method. The SNO was selected as a promoter to boost the catalytic activity of nanoraspberry-like palladium (NRPd) toward electrooxidation of five light fuels (LFs): methanol, ethanol, formaldehyde, formic acid, and ethylene glycol. The X-ray powder diffraction, Fourier-transform infrared spectroscopy (FT-IR), scanning electron microscopy, and field emission scanning electron microscope techniques were used for the materials characterization. In comparison with nonpromoted Pd, the NRPd-SNO electrocatalyst shown an excellent efficiency in parameters like the electrochemical active surface area and anti-CO poisoning behavior. The turnover data and the parameters, including reaction order, activation energy, and the coefficients of electron transfer and diffusion, were evaluated for the each process of LFs electrooxidation. The outcome for NRPd-SNO activity toward LFs electrooxidation was compared to some reported electrodes. The SNO increases the removal of intermediates created in the oxidation of LFs that can poison the surface of palladium catalyst. This is due to the presence of the lattice oxygens in SNO structure and Ni switching between its high and low valances. The compatibility of the adsorption process of LFs on the surface of the NRPd-SNO catalyst with different isotherms was determined by studying the Tafel polarization and calculating the surface coverage.     

Influence of α′‐/α‐crystal polymorphism on properties of poly(l‐lactic acid)

Poly(l ‐lactic acid) (PLLA) is a biodegradable and biocompatible thermoplastic polyester produced from renewable sources, widely used for biomedical devices, in food packaging and in agriculture. It is a semicrystalline polymer, and as such its properties are strongly affected by the developed semicrystalline morphology. As a function of the crystallization temperature, PLLA can form different crystal modifications, namely α′‐crystals below about 120 °C and α‐crystals at higher temperatures. The α′ modification is therefore of special importance as it may be the preferred polymorph developing at processing‐relevant conditions. It is a metastable modification which typically transforms into the more stable α‐crystals on annealing at elevated temperature. The structure, kinetics of formation and thermodynamics of α′‐ and α‐crystals of PLLA are reviewed in this contribution, together with the effect of α′‐/α‐crystal polymorphism on the properties of PLLA. © 2018 Society of Chemical Industry     

Description of the thermodynamic properties and fluid-phase behavior of aqueous solutions of linear,branched, and cyclic amines

The SAFT-γ Mie group-contribution equation of state is used to represent the fluid-phase behavior of aqueous solutions of a variety of linear, branched, and cyclic amines. New group interactions are developed in order to model the mixtures of interest, including the like and unlike interactions between alkyl primary, secondary, and tertiary amine groups (NH₂, NH, N), cyclic secondary and tertiary amine groups (cNH, cN), and cyclic methine-amine groups (cCHNH, cCHN) with water (H₂O). The group-interaction parameters are estimated from appropriate experimental thermodynamic data for pure amines and selected mixtures. By taking advantage of the group-contribution nature of the method, one can describe the fluid-phase behavior of mixtures of molecules comprising those groups over broad ranges of temperature, pressure, and composition. A number of aqueous solutions of amines are studied including linear, branched aliphatic, and cyclic amines. Liquid–liquid equilibria (LLE) bounded by lower critical solution temperatures (LCSTs) have been reported experimentally and are reproduced here with the SAFT-γ Mie approach. The main feature of the approach is the ability not only to represent accurately the experimental data employed in the parameter estimation, but also to predict the vapor–liquid, liquid–liquid, and vapor–liquid–liquid equilibria, and LCSTs with the same set of parameters. Pure compound and binary phase diagrams of diverse types of amines and their aqueous solutions are assessed in order to demonstrate the main features of the thermodynamic and fluid-phase behavior.     

Nano fibrillated cellulose-based foam by Pickering emulsion: Preparation,characterizations, and application as dye adsorbent

An ecofriendly and biodegradable porous structure was prepared from drying aqueous foams based on nano fibrillated cellulose (NFC), extracted from softwood pulp by subcritical water/CO₂ treatment (SC-NFC). The primary aim of this work was to use the modified SC-NFC as stabilizer for a water-based Pickering emulsion which upon drying, yielded porous cellulosic materials, a good dye adsorbent. In order to exploit the carboxymethylated SC-NFC (CMSC-NFC, with a degree of substitution of 0.35 and a charge density of 649 μeqv/g) as a stabilizer for water-based Pickering emulsion in subsequent step, an optimized quantity of octyl amine (30 mg/g of SC-NFC) was added to make them partially hydrophobic. A series of dry foam structures were prepared by varying the concentrations of treated CMSC-NFCs and 4 wt% was found to be the optimum concentration to yield foam with high porosity (99%) and low density (0.038 g/cc) along with high compression strength (0.24 MPa), superior to the conventionally extracted NFC. The foams were applied to capture as high as 98% of methylene blue dyes, making them a potential green candidate for treating industrial effluent. In addition, the dye adsorption kinetics and isotherms were found to be well suited with second order kinetics and Langmuir isotherm models.     

Synthesis of thermoresponsive copolymer/silica-coated magnetite nanoparticle composite and its application for heavy metal ion recovery

To enhance chemical stability and suppress of aggregation of magnetite nanoparticles (MNPs), which are used as a support for thermoresponsive copolymer immobilization, silica coating of the MNPs is applied via the electrooxidation method. Although the resulting silica coated-MNPs also formed aggregates, the size distribution of the aggregate shifted to smaller size range. Because of that, the surface area available for copolymer immobilization increased approximately 6.7 times at maximum as compared with that of the uncoated MNPs. It contributed to the increase of the amount of the immobilized copolymer on the silica-coated MNPs, which is approximately four times larger than that on the uncoated MNPs. Fe₃O₄ dissolution test confirmed enhancement of chemical stability of MNPs. The thermoresponsive copolymer immobilized on the silica-coated MNPs shows the ability to recycle Cu(II) ion from Cu(II) containing solution by changing temperature with significantly shorter time than those in other thermoresponsive adsorbents in gel form.     

Prediction of methane adsorption content in continental coal-bearing shale reservoir using SLD model

Shale gas, as an important unconventional resource, has drawn global attention. It is mainly composed of adsorption gas and free gas. Adsorption gas content could play an important guiding role on both the selection of favorable perspective area and the exploration and exploitation of shale gas resources. In order to accurately measure adsorption gas content, a new approach was established to predict the adsorption isotherm of methane on shale. Based on the simplified local-density (SLD) method, both the adsorption isotherms of illite, illite/smectite mixed-layer, cholorite and type III kerogen and the total shale rock could be well fitted. The fitting results show good coincidences with the true experimental test data, which proves the method is reasonable and dependable and the prediction results are effective and credible. In addition, the good simulation results show that the SLD parameters can reflect the pore structure characteristics and corresponding adsorption characteristics of the shale samples, which can be used for the quantitative characterization of shale pore system.     

Material design and development: From classical thermodynamics to CALPHAD and ICME approaches

This paper presents an overview and examples of material design and development using (1) classical thermodynamics; (2) CALPHAD (calculation of phase diagrams) modeling; and (3) Integrated Computational Materials Engineering (ICME) approaches. Although the examples are given in lightweight aluminum and magnesium alloys for structural applications, the fundamental methodology and modeling principles are applicable to all materials and engineering applications. The examples in this paper have demonstrated the effectiveness and limitations of classical thermodynamics in solving specific problems (such as nucleation during solidification and solid-state precipitation in aluminum alloys). Computational thermodynamics and CALPHAD modeling, when combined with critical experimental validation, have been used to guide the selection and design of new magnesium alloys for elevated-temperature applications. The future of material design and development will be based on a holistic ICME approach. However, key challenges exist in many aspects of ICME framework, such as the lack of diffusion/mobility databases for many materials systems, limitation of current microstructural modeling capability and integration tools for simulation codes of different length scales.     

Synthesis and characterization of a novel Ca-alginate-biochar composite as efficient zinc (Zn2+) adsorbent: Thermodynamics,process design,mass transfer and isotherm modeling

In this present work, Ca-alginate-biochar adsorbent has been synthesized, characterized and tested its effectiveness in the removal of aqueous phase Zn²⁺ metal. The removal efficiency was studied under various physicochemical process parameters. External mass transfer model, intraparticle diffusion model and pseudo-first-order and pseudo-second-order models were used to fit the experimental Zn²⁺ adoption kinetic results and to identify the mechanism of adsorption. The desorption studies indicate the possibilities of ion-exchange and physical–chemical adsorption of Zn^2+. The adsorption was best described by Langmuir isotherm model. Thermodynamic parameters suggested that the adsorption process becomes spontaneous, endothermic and irreversible in nature.