Synthesis of Ionic Ultramicroporous Polymers for Selective Separation of Acetylene from Ethylene

The design of highly stable and efficient porous materials is essential for developing breakthrough hydrocarbon separation methods based on physisorption to replace currently used energy-intensive distillation/absorption technologies. Efforts to develop advanced porous materials such as zeolites, coordination frameworks, and organic polymers have met with limited success. Here, a new class of ionic ultramicroporous polymers (IUPs) with high-density inorganic anions and narrowly distributed ultramicroporosity is reported, which are synthesized by a facile free-radical polymerization using branched and amphiphilic ionic compounds as reactive monomers. A covalent and ionic dual-crosslinking strategy is proposed to manipulate the pore structure of amorphous polymers at the ultramicroporous scale. The IUPs exhibit exceptional selectivity (286.1–474.4) for separating acetylene from ethylene along with high thermal and water stability, collaboratively demonstrated by gas adsorption isotherms and experimental breakthrough curves. Modeling studies unveil the specific binding sites for acetylene capture as well as the interconnected ultramicroporosity for size sieving. The porosity-engineering protocol used in this work can also be extended to the design of other ultramicroporous materials for the challenging separation of other key gas constituents.     

Analysis of nitrogen oxide emissions from modern vehicles using hydrogen or other natural and synthetic fuels in combustion chamber

The paper presents a calculated analysis of the equilibrium emission of nitrogen oxides on the exhaust of carburetor and diesel internal combustion engines. The temperature of fuel oxidation is assumed to be 1,400 °C while the pressure for carburetor and diesel engines is assumed to be 60 atm and 80 atm respectively. The studies have been carried out for natural and synthetic fuels such as hydrogen, ethanol, methanol, petroleum, diesel fuel and methane at the excess air coefficient corresponding to the fuel oxidation temperature of 1,400 °C. In the paper, the method for calculating the equilibrium composition based on the equilibrium constant and mass conservation equations has been applied. It is shown that with an increase in pressure from 1 atm to 60 atm for carburetor engines and up to 80 atm for diesel engines, the reaction of nitrogen dioxide formation may shift towards an increase in NO₂. The formation of NO may be not affected by the increase in pressure by virtue of the fact that the reaction proceeds without changes in the amount. It has been determined that NO is the major atmospheric pollutant. However, it would be advisable to use more extensively the fuels characterized by the lowest output of nitrogen dioxide (methane and methanol), since nitrogen dioxide (NO₂) related to the 2nd hazard class is appeared to be the most dangerous to humans. It has been revealed that the reduction in oxidation temperature using hydrogen as a fuel for electrochemical current generators may allow reducing nitrogen oxide emissions by more than an order of magnitude as compared to the best results for ICE.     

Enhancing cation exchange capacity of chars through ozonation

The use of ozone to increase the cation exchange capacity (CEC) of two chars produced from pyrolysis of Douglas fir (Pseudotsuga menziessii) and a control bituminous coal activated carbon (AC) is reported. Chars were produced from the wood fraction of Douglas fir (DFWC) and the bark (DFBC) at 500 °C using an auger driven reactor with a nitrogen sweep gas under mild vacuum. Five ozone treatment times, ranging from 5 min to 60 min, were investigated. The initial properties of each char were found to differ significantly from the other samples in terms of surface area, proximate composition, and elemental composition. DFWC did not show significant mass loss or temperature variation during ozone treatment; however, after 1 h of oxidation both DFBC and AC samples resulted in 20% and 30% mass loss, respectively, and reactor temperatures in excess of 60 °C. Analysis of the pore size distribution of each treatment shows that ozone treatment did not significantly affect small micropores after 30 min of treatment for any material, but did reduce the apparent surface area of mesopores. Increases in carboxylic groups were identified with ozone treatment and found to correlate strongly with changes in measured CEC. The formation of lactone was found to correlate positively with reactor temperature during oxidation. These results indicate that the properties of chars, including surface area, pore structure, and chemical composition, as well as reactor conditions strongly affect the ozone oxidation of chars.     

Detection of correlation characteristics between financial time series based on multi-resolution analysis

Interactions between financial time series are complex and changeable in both time and frequency domains. To reveal the evolution characteristics of the time-varying relations between bivariate time series from a multi-resolution perspective, this study introduces an approach combining wavelet analysis and complex networks. In addition, to reduce the influence the phase lag between the time series has on the correlations, we propose dynamic time-warping (DTW) correlation coefficients to reflect the correlation degree between bivariate time series. Unlike previous studies that symbolized the time series only based on the correlation strength, the second-level symbol is set according to the correlation length during the coarse-graining process. This study presents a novel method to analyze bivariate time series and provides more information for investors and decision makers when investing in the stock market. We choose the closing prices of two stocks in China’s market as the sample and explore the evolutionary behavior of correlation modes from different resolutions. Furthermore, we perform experiments to discover the critical correlation modes between the bull market and the bear market on the high-resolution scale, the clustering effect during the financial crisis on the middle-resolution scale, and the potential pseudo period on the low-resolution scale. The experimental results exactly match reality, which provides powerful evidence to prove that our method is effective in financial time series analysis.     

Effect of chemical phosphorylation on solubility of buffalo milk proteins

Buffalo milk proteins (casein, co-precipitate or whey protein concentrate) were phosphorylated with phosphorus oxychloride (POCl₃) at three different pH values (5.0, 7.0 and 9.0). The solubilities of phosphorylated milk proteins were examined over the pH range 3.0–9.0 in water and ionic (0.1 m NaCl or 10–70 mm Ca²⁺) systems. The solubilities of buffalo milk proteins decreased at pH 3.0, while there was an increase in the solubilities of casein and co-precipitate near their isoelectric points upon phosphorylation. Solubilities of these phosphorylated milk proteins were pH dependent in 0.1 m NaCl but there was a decrease in their solubilities with increase in calcium ion concentration. This alteration could be due to the shifting of isoionic points of phosphorylated buffalo milk proteins towards acidic pH.     

3D polymeric microfluidic device fabrication via contact liquid photolithographic polymerization (CLiPP)

In this contribution, a new method for the fabrication of complex polymeric microfluidic devices is presented. The technology, contact liquid photolithographic polymerization (CLiPP), overcomes many of the drawbacks associated with other rapid prototyping schemes, such as limited materials choices and time-consuming microassembly protocols. CLiPP shares many traits with other photolithographic methods, but three distinct features: (i) liquid photoresists in contact with the photomask, (ii) readily removed sacrificial materials, and (iii) living radical processes, enable multiple polymeric chemistries and mechanical properties while simultaneously enabling facile fabrication of 3D geometries and surface chemistry control. This contribution details fabrication techniques and methods for the fabrication of high aspect ratio posts covalently bonded to a polymeric substrate, an array of independently stacked bars on top of perpendicular bars, multiple undercut structures fabricated simultaneously, and a complex 3D geometry with intertwined channels.     

Deformation behaviour of iron-doped alumina

Compressive creep tests in air were carried out on 1 cat.% Fe-doped alumina at a temperature T=1400 °C. Iron doping affected the plastic deformation by different ways in relation with Fe²⁺ cations population. Fe²⁺ cations sped up the deformation rates. FeAl₂O₄ spinel precipitates were identified and they were found (i) to interact with alumina grain boundaries (ii) to limit the grain growth within a range of strain. The Fe²⁺ cations underwent oxidation and this resulted in the dissolution of the some precipitates and in the decrease of deformation rates. It was suggested that deformation sped up this evolution through mass transport and that time was not a dominating parameter.     

Electrochemical characteristics of heme proteins in hydroxyethylcellulose film

A stable film made from hydroxyethylcellulose (HEC) on pyrolytic graphite (PG) electrode was employed for incorporating hemoglobin (Hb), myoglobin (Mb) and horseradish peroxidase (HRP), and the electrochemical characteristics of the proteins were studied correspondingly. Experimental results revealed that HEC film could greatly accelerate electron transfer between the proteins and electrode, and the proteins showed a thin layer electrochemical behavior in the film. Moreover, all the proteins in the film exhibited good catalytic activity towards the reduction of hydrogen peroxide (H₂O₂) in the low H₂O₂ concentration range. In the high concentration range, H₂O₂ would exhibit toxicity effect on the proteins. The electrochemical properties and electrocatalytic abilities of the three heme proteins in HEC film have been compared, and the optimal conditions for H₂O₂ biosensor fabrication have been obtained.     

Desktop inkjet printer as a tool to print conducting polymers

In order to exploit mechanical flexibility of organic-based electronic devices, conducting polymer anodes, such as polyaniline or poly(3,4-ethylenedioxy)-thiophene-poly(styrene sulfonate) (PEDOT-PSS), have been extensively studied. Along with the use of solution based processing techniques, conducting polymers can simplify the device fabrication procedure and yield themselves easily to printing techniques. In this paper, we present the results of utilizing desktop inkjet printer as a tool for direct printing and patterning of conducting polymer. Design of printable patterns and adjustment of printing parameters can be performed using any software such as Power Point. PEDOT-PSS suspension can be loaded into an inkjet cartridge and deposited on a given substrate in any designed pattern. The gray-scale color scheme can be employed to control the layer thickness and sheet resistivity of the inkjet printed layers. These layers are then used as anodes in organic light-emitting devices (OLEDs).