Deformation of AUK microporous carbon adsorbent induced by methane adsorption

The dependence of the relative linear deformation of AUK microporous carbon adsorbent on pressure is studied upon the adsorption of methane in the pressure range of 1 Pa to 6 MPa at 177.65, 216.2, 243.3, 273.15, 313, 333, and 393 K. It is found that the curves of adsorption-induced deformation show similar behavior; except for in the initial pressure range (p < 0.2 MPa), the adsorption-induced deformation increases with pressure and drops as the temperature rises. At low temperatures, a shrinkage region is observed in the initial part of the deformation curves that narrows with a rise in temperature. At temperatures above 350 K, the initial shrinkage is absent and the adsorbent expands with an increase in methane pressure. In the pressure and temperature ranges under investigation, the contribution of deformation to the differential isosteric heat of adsorption of AUK carbon adsorbent does not exceed 2%. It is shown that, upon the adsorption of CO₂, N₂, Ar, and CH₄ at 273 K and pressures below 6 MPa, the maximum deformation of AUK adsorbent varies cymbately with variations in the Lennard-Jones (6–12) potential constants for the pair interaction of gas molecules.     

Sorbostriction and the Rehbinder effect

The possibility of the inversion of the Rehbinder effect in the sorbostriction phenomena in brittle porous bodies is discussed.     

Size effect and mechanochemical contraction of the Si(100) specimens

Variation of thickness of specimens of single crystalline silicon Si(100) prepared by scribing of the water of 100 mm diameter to parts of smaller size under atmospheric conditions is studied. It is shown that the thickness of specimens having small surface (∼1 cm²) decreases after scribing by 0.8–1.0% (with the error of measurements < 0.3%). The observed decrease in the thickness is explained by the effect of sorption of vapors of atmospheric moisture in micropores with the decrease in the external surface of specimens of Si(100) (the sorbostriction phenomenon).     

The influence of bending on the performance of flexible carbon black/polymer composite gas sensors

The performance of electronics on flexible substrates suffers under substrate bending leading to reduced device performance. In this article, we highlighted the influence of bending strain on a conductive polymer composite gas sensor and developed a model to investigate the influence of strain. We evaluated the strain influence on the resistance of a gas sensor with respect to sensitivity, filler content, cyclic loading, and electrode orientation. The sensitivity of gas sensors increased with decreasing tensile bending radii. The influence of strain was dominant for gas sensors with less carbon black concentration. Cyclic bending tests showed a decrease of sensor resistance versus time and a plastic deformation. A sensor geometry orientations effect to reduce the sensitivity to bending strain was achieved by aligning the electrode fingers parallel to the strain. A model was successfully implemented to simulate strain influences inside the polymer incorporating the Poisson ratio. We suggest a concept to achieve a strain insensitive gas sensor by creating an orientation between single particles inside the composite. Implementing this results into existing gas sensors will improve the measurement quality and reliability of sensors on flexible substrates. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013     

Quantitative Analysis of Main Components of Natural Gas Based on Raman Spectroscopy

Natural gas is composed of methane, ethane, propane, carbon dioxide, nitrogen, hydrogen, carbon monoxide and unknown alkane components of C4 or more (denoted as C4⁺) after desulfurization and dehydration treatment. The concentrations of the first seven components account for more than 90% of natural gas. When analyzing the natural gas composition using Raman spectral analysis methods, a small amount of unknown alkane components C4⁺ will have a negative impact on the analytical precision. In this work, a novel method that consists of an automatic decomposition algorithm of Raman spectra and a model for quantitative analysis was developed for the analysis of components of natural gas. The Raman spectrum of a natural gas sample could be decomposed into the sum of the Raman spectra of pure constituents and several Lorentz peaks by a nonlinear least-square optimization algorithm based on a linear additivity of Raman spectra. The concentration of the unknown alkane component C4⁺ was determined according to the area of the C-H deformation vibration peak which was common for most alkane molecules. Some training samples were used to establish the model between Raman characteristic peak areas and corresponding concentrations for each component. Compared with the existing Raman analysis methods, the new method solved the problem of analyzing natural gas containing unknown alkane components with good stability and accuracy. The experiments showed that the maximum absolute errors of this algorithm for methane, ethane, propane, carbon dioxide, nitrogen, hydrogen, and carbon monoxide respectively reached 0.57%, 0.37%, 0.21%, 0.07%, 0.18%, 0.04%, 0.13%, and the correlation coefficient to gas chromatographic results also reached 0.997, 0.986, 0.991, 0.998, 0.993, 1.000, 0.995, 0.982, respectively.     

Strain of plates of aluminum, glass, and silicon at sorption of water vapor

It has been suggested and realized a kinetic approach to the investigation of sorbostriction isotherms on plates of aluminum, glass, and monocrystalline silicon at the sorption of water from its vapor. It is established increasing the plate area and decreasing the plate thickness with passing the contraction through a minimum in the process of sorption. The strain observed is explained by the interference of two effects: the influence of variation of the surface tension of the outer surface of samples and the role of micropores (with possible chemisorption in them).     

Deformation Behavior of Three-Dimensional Carbon Structures Under Hydrostatic Compression

The paper presents the results of numerical simulation aimed at studying the deformation behavior of carbon structures containing carbon atoms with various coordination numbers and, consequently, various electronic configurations and properties. Namely, the method of molecular dynamics was used to study the deformation behavior of two different structures of crumpled graphene (sp²-material formed by graphene flakes bonded by Van der Waals forces) and carbon diamond-like phases (rigid sp³-structures) under hydrostatic compression. Stress-strain curves have been obtained, structural features have been shown to affect mechanical properties of three-dimensional carbon structures.     

Structure of carbon nanoparticles synthesized by adiabatic compression of acetylene and their application in supercapacitors

The work reports the study of the structure of carbon nanoparticles prepared by the pyrolysis of heliumdiluted acetylene under adiabatic compression in a piston reactor. At a pushing gas pressure of 0.5 MPa, 0.7 MPa, and 0.9 MPa the reaction gas was heated to temperatures of 400 °C, 600 °C, and 750 °C. By transmission electron microscopy it is found that carbon nanoparticles have a spherical shape and their size varies from 20 nm to 60 nm. The structural features of carbon nanoparticles are determined from the X-ray photoelectron spectroscopy data and the analysis of the near-edge X-ray absorption fine structure spectroscopy. Carbon nanoparticles prepared at a pushing gas pressure of 0.5 MPa have an amorphous structure and consist of hydrogenated carbon with impurities of polycyclic aromatic fragments. At a stronger compression ratio, carbon nanoparticles with a layered structure consisting mainly of sp² hybridized carbon atoms are formed. The capacitance behavior and electrochemical impedance of carbon nanoparticle-based supercapacitors are compared.     

Reforming of Carbon Dioxide to Methane and Methanol by Electric Impulse Low-Pressure Discharge with Hydrogen

Basic phenomena of the reduction of carbon dioxide to reusable organic materials including methane and methanol were investigated by using a radio frequency impulse discharge in a low gas pressure range without catalysis. The discharge took place under different discharge parameters such as voltage, gas flow rate, gas-mixing ratio, and gas residence time, where the carbon dioxide was mixed with hydrogen at total gas pressure of 1–10 Torr. Organic materials such as methane and methanol were observed. Carbon monoxide was a major product from carbon dioxide. Methane was the dominant organic species produced by the discharge. The concentration of methane increased with discharge voltage, and its volume fraction attained 10–20% of the products containing carbon that came from carbon dioxide. This fraction was also dependent on the mixing ratio of carbon dioxide and hydrogen. We also observed the formation of methanol, though its fraction was low, a few %, compared with methane.     

Natural gas storage cycles: Influence of nonisothermal effects and heavy alkanes

A mathematical model is developed for examining the influence of nonisothermal effects and accumulation of heavy alkanes on natural gas storage cycles. The model is solved for the charge and discharge steps of the cycle. This is the first study to solve the natural gas storage problem for a nonisothermal charge of natural gas containing impurities. We examine both adiabatic and isothermal operation of natural gas and pure methane storage cycles on BPL carbon and an activated carbon prepared from coconut shells. Our simulations show for both carbons that the adiabatic gas storage cycles operate under subcooled conditions with respect to the feed temperature due to long discharge times and the desorption heat. It is also shown that degradation of gas storage performance due to impurities depends more on selectivity of the material for heavy alkanes than on adsorption capacities.     

Controllable water channel gating of nanometer dimensions

The dynamics of water molecules in a single-walled carbon nanotube (SWNT) under continuous deformations was studied with molecular dynamics simulations. The flux and occupancy remain almost fixed within a deformation of 2.0 A but decrease sharply for a further deformation of 0.6 A. The nanopore is an excellent on-off gate that is both effectively resistant to deformation noises and sensitive to available signals. Biological water channels are expected to share this advantage due to similar wavelike water distributions. The minimal external force required for triggering an open-close transition falls within the working range of many available experimental facilities, which provides the possibility of developing SWNT-based nanoscale devices.     

Thermoregulated Phase‐Transition Synthesis of Two‐Dimensional Carbon Nanoplates Rich in sp2 Carbon and Unimodal Ultramicropores for Kinetic Gas Separation

The development of highly selective, chemically stable and moisture‐resistant adsorbents is a key milestone for gas separation. Porous carbons featured with random orientation and cross‐linking of turbostratic nanodomains usually have a wide distribution of micropores. Here we have developed a thermoregulated phase‐transition‐assisted synthesis of carbon nanoplates with more than 80 % sp² carbon, unimodal ultramicropore and a controllable thickness. The thin structure allows oriented growth of carbon crystallites, and stacking of crystallites in nearly parallel orientation are responsible for the single size of the micropores. When used for gas separation from CH₄, carbon nanoplates exhibit high uptakes (5.2, 5.3 and 5.1 mmol g^?1) and selectivities (7, 71 and 386) for CO₂, C₂H₆ and C₃H₈ under ambient conditions. The dynamic adsorption capacities are close to equilibrium uptakes of single components, further demonstrating superiority of carbon nanoplates in terms of selectivity and sorption kinetics.     

Carbon molecular sieves produced by the fixation of sulphur surface complexes

Summary A Saran carbon has been treated with carbon disulphide and sulphur in order to introduce sulphur surface complexes, a commercial activated carbon was also used. Samples obtained were characterized by their surface areas and porosities. The adsorption of n-hexane, benzene and cyclohexane has been measured out at high temperatures and under dynamic conditions using a gas chromatographic technique. Results were compared with those obtained when oxygen-surface complexes were introduced and it can be concluded that when CS₂ is used with a highly microporous carbon, such as Saran, a molecular sieve for cyclohexane (mean size 0.58 nm) is produced at determined amounts of sulphur fixed.     

In situ Nanomechanical Research on Large-Scale Plastic Deformation of Individual Ultrathin Multi-walled Carbon Nanotube

Carbon nanotubes are a promising candidate for the application of flexible electronics due to the ultrahigh intrinsic conductivity and excellent mechanical flexibility. In the present work,the morphology of the ultrathin (diameter<20 nm) multi-walled carbon nanotubes (MWCNTs) under an axial compression was investigated by using in-situ transmission electron microscopy. Moreover, the overall dynamic deformation processes and the force-displacement (F-D) curves of the MWCNTs were also examined. Interestingly, the MWCNTs almost restored their original morphology after 15 loading-unloading cycles. The deformation and recovery process indicate that the MWCNTs are flexible and exhibit excellent durability against compression. The Young’s modulus of the MWCNTs is estimated with the value of ∽0.655 TPa derived from the F-D curves fitting. Our results suggest that the ultrathin carbon nanotube structures may have great application potentials in flexible devices.     

Synthesis gas as substrate for the biological production of fuels and chemicals

Synthesis gas provides a simple substrate for the production of fuels and chemicals. Synthesis gas can be produced via established technologies from a variety of feedstocks including coal, wood, and agricultural and municipal wastes. The gasification is thermally efficient and results in complete conversion of the feedstock to fermentable substrate.Clostridium ljungdahlii grows on the synthesis gas components, carbon monoxide, hydrogen, and carbon dioxide. Production of acetic acid and ethanol accompanies growth with synthesis gas as sole source of energy and carbon. Rate and yield parameters are compared forC. ljungdahlii grown on carbon monoxide, or hydrogen with carbon dioxide.

     

Evaluation of error sources in a gravimetric technique for preparation of a reference gas mixture (carbon dioxide in synthetic air)

One method of preparing a primary reference gas mixture is the gravimetric blending method. Uncertainty of a few mg in mass measurements is unavoidable when preparing reference gas mixtures under current laboratory conditions with our facilities, equipment, and materials. There are many sources of errors when using this method. In this study, several sources of errors were re-evaluated for our process for preparation of carbon dioxide in synthetic air. As a consequence of the re-evaluation, it was found that some sources of errors had significant effects on gravimetric concentrations of the gas mixtures. These sources are: (1) different masses of the reference cylinder and sample cylinder (an error in the readings of the electronic mass comparator), (2) leakage of the inner gas from valves of the cylinders, and (3) cooling of the gas cylinder caused by filling with high-pressure liquefied carbon dioxide gas. When the mass measurements were performed under uncontrolled conditions, the errors due to sources (1), (2), and (3) were as high as 20 mg, 24 mg, and 13 mg, respectively. In this paper, the detailed results from re-evaluation of these sources of errors are discussed. Figure Evaluation of the source of error (1)     

Prediction of adsorption behavior of activated carbons

A study was made of the effect of temperature on predictive equations recently developed and applied to gas adsorption by beds of activated and impregnated carbons. Adsorption parameters, obtained for the adsorbate DMMP on small gram quantities of impregnated carbon at 25°C and applied to carbon bed breakthru times, were analyzed for changes resulting from direct temperature effects on gas diffusion, adsorption—desorption equilibria, volume expansion, relative pressure, and adsorbate—adsorbent interactions. Modifications in the adsorption parameters, calculated for bed temperatures ranging between 40.3 and 46.7°C, were used in the kinetic equations to predict breakthru times for M10 gas filters, each containing 13,847 g of carbon. The predicted values compared very well with those experimentally determined, the mean deviation in breakthru time being 5.82%, without regard to sign. A general analysis of a 10°C rise in temperature, from 25 to 35°C, for the M10 gas filter under the test conditions used, showed that the breakthru time would be lowered 20.0 min, 87% of this lowering due to a reduced adsorption rate constant, 9% due to a reduced adsorption capacity, and 4% due to volume expansion effects on concentration and flowrate.     

压力对塔里木原油四组分热解性能的影响

压力对深层油藏原油热化学过程的影响尚存在较大争议,为研究其在油藏原油热解成气过程中的作用机理,我们在450℃、5~40 MPa压力下对塔里木原油四组分(饱和分、芳香分、胶质和沥青质)进行了封闭体系的热解实验,通过气相色谱(GC)和气相色谱/质谱(GC/MS)分别对原油四组分热解反应的气体产物及饱和分热解过程的液态产物进行了分析。结果表明,在450℃、24 h及不同压力下,沥青质热解产气率高于胶质、芳香分和饱和分;四组分的气相热解产物中,C1的产率明显高于C2~C5组分。增大压力抑制沥青质、胶质及芳香分的热解产气过程而促进饱和分的热解产气过程。随压力的增大,饱和分热解的液态产物的主峰组分碳数先减小,再增大。压力低于20 MPa时,饱和分热解过程中以裂解反应为主;高于30 MPa时,增大压力有利于缩合反应。研究结果可为认识深层油藏原油的稳定程度及天然气的成因提供一定的理论参考。     

Thermal degradation of poly(alkyl methacrylates)

The thermal degradation of selected poly(alkyl methacrylates) at temperatures between 300 and 800 °C was investigated by pyrolysis gas chromatography. Quantitative characterization of the pyrolysis products yields insights into the mechanism for thermal degradation of poly(alkyl methacrylates) under these conditions. Unsaturated monomeric alkyl methacrylates, carbon dioxide, carbon monoxide, methane, ethane, methanol, ethanol, and propanol were formed during thermal degradation of poly(alkyl methacrylates).     

Formation of inhomogeneities in polyacrylamide gel in the course of frontal polymerization

The deformation of gas bubbles in the course of photoinduced polymerization of polyacrylamide gel in monomer solution under microgravity conditions has been studied experimentally. The use of optical methods allows one to identify the specific features of changes in the shape of gas bubbles and to correlate these changes with different stages of polymerization. At the initial stage of the polymerization reaction, the development of gel inhomogeneities is caused by reflection and scattering of the initiating light and, correspondingly, by different rates of gel formation near the surface of a gas bubble. After its contact with the polymerization front, further deformation of the bubble is caused by the inhomogeneous development of the reaction in the formed gel. Using the interference method, the characteristic dimensions of structural inhomogeneities in the formed gel induced in the vicinity of the transparent inclusion are measured.