Nanogrooved carbon microtubes for wet three‐dimensional printing of conductive composite structures

Recent advances in three‐dimensional (3D) printing have enabled the fabrication of interesting structures which are not achievable using traditional fabrication approaches. The 3D printing of carbon microtube composite inks allows fabrication of conductive structures for practical applications in soft robotics and tissue engineering. However, it is challenging to achieve 3D printed structures from solution‐based composite inks, which requires an additional process to solidify the ink. Here, we introduce a wet 3D printing technique which uses a coagulation bath to fabricate carbon microtube composite structures. We show that through a facile nanogrooving approach which introduces cavitation and channels on carbon microtubes, enhanced interfacial interactions with a chitosan polymer matrix are achieved. Consequently, the mechanical properties of the 3D printed composites improve when nanogrooved carbon microtubes are used, compared to untreated microtubes. We show that by carefully controlling the coagulation bath, extrusion pressure, printing distance and printed line distance, we can 3D print composite lattices which are composed of well‐defined and separated printed lines. The conductive composite 3D structures with highly customised design presented in this work provide a suitable platform for applications ranging from soft robotics to smart tissue engineering scaffolds. © 2019 Society of Chemical Industry     

Switching from Ethylene Trimerization to Ethylene Polymerization by Chromium Catalysts Bearing SNS Tridentate Ligands: Process Optimization Using Response Surface Methodology

Two types of chromium catalysts bearing pyridine and amine based SNS ligands under the title of (pyridine-SNS-alkyl/CrCl₃) and (amine-SNS-alkyl/CrCl₃) were synthesized. Different thiolates such as octyl, pentyl, butyl, cyclohexyl and cyclopentyl thiolates were reacted with 2,6-pyridine-dimethylene-ditosylate (PMT)/THF solution at room temperature. Then, the purified pyridine-based SNS ligands (1–5) were reacted with CrCl₃ (THF)₃ to obtain the pyridine-SNS-alkyl/CrCl₃ catalysts (6–10) in 50–70% yields. MMAO-activated pyridine-SNS-alkyl/CrCl₃ catalysts were capable of oligomerizing ethylene. Statistical experimental design was conducted using the central composite design method and surface methodology to study of the effect of important parameters such as ethylene pressure, Al/Cr ratio, catalyst concentration and the reaction temperature on 1-C₆ productivity of catalyst (7). A quadratic polynomial equation was developed to predict the 1-C₆ productivity. Ethylene oligomerization using the catalyst (7) was lead to a optimized reaction conditions, including the ethylene pressure of 19.5 bar, the temperature of 58.2 °C, the MMAO co-catalyst, Al/Cr?=?841 and the catalyst concentration of 8.7 µmol. The catalytic properties for ethylene oligomerization are strongly affected by reaction temperature. The experimental results indicated the reasonable agreement with the predicted values. The transformation from ethylene trimerization to ethylenev polymerization of catalyst system (7) was occurred by exchanging the reaction pressure. Influence of ligand structure with different substitutions on sulphur atom on productivity and selectivity was investigated. 1-C₆ with the high selectivity and productivity 4318 (g 1-C₆/g Cr h) was obtained for catalyst (7). In the second part, 1-C₆ was obtained with high selectivity and productivity around 141?×?10³ (g 1-C₆/g Cr h) for amine-based catalyst. All amine-based catalysts (14–16) showed considerably higher catalytic activities compared to pyridine-based catalysts. According to the TGA analysis the thermal stability of pyridine-based catalysts was found to be higher than the amine-based catalysts.

Graphical Abstract

Chromium complexes bearing pyridine and amine based SNS ligands have been synthesized and their catalytic performance in ethylene oligomerization has been investigated. A switching from ethylene trimerization to ethylene polymerization of the catalyst (7) was obtained utilizing exchanging of the ethylene pressure.

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MnO2 Nanoparticles as Efficient Oxidant for Ultrasound-Assisted Synthesis of 2-substituted Benzimidazoles under Mild Conditions

In this article, a novel method for synthesis of 2-substituted benzimidazoles using MnO₂ nanoparticles as a convenient oxidant agent in ethanol-water (1:1) as solvent under ultrasound irradiation was demonstrated. In this protocol the desired products were purely obtained in high yields. The main advantages of this research are: mild procedure, simplicity of method, easily work-up, high yields, and short reaction times. The MnO₂ nanoparticles were synthesized through a solid-state reaction route using simple strarting materials. Furthermore, their structure was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and Fourier transform infrared spectroscopy (FT-IR).     

Magnetic solid phase extraction of copper from aquatic samples by Fe3O4/SiO2 nanoparticles followed by atomic absorption spectrometric determination

A magnetic solid phase extraction was developed for preconcentration of Cu(II) as a 4-bromo-2-(2,4-dichloro-phenylimino)-phenol complex on Fe₃O₄/SiO₂ nanoparticles prior to its determination by atomic absorption spectroscopy. The effect of different parameters influencing the formation of the Cu complex and the extraction efficiency of the Cu complex were studied. Under optimal conditions, the calibration graph showed linearity in the range of 0.946–700 µg L^?1 (R² = 0.9995) of Cu(II). The limit of detection and relative standard deviation of the method (n = 6) were 0.283 µg L^?1 and 3.0%, respectively. The method was successfully applied to determine copper (II) in water samples.     

Facile catalytic ring opening polymerization of lactic acid: Comparing the performance of Fe and Zn metal species

As a bio‐compatible/degradable polymer, poly(lactic acid) (PLA) has been widely noticed in tissue engineering and medical applications. Proper catalytic ring‐opening polymerization of lactic acid is pertinent to development of active metal species capable of producing high‐molecular‐weight polymers. In this work, ligand catalyst (2,4‐di‐tertio‐butyl‐6‐{[(2‐di‐methyl‐amino ethyl) methyl amino] methyl} phenol) was synthesized and then attached to Fe‐based and Zn‐based metal substitutes, and performance of metal species toward ring opening polymerization of lactic acid has been investigated. Regulation of reaction condition at 180°C for 36 h with Zn‐based catalyst allowed for late‐stage production of a high‐molecular‐weight PLA, while Fe‐based facilitated polymerization at early stages leading to PLAs with comparatively twofold higher molecular weight at lower time, monomer‐to‐initiator ratio, and temperature (at 170°C). A ratio of monomer to initiator of 5000 with Fe catalyst resulted in the highest molecular weight. Thus, polymerization has been facilitated by the use of Fe‐based catalyst. For this class of catalyst with Fe substitute, the product was characterized by means of ¹H‐NMR, Fourier transform infrared spectroscopy, and differential scanning calorimetry analyses. J. VINYL ADDIT. TECHNOL., 25:215–224, 2019. © 2018 Society of Plastics Engineers     

Thermo-oxidative aging of epoxy coating systems

The thermo-oxidative behavior of unformulated (unfilled) samples of epoxy coatings has been studied at five temperatures ranging from 70 °C to 150 °C. Two epoxy networks based on diglycidyl ether of bisphenol A (DGEBA), respectively, cured by jeffamine (POPA) or polyamidoamine (PAA) were compared. Infrared spectrophotometry (IR), differential scanning (DSC) and sol–gel analysis (SGA) were used to monitor structural changes.     

Ghezeljeh nanoclay as a new natural adsorbent for the removal of copper and mercury ions:Equilibrium,kinetics and thermodynamics studies

Heavy metal determination was carried out by applying the solid phase extraction (SPE) method in batch mode followed by atomic absorption spectroscopy (AAS) and inductively coupled plasma atomic emission spectrosco-py (ICP-AES) from aqueous solutions using Ghezeljeh montmoril onite nanoclay as a new natural adsorbent. The Ghezeljeh clay is characterized by using Fourier Transform Infrared (FT-IR) Spectroscopy, Scanning Electron Mi-croscopy–Energy Dispersive Spectrometry (SEM–EDS) and X-ray Diffractometry (XRD) and X-ray Fluorescence (XRF). The results of XRD and FT-IR of nanoclay confirm that montmoril onite is the dominant mineral phase. Based on SEM images of Ghezeljeh clay, it can be seen that the distance between the plates is Nano. The effects of varying parameters such as initial concentration of metal ions, pH and type of buffer solutions, amount of ad-sorbent, contact time, and temperature on the adsorption process were examined. The effect of various interfer-ing ions was studied. The adsorption data correlated with Freundlich, Langmuir, Dubinin–Radushkevich (D–R), and Temkin isotherms. The Langmuir and Freundlich isotherms showed the best fit to the equilibrium data for Hg(I ), but the equilibrium nature of Cu(II) adsorption has been described by the Langmuir isotherm. The kinetic data were described with pseudo-first-order, pseudo-second-order and double-exponential models. The adsorp-tion process follows a pseudo-second-order reaction scheme. Calculation ofΔG0,ΔH0 andΔS0 showed that the nature of Hg(II) ion sorption onto the Ghezeljeh nanoclay was endothermic and was favored at higher temper-ature, and the nature of Cu(II) ion sorption was exothermic and was favored at lower temperature.