Adsorption of CO2 from dry gases on MCM-41 silica at ambient temperature and high pressure. 2: Adsorption of CO2/N2, CO2/CH4 and CO2/H2 binary mixtures

Adsorption equilibrium capacity of CO₂, CH₄, N₂, H₂ and O₂ on periodic mesoporous MCM-41 silica was measured gravimetrically at room temperature and pressure up to 25 bar. The ideal adsorption solution theory (IAST) was validated and used for the prediction of CO₂/N₂, CO₂/CH₄, CO₂/H₂ binary mixture adsorption equilibria on MCM-41 using single components adsorption data. In all cases, MCM-41 showed preferential CO₂ adsorption in comparison to the other gases, in agreement with CO₂/N₂, CO₂/CH₄, CO₂/H₂ selectivity determined using IAST. In comparison to well known benchmark CO₂ adsorbents like activated carbons, zeolites and metal-organic frameworks (MOFs), MCM-41 showed good CO₂ separation performances from CO₂/N₂, CO₂/CH₄ and CO₂/H₂ binary mixtures at high pressure, via pressure swing adsorption by utilizing a medium pressure desorption process (PSA-H/M). The working CO₂ capacity of MCM-41 in the aforementioned binary mixtures using PSA-H/M is generally higher than 13X zeolite and comparable to different activated carbons.     

Adsorption and separation of CH4/CO2/N2/H2/CO mixtures in hexagonally ordered carbon nanopipes CMK-5

Adsorption and separation of N₂, CH₄, CO₂, H₂ and CO mixtures in CMK-5 material at room temperature have been extensively investigated by a hybrid method of grand canonical Monte Carlo (GCMC) simulation and adsorption theory. The GCMC simulations show that the excess uptakes of pure CH₄ and CO₂ at 6.0 MPa and 298 K can reach 13.18 and 37.56 mmol/g, respectively. The dual-site Langmuir–Freundlich (DSLF) model was also utilized to fit the absolute adsorption isotherms of pure gases from molecular simulations. By using the fitted DSLF model parameters and ideal adsorption solution theory (IAST), we further predicted the adsorption separation of N₂–CH₄, CH₄–CO₂, N₂–CO₂, H₂–CO, H₂–CH₄ and H₂–CO₂ binary mixtures. The effect of the bulk gas composition on the selectivity of these gases is also studied. To improve the storage and separation performance, we finally tailor the structural parameters of CMK-5 material by using the hybrid method. It is found that the uptakes of pure gases, especially for CO_2, can be enhanced with the increase of pore diameter D_i, while the separation efficiency is apparently favored in the CMK-5 material with a smaller D_i. The selectivity at D_i=3.0 nm and 6.0 MPa gives the greatest value of 8.91, 7.28 and 27.52 for S_CO2/N2, S_CH4/H2 and S_CO2/H2, respectively. Our study shows that CMK-5 material is not only a promising candidate for gas storage, but also suitable for gas separation.     

Selective transport of CO2, CH4, and N2 in coals: insights from modeling of experimental gas adsorption data

Selective adsorption and transport of gases in coal are important for natural gas recovery and carbon sequestration in depleted coal seams for environmental remediation. Gases are stored in coal mainly in the adsorbed state. In this study, the interaction energies of adsorbates (CO₂, CH₄, and N₂) and micropores with various widths are investigated using a slit-shape pore model. The experimental adsorption rate data of the three gases conducted on the same coal sample are numerically simulated using a bidisperse model and apparent diffusivities of each adsorbate in the macropore and micropore are determined. The results indicate that the relative adsorbate molecule size and pore structure play an important role in selective gas adsorption and diffusion in micropores. Generally, the microporous coals diffusion is activated and the apparent micropore diffusivities of gases in coal decrease strongly with increase in gas kinetic diameters. Apparent micropore diffusivity of CO₂ is generally one or two order of magnitude higher than those of CH₄ and N₂ because their kinetic diameters have the relation: CO₂ (0.33 nm)<N₂ (0.36 nm)<CH₄ (0.38 nm). In contrast to theoretical values, apparent macropore diffusivity of CO₂ is also larger than those of CH₄ and N₂, suggesting that coal has an interconnected pore network but highly constricted by ultra micropores with width <∼0.6 nm. It is also found that the apparent diffusivity strongly decreases with an increase in gas pressure, which may be attributed to coal matrix swelling caused by gas adsorption. Therefore, rigorous modeling of gas recovery and production requires consideration of specific interaction of gas and coal matrix.     

Ar, O2, CHF3, and SF6 plasma treatments of screen-printed carbon nanotube films for electrode applications

This paper investigates the consequence of the material property and the plasma gas chemistry (herein referred to the plasma gas-feeding species and methods) on the electrode performance in plasma treatments of screen-printed carbon nanotube (CNT) films. Four plasma gases (Ar, O₂, SF₆, and CHF₃) and three gas-feeding methods were examined. The surface morphology, microstructure, and composition of 11 sample groups have been carefully characterized. Tests of the CNT film electrode subjected to gas discharge and field emission show that surface morphology modification is the most influential factor in respect of lowering the onset voltages. In detail, O₂/Ar (O₂ followed by Ar) and Ar + CHF₃ + SF₆ (mixed three gases) treatments are the best choices for ionization and field emission applications, respectively. The relevant results are even better than that of the samples of aligned CNT films prepared by chemical vapor deposition. The underlying mechanisms are modeled by two opposing processes (etching and coating), which phenomenally produce three competing effects, i.e., CNT protruding, bundle forming, and neo-nanostructure forming. The results and the correct behavior of our model suggest that the plasma gas chemistry is the most fundamental factor in the process of plasma treatments of CNT films.     

Evaluation of CO2 permeation through functional assembled mono-layers: Relationships between structure and transport

CO₂ transport through functional assembled mono-layers was evaluated in relation to H₂O and nonpolar gases such as CH₄, O₂, N₂. Membranes based on Pebax^®2533 were functionalised by incorporating chemical compounds containing free hydroxyl, N-alkyl sulphonamide, bulky benzoate groups. The effects of both the chemical nature and concentration of the modifier on the gas transport were reported, respectively. The permeability coefficients of different penetrating chemical species were compared, evidencing the higher affinity of the layers to water vapour and carbon dioxide, due to favourable interactions between polar moieties and penetrant. The condensability of the penetrant directed the permeability of the species considered and was responsible for the high solubility selectivity between H₂O and CO₂ (i.e. , DH₂O/D₂CO=0.6, SH₂O/S₂CO=11.4 at 25 °C for Pebax/KET 50/50 w/w). An increase in polar moieties resulted in enhanced permeability and selectivity with respect to the pure polymer. In contrast, the functionalised polymer was not capable to discriminate between the smallest penetrants such as O₂ and N₂, with consequent decrease in the ideal selectivity (P₂CO/O₂, P₂CO/N₂). The functional layers exhibited permeability and selectivity covering broad ranges of values.     

Processing and properties of Pb(Mg1/3Nb2/3)O3–PbTiO3-based ceramics

Ceramic compositions of a combination between lead magnesium niobate, Pb(Mg_1/3Nb_2/3)O₃, and lead titanate, PbTiO₃, were fabricated using the Mg₄Nb₂O₉ precursor technique. Their electrical properties with respect to temperature and frequency were examined and the effect of sintering conditions on phase formation, densification, microstructure and electrical properties of the ceramics were examined. It has been found that optimisation of sintering conditions can lead to a highly dense and pyrochlore-free PMN–PT ceramics. The gradual decrease of the physical properties of the sintered ceramics was related to the gradual decrease of density and inhomogeneous microstructure. The results also revealed that for the lower concentration of lead titanate, a relaxor behaviour is noticed with a high electrostrictive effect, which was almost hysteretic free. However, higher amount of lead titanate led to a normal ferroelectric behaviour.     

Investigation of flue-gas treatment with O3 injection using NO and NO2 planar laser-induced fluorescence

Direct ozone (O₃) injection is a promising flue-gas treatment technology based on oxidation of NO and Hg into soluble species like NO₂, NO₃, N₂O₅, oxidized mercury, etc. These product gases are then effectively removed from the flue gases with the wet flue gas desulfurization system for SO₂. The kinetics and mixing behaviors of the oxidation process are important phenomena in development of practical applications. In this work, planar laser-induced fluorescence (PLIF) of NO and NO₂ was utilized to investigate the reaction structures between a turbulent O₃ jet (dry air with 2000 ppm O₃) and a laminar co-flow of simulated flue gas (containing 200 ppm NO), prepared in co-axial tubes. The shape of the reaction zone and the NO conversion rate along with the downstream length were determined from the NO-PLIF measurements. About 62% of NO was oxidized at 15d (d, jet orifice diameter) by a 30 m/s O₃ jet with an influence width of about 6d in radius. The NO₂ PLIF results support the conclusions deduced from the NO-PLIF measurements.     

Long-term degradation of Ta2O5-doped Bi2O3 systems

Bismuth oxide in δ-phase is a well-known high oxygen ion conductor and can be used as an electrolyte for intermediate temperature solid oxide fuel cells (IT-SOFCs). 5-10 mol% Ta₂O₅ are doped into Bi₂O₃ to stabilize δ-phase by solid state reaction process. One Bi₂O₃ sample (7.5TSB) was stabilized by 7.5 mol% Ta₂O₅ and exhibited single phase δ-Bi₂O₃-like (type I) phase. Thermo-mechanical analyzer (TMA), X-ray diffractometry (XRD), AC impedance and high-resolution transmission electron microscopy (HRTEM) were used to characterize the properties. The results showed that holding at 800-850 °C for 1 h was the appropriate sintering conditions to get dense samples. Obvious conductivity degradation phenomenon was obtained by 1000 h long-term treatment at 650 °C due to the formation of α-Bi₂O₃ phase and Bi₃TaO₇, and 〈1 1 1〉 vacancy ordering in Bi₃TaO₇ structure.     

Properties of cold lake bitumen saturated with pure gases and gas mixtures

This paper presents new data for the viscosity, density and gas solubility of Cold Lake bitumen saturated with light gases and gas mixtures over a temperature range of 15 to 103°C at up to 10 MPa pressure. Specifically, the gases whose effects on the bitumen properties were measured are N₂, CH₄, CO₂ and C₂H₆, and two mixtures of CO₂ and CH₄. With CO₂ and C₂H₆, experiments were also performed in the liquid-liquid region, and the results of these experiments generally agree with the previously published predictions. The viscosity of the gas-free Cold Lake bitumen is comparable to that of a Marguerite Lake bitumen that was tested previously. Due to the large solubilities of C0₂ and C₂H₆, the reduction in gas-saturated bitumen viscosity is quite dramatic. The density of the gas-saturated bitumen decreases with increased amounts of the dissolved CH₄ and C₂H₆ gases, but no such trends are evident for the N₂ and CO₂ gases. The results of the experiments with two binary gas mixtures (i.e., CO₂ and CH₄) indicate that the bitumen properties are affected largely by the major gas constituent.     

XPS investigation of the reaction of carbon with NO, O2, N2 and H2O plasmas

The interaction of graphite with plasmas of pure gases (O₂, N₂ or H₂O), air or mixtures of gases containing NO has been studied by XPS “in situ” analysis. Depending on the type of plasma, different species of nitrogen, oxygen and carbon have been detected on the surface of graphite. The nitrogen containing species have been attributed to pyridinic, pyrrol, quartenary and oxidized groups adsorbed on the surface. The evolution with the treatment time of the relative intensity of the different nitrogen bands for Ar + NO, N₂ + NO, air or N₂ plasmas has served to propose a model accounting for the reactions of graphite with plasmas of NO containing gases. The model explains why carbon materials (in the form of graphite, soot particles, etc.) can be very effective for the removal of the NO present in exhaust combustion gases excited by a plasma. The analysis of the C1s and O1s photoemission peaks reveals the formation of C/O adsorbed species up to a maximum concentration on the surface of around 10% atomic oxygen. A general evolution is the progressive formation of C/O species where the carbon is sp³ hybridized. This tendency is enhanced when graphite is treated with the plasma of water.     

Fabrication and characterization of Matrimid/MIL-53 mixed matrix membrane for CO2/CH4 separation

In this study, gas separation properties of Matrimid/MIL-53 mixed matrix membranes with different MOF weight percentages (0–20 wt.%) were investigated. TEM, XRD and DLS analysis were implemented to investigate MIL-53, structure and particles size distribution. SEM, FTIR, DSC and TGA analyses were conducted to characterize the fabricated membranes. The SEM images of these membranes showed good adhesion between polymer and particles, although for 20% MIL-53 loading, particles agglomeration was observed in some areas. Moreover, surface images of the membranes showed adequate dispersion of the particles in the polymer matrix, especially at lower MOF loadings. The permeability of pure CO₂ and CH₄ gases for all membranes were measured and the ideal CO₂/CH₄ selectivity was calculated. CH₄ permeability of membranes increased slightly as the percentage of loading increased. At 20 wt.% MOF loading, void formation led to a significant increase in CH₄ permeability (300% over pure Matrimid). CO₂ permeability showed the same trend; there was a 94% increase in permeability compared to pure Matrimid for 15 wt.% MMMs. CO₂/CH₄ selectivity also increased as MOF loading increased. The highest selectivity was shown for 15 wt.% MOF loading. This membrane had 84% growth in selectivity over pure Matrimid. Although at 20 wt.% MIL-53 loading, membrane separation performance was destroyed.     

Effect of particle diameter on the permeability of polypropylene/SiO2 nanocomposites

In this contribution the permeation behaviour of polypropylene composites containing silica nanospheres of different diameters is reported. The composite materials were produced by melt compounding polypropylene with silica nanospheres, with diameters ranging from 12 to 150 nm, produced using standard sol-gel methods. The permeability of O₂, N₂ and H₂O through the materials was tested. The results indicate that the addition of nanospheres with diameters of ≥30 nm results in an increase in the O₂ and N₂ permeability and is directly proportional to the nanosphere diameter. In the case of the water vapour transmission rate, it was found that there is also an increase, but the effect is inversely related with the nanospheres diameter. Incorporation of spheres with a diameter of 12 nm produces a decrease in the permeability of polypropylene composites in all instances, due to its formation of aggregates in composites.     

Modeling char conversion under suspension fired conditions in O2/N2 and O2/CO2 atmospheres

The aim of this investigation has been to model combustion under suspension fired conditions in O₂/N₂ and O₂/CO₂ mixtures. Experiments used for model validation have been carried out in an electrically heated Entrained Flow Reactor (EFR) at temperatures between 1173 K and 1673 K with inlet O₂ concentrations between 5 and 28 vol.%. The COal COmbustion MOdel, COCOMO, includes the three char morphologies: cenospheric char, network char and dense char each divided between six discrete particle sizes. Both combustion and gasification with CO₂ are accounted for and reaction rates include thermal char deactivation, which was found to be important for combustion at high reactor temperatures and high O₂ concentrations. COCOMO show in general good agreement with experimental char conversion profiles at conditions covering zone I-III. From the experimental profiles no effect of CO₂ gasification on char conversion has been found. COCOMO does however suggest that CO₂ gasification in oxy-fuel combustion at low O₂ concentrations can account for as much as 70% of the overall char consumption rate during combustion in zone III.     

Experimental study of vapor permeation of C5C7 alkane through PDMS membrane

Vapor permeation through dense membrane is regarded as an effectively way to separate volatile organic compounds (VOC) from industrial gas stream. This study proposes a new method to get the solubility and diffusivity of pure VOC vapor in dense membrane. C₅H₁₂, C₆H₁₄ and C₇H₁₆ were selected as sample VOC components to conduct newly developed sorption experiment with polydimethylsiloxane (PDMS) membrane. For each considered VOC component, its solubility was obtained from measured sorption equilibrium concentration in PDMS membrane, and its diffusivity was determined by fitting diffusion equation to the measured transient concentration of VOC component. The permeation behavior of VOCs in PDMS membrane was analyzed in terms of their solubility, diffusivity and permeability. Furthermore, the obtained solubility of these VOC components was utilized to get the vapor–membrane interaction parameters in UNIQUAC model. This opens an effective way to obtain the activity coefficient of VOC components for predicting their permeation performance in PDMS membrane.     

Elaboration and characterization of PVP-assisted NiO thin films for enhanced sensitivity toward H2 and NO2 gases

It is widely demonstrated that the synthesis conditions of sol-gel films have a great impact on their gas sensing properties. In this work, transparent PVP-assisted nickel oxide thin films with an average grain size of ~5?nm were synthesized using two distinctive deposition procedures combining the sol-gel method with the spin-coating technique then tested as optical gas sensors for the detection of hazardous pollutant gases. The first method is ascribed to a typical spin-coating deposition followed by a thermal annealing, and the second method consisted on a multistep coating annealing process. Structural and morphological studies showed enhanced crystallization rate and homogeneous surface morphology using a multistep deposition. The as prepared films exhibit a clear and reversible response toward H₂, CO and NO₂ gases and the multistep deposition process enhanced the sensitivity of about 113% and 194% toward 1% of H₂ and 0.1% of NO₂ respectively. The shrinkage of the band gap from 4.07 to 3.91?eV and the increased PL intensity indicate the presence of higher rate of charge density and intrinsic defect states that promoted the sensitivity of the film. Furthermore, improved response intensity was detected in the near UV region and higher stability with fast response was obtained for hydrogen gas.     

Ionic and electronic transport in stabilized β-La2Mo2O9 electrolytes

Increasing temperature from 973 to 1173 K leads to a substantial increase of the electronic contribution to the total conductivity of undoped lanthanum molybdate and La₂Mo₂O₉-based solid electrolytes, including La₂Mo_1.7W_0.3O₉, La₂Mo_1.95V_0.05O₉ and La_1.7Bi_0.3Mo₂O₉, where the stabilization of β-La₂Mo₂O₉ down to room temperature was confirmed by high-resolution X-ray diffraction (XRD) and differential scanning calorimetry (DSC) data. In air, the ion transference numbers determined by the modified Faradaic efficiency (FE) technique, decrease from 0.991-0.997 at 973-1023 K down to 0.977-0.984 at 1173 K. Reducing oxygen partial pressure also increases electronic conduction evaluated by the emf and oxygen permeability (OP) measurements, which indicates that the electronic transport is n-type, resulting from decreasing oxygen content in the molybdate lattice. The level of n-type electronic conductivity in air is quite similar for all La₂Mo₂O₉-based ceramics. The results show that these materials can be used as solid electrolytes only under oxidizing conditions and only at temperatures below 1073 K. Their practical applications may also be complicated due to relatively high thermal expansion coefficients (CTEs), (14.1-14.8)×10⁻⁶ K⁻¹ at 300-700 K and (16.4-22.5)×10⁻⁶ K⁻¹ at 850-1070 K, which are close to those of stabilized δ-Bi₂O₃ and γ-Bi₂VO_5.5 electrolytes.     

Permeability of the porous Al2O3 ceramic with bimodal pore size distribution

Porous Al₂O₃ ceramics with bimodal pore size distribution were fabricated by partial sintering with monodispersed PMMA micro balls as pore agent. The porosity of the fabricated porous Al₂O₃ is increased with content of the pore agent increase, the bulk density and bending strength are decreased, accordingly. Relations between pressure drop and flow velocity of the air through the porous Al₂O₃ fit the Forchheimer's equation well for compressible fluid. Due to pores introduced by the pore agent, the Darcy permeability and inertial permeability of the porous Al₂O₃ are increased obviously. For given flow velocity, with increase of the PMMA content, the Forchheimer's number of the fluid through the porous Al₂O₃ is decreased, which results in decrease of the inertial resistance ratio to the total pressure drop. The porous Al₂O₃ ceramics with pores introduced by the monodispersed PMMA micro balls show higher permeability while the filtration selectivity is not deteriorated.     

Preparation and properties of β-CaSiO3/ZrO2 (3Y) nanocomposites

β-CaSiO₃/ZrO₂ (3Y) nanocomposites were successfully fabricated by spark plasma sintering (SPS) technique. The addition of nanocrystalline ZrO₂ could inhibit the phase transition of micrometer sized CaSiO₃ and increase its phase transitional temperature. The relative densities of the dense β-CaSiO₃/ZrO₂ nanocomposites were above 98%. Nanocrystalline ZrO₂ has formed a network structure in the nanocomposites, which could improve the mechanical properties of nanocomposites. The fracture strength and fracture toughness of the nanocomposites were as high as 395 MPa and 4.08 MPa m^1/2, respectively. The nanocomposites showed good in vitro bioactivity with hydroxyapatite (HA) layer formation on the ZrO₂ network of the nanocomposites in simulated body fluid. The spark plasma sintered β-CaSiO₃/ZrO₂ (3Y) nanocomposite may provide a new bone graft for load bearing applications.     

Dielectric,magnetic and magnetoelectric properties of Ni0.5Zn0.5Fe2O4+Pb(Zr0.48Ti0.52)O3 composite ceramics

Magnetoelectric composite ceramics of spinel ferrite Ni_0.5Zn_0.5Fe₂O₄ (NZFO) with high magnetic permeability and tetragonal perovskite Pb(Zr_0.48Ti_0.52)O₃ (PZT) with high piezoelectric constant were synthesized by common solid state reaction method. XRD and SEM showed that high dense composite ceramics without any foreign phases were obtained. The ceramics showed excellent dielectric and magnetic properties, which were stable in a large frequency range. The dielectric peak became wider with the ferrite content in the permittivity spectrum with temperature. With the increase in the ferrite content, the magnetic Curie temperature shifted to higher temperature and closed to that of the pure ferrite. In addition, the magnetoelectric coefficient enhanced as the increase in the ferrite content. The properties of the composite ceramics could be adjusted by the ferrite content. These research results provided a powerful experimental basis for the sensor and transducer in microelectronic and microwave devices.