Morphological Investigation of Midblock‐Sulfonated Block Ionomers Prepared from Solvents Differing in Polarity

Recent developments regarding charged multiblock copolymers that can form physical networks and exhibit robust mechanical properties herald new and exciting opportunities for contemporary technologies requiring amphiphilic attributes. Due to the presence of strong interactions, however, control over the phase behavior of such materials remains challenging, especially since their morphologies can be solvent‐templated. In this study, transmission electron microscopy and microtomography are employed to examine the morphological characteristics of midblock‐sulfonated pentablock ionomers prepared from solvents differing in polarity. Resultant images confirm that discrete, spherical ion‐rich microdomains form in films cast from a relatively nonpolar solvent, whereas an apparently mixed morphology with a continuous ion‐rich pathway is generated when the casting solvent is more highly polar. Detailed 3D analysis of the morphological characteristics confirms the coexistence of hexagonally‐packed nonpolar cylinders and lamellae, which facilitates the diffusion of ions and/or other polar species through the nanostructured medium.

     

Measurement and modeling of metoclopramide hydrochloride (anti-emetic drug) solubility in supercritical carbon dioxide

Knowledge of drug solubility data in supercritical carbon dioxide (SC-CO₂) is a fundamental step in producing nano and microparticles through supercritical fluid technology. In this work, for the first time, the solubility of metoclopramide hydrochloride (MCP) in SC-CO₂ was measured in pressure and temperature range of 12 to 27 MPa and 308 to 338 K, respectively. The results represented a range mole fractions of 0.15 × 10^-5 to 5.56 × 10^-5. To expand the application of the obtained data, six semi-empirical models and three models based on the Peng-Robinson equation of state (PR + VDW, PR + WS + Wilson and PR + MHV1 + COSMOSAC) with different mixing rules and various ways to describe intermolecular interactions were investigated. Furthermore, total enthalpy, sublimation enthalpy and solvation enthalpy relevant to MCP solvating in SC-CO₂ were estimated.     

Anti-corrosion and anti-microbial evaluation of novel water-soluble bis azo pyrazole derivative for carbon steel pipelines in petroleum industries by experimental and theoretical studies

In this research, we investigated the synthesis of a novel water-soluble bis azo pyrazolin-5-one (ABP) which was synthesized efficiently via the regioselective reaction of hydrazine with coumarin hydrazone (CMH). Also, we evaluate their anti-corrosion and anti-bacterial behavior. The inhibition efficiency of ABP in an acidic medium (1.0 M HCl) was evaluated using various electrochemical and surface morphology measurements. The novel bis pyrazole-based azo dye ABP (16 × 10^?6 M) demonstrated a higher protection capacity (93.3 %). Tafel curves revealed that ABP was a mixed-type inhibitor. The adsorption of ABP on the C-steel (CS) surface is proven by the alteration in (R_ct and C_dl) impedance characteristics and obeyed the Langmuir isotherm model. SEM/EDX, AFM, and XPS surface examinations confirmed the enhancement of an adsorbed film protects the CS surface from acid corrosion at the appropriate dose. Furthermore, theoretical calculations using DFT and MC simulations were performed to identify the active sites on ABP molecules in charge of the adsorption and surface protection of the CS. The adsorption of bis pyrazole-based azo dye on the metal surface explained the protection mechanism. Moreover, the ABP screened for its antimicrobial activity against sulfate-reducing bacteria (SRB), and the calculated inhibition efficiency was 100 %. The current work presents significant results in manufacturing and producing novel water-soluble bis pyrazole-based azo dye derivative with high anti-corrosion and anti-microbial efficiency.     

Submicron carbon-based hybrid nano-pour-point depressant with outstanding pour point depressant and excellent viscosity depressant

We have investigated the effective utilization potential of carbon nanomaterials in the field of pour point depressants, and reported three kind of carbon-based hybrid nano-pour-point depressants with different dimensions. In this paper, poly-α-olefins-acrylate high-carbon ester pour point depressant (PAA-18) was prepared by esterification and polymerization as the basic pour point depressant. Then, the basic pour point depressant PAA18 was modified by solvothermal method with graphene oxide (GO), carbon nanospheres (Cna) and carbon nanotubes (OCNTs). The morphology and structure of the composites were analyzed by SEM, FTIR and XRD. The results showed that PAA18 was successfully in situ polymerized on GO, Cna and OCNTs. We took the simulated oil as the experimental object, and evaluated its pour point, rheological properties and wax crystal morphology, and achieved excellent results. In the three carbon-based hybrid nano-pour-point depressants with different carbon contents, the oxidation carbon nanotubes composite pour point depressant (PAA18-1 % OCNTs) with carbon content of 1 % had the best pour point and viscosity reduction effect when the dosage was 1250 ppm, which could make the pour point of the simulated oil containing wax decrease by 16 °C. PAA18-1 % OCNTs reduced the pour point by 5 °C more than PAA18. This paper provides reference for the application of carbon nanomaterials in the field of pour point depressant.     

A comparative study of the adsorption equilibrium of progesterone by a carbon black and a commercial activated carbon

In this paper the adsorption process of a natural steroid hormone (progesterone) by a carbon black and a commercial activated carbon has been studied. The corresponding equilibrium isotherms have been analyzed according to a previously proposed model which establishes a kinetic law satisfactorily fitting the C versus t isotherms. The analysis of the experimental data points out the existence of two well-defined sections in the equilibrium isotherms. A general equation including these two processes has been proposed, the global adsorption process being fitted to such equation. From the values of the kinetic equilibrium constant so obtained, values of standard average adsorption enthalpy () and entropy () have been calculated. Finally, information related to variations of differential adsorption enthalpy () and entropy () with the surface coverage fraction (θ) was obtained by using the corresponding Clausius-Clapeyron equations.     

Carbon–metal interfaces analyzed by aberration-corrected TEM: How copper and nickel nanoparticles interact with MWCNTs

Experimental confirmation for the stronger interaction of Ni with multi-walled carbon nanotubes (MWCNTs) compared to Cu with MWCNTs is presented. The interfaces between Cu (Ni) nanoparticles side-on oriented onto MWCNTs are analyzed with high spatial resolution electron energy-loss spectroscopy (EELS) of the carbon K-edge. The EEL spectra reveal a rehybridization from sp² to sp³ hybridized carbon of the outermost MWCNT layer at the Ni interface, but no such rehybridization can be observed at the Cu interface. The EELS results are supported by transmission electron microscopy (TEM) images, which show a better wetting behavior of Ni and a smaller gap at the Ni–MWCNT interface, as compared to the corresponding Cu interfaces. The different behavior of Cu and Ni can be explained in terms of differing valence d-orbital occupancy. For the successful experimental demonstration of this effect the use of a soft chemical metal deposition technique is crucial.     

A study of the gasification of carbon black with molten salt of Li2CO3 and K2CO3 for application in the external anode media of a direct carbon fuel cell

The characteristics of gasification reactions for carbon–carbonate mixtures were experimentally investigated at high temperatures up to 900 °C, considering the application of the mixtures to the external anode media of a direct carbon fuel cell. A thermo-gravimetric analysis (TGA) was conducted in either a nitrogen or carbon dioxide ambient environment for Li₂CO₃, K₂CO₃ and a mixture of these two substances with carbon black. Changes in the exit gas composition were also monitored during the heating process. It was shown that gasification in the mixture media occurs much more rapidly than carbonate decomposition at elevated temperatures, even for low concentrations of CO₂. It was also shown that the loading of carbonates to carbon significantly affects the global gasification reaction; it increased the reaction rate by an order of magnitude and decreased its activation energy. Based on the experimental observations, a simplified reaction model of gasification was suggested for the anode media of a DCFC, regarding carbonate-catalysed and metal-catalysed pathways of Boudouard reactions.     

A Protic Ionic Liquid Catalyzes CO2 Conversion at Atmospheric Pressure and Room Temperature: Synthesis of Quinazoline‐2,4(1H,3H)‐diones

The chemical fixation of CO₂ under mild reaction conditions is of significance from a sustainable chemistry viewpoint. Herein a CO₂‐reactive protic ionic liquid (PIL), [HDBU⁺][TFE^?], was designed by neutralization of the superbase 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) with a weak proton donor trifluoroethanol (TFE). As a bifunctional catalyst for simultaneously activating CO₂ and the substrate, this PIL displayed excellent performance in catalyzing the reactions of CO₂ with 2‐aminobenzonitriles at atmospheric pressure and room temperature, thus producing a series of quinazoline‐2,4(1H,3H)‐diones in excellent yields.     

Preparation of MnO2 Loaded Hydrothermal Carbon-coated Electrospun PAN Fiber Membranes for Highly Efficient Adsorption and Separation of Cationic Dye

Hydrothermal carbonaceous materials and MnO₂ have been proved to be promising adsorbents to remove organic dyes from wastewater. In this study, flexible MnO₂ loaded hydrothermal carbon-coated electrospun poly-acrylonitrile(AC/MnO₂/PAN) fiber membranes were fabricated by a facile one-step hydrothermal method and activated by NaOH solution. The composite fibers exhibited large adsorption capacity toward cationic dyes and excellent mechanical properties. The adsorption performance can be fitted well with pseudo-second-order model and Langmuir isotherm model. The maximum adsorption for methylene blue(MB), methyl violet(MV) and malachite green(MG) are 1173.27,1106.31 and 1129.89 mg/g, respectively, according to Langmuir fitting. The AC/MnO₂/PAN fiber membrane also showed satisfactory performances for selective adsorption and recyclability. In addition, based on selective adsorption, the AC/MnO₂/PAN fiber membranes that are repulsive to the anionic dye methyl orange(MO) can separate the MB/MO mixture solution by dynamic filtration. Thus, this work not only provides a facile strategy to fabricate large capacity adsorbents, but also demonstrates the potential applications in the dye wastewater treatment field.