Fabrication of BSCF-based mixed oxide ionic-electronic conducting multi-layered membrane by sequential electrophoretic deposition process

The Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3-δ (BSCF)-based multi-layered oxygen separation membrane was fabricated by the sequential electrophoretic deposition (EPD) process. A thin porous/dense bi-layer of BSCF was formed on a thick porous support of BSCF. The porous support prepared by a sacrificial template method using BSCF powder mixed with wheat starch (30 wt%) as a pore-forming agent, followed by uniaxial pressing and low-temperature sintering, was directly used as an EPD electrode. A thin BSCF layer was first formed on the porous support, and then a thin BSCF + PMMA (polymethyl methacrylate) layer was sequentially formed on the thin BSCF layer using a bimodal suspension of BSCF and PMMA. A 30-μm thin porous/dense bi-layer of BSCF of which the total thickness was obtained by optimizing the processes of EPD and subsequent co-sintering. The oxygen separation performance of 3.7 ml (STP) min^?1 cm^?2 at 860 °C was achieved for the BSCF-based multi-layered oxygen separation membrane.     

An effective strategy to boost hydrogen separation performance through stable mixed proton-electron conducting membrane

Hydrogen separation and purification are key to widespread application of hydrogen energy. Hydrogen permeable membranes based on lanthanum tungstate (LWO) attract attention due to favorable mechanical strength and chemical stability. However, industrial application of LWO-based membranes has remained challenging because of modest hydrogen permeances. Here we report a novel graded porous supported symmetric (GPSS) LWO-based membrane with improved transport properties, gas exchange dynamics, and operational stability, boosting stable hydrogen flux by several times over previously reported state-of-the-art membranes.     

Yttria-stabilized zirconia closed end tubes prepared by electrophoretic deposition

The electrophoretic deposition technique was used for the preparation of ZrO₂:8 mol% Y₂O₃ (yttria-stabilized zirconia, 8YSZ) closed end tubes for application in high temperature oxygen sensing devices. The 8YSZ ceramic suspensions with different average particle sizes were investigated looking for the best conditions for electrophoretic deposition of thin wall closed end ceramic tubes. High deposition rate of the ceramic particles onto graphite were obtained with isopropanol as solvent and 4-hydroxybenzoic acid as dispersant, with good surface quality of the deposited layer. The green tubes were dried and sintered at 1500 °C, and their properties were analyzed by X-ray diffraction for determination of the structural phases, scanning probe microscopy for observation of grain morphology, and impedance spectroscopy for evaluation of the oxide ion electrical resistivity. Pt/YSZ tube/Pt electrochemical cells were assembled for exposure to oxygen in the 60-650 ppm range using an electrochemical YSZ oxygen pump and sensor system. The signal response of the electrophoretic deposited sensor was similar to the response of the sensor of the oxygen pump. Several thin wall 4 mm diameter × 30 mm length closed end tubes may be obtained in a single operation, showing the ability of this technique for processing large quantities of tubular solid electrolytes with electrical properties suitable for use in high temperature devices.     

High-flux CO2-stable oxygen transport hollow fiber membranes through surface engineering

The influences of bulk diffusion and surface exchange on oxygen transport of (La_0.6Ca_0.4)(Co_0.8Fe_0.2)O_3-δ (LCCF) hollow fiber membranes were investigated. As an outcome, two strategies for increasing the oxygen permeation were pursued. First, porous LCCF hollow fibers as support were coated with a 22 μm dense LCCF separation layer through dip coating and co-sintering. The oxygen permeation of the porous fiber with dense layer reached up to 5.10 mL min^?1 cm^-2 at 1000 °C in a 50 % CO₂ atmosphere. Second, surface etching of dense LCCF hollow fibers with H₂SO₄ was applied. The surface etching of both inner and outer surfaces leads to a permeation improvement up to 86.0 %. This finding implies that the surface exchange reaction plays a key role in oxygen transport through LCCF hollow fibers. A good long-term (>250 h) stability of the asymmetric hollow fiber in a 50 % CO₂ atmosphere was found at 900 °C.     

Particle size separation by alternating electrophoretic deposition

This paper describes a study of the size distribution of the particles deposited under different frequencies by alternating electrophoretic deposition. A low concentration suspension of SnO₂ particles was prepared in acetone and particles of SnO₂ were deposited on electrodes by the low frequency alternating electrophoretic deposition method. Scanning electron microscopy (SEM) showed that increasing the frequency from 0 to 1000 Hz reduces the average size of the SnO₂ particles deposited. Particle size distributions obtained from the SEM images show the sizing capability of the alternating electrophoretic deposition method.     

Gold nanoparticle thin films fabricated by electrophoretic deposition method for highly sensitive SERS application

We report an electrophoretic deposition method for the fabrication of gold nanoparticle (GNP) thin films as sensitive surface-enhanced Raman scattering (SERS) substrates. In this method, GNP sol, synthesized by a seed-mediated growth approach, and indium tin oxide (ITO) glass substrates were utilized as an electrophoretic solution and electrodes, respectively. From the scanning electron microscopy analysis, we found that the density of GNPs deposited on ITO glass substrates increases with prolonged electrophoresis time. The films possess high mechanical adhesion strength and exhibit strong localized surface plasmon resonance (LSPR) effect by showing high SERS sensitivity to detect 1 × 10⁻⁷ M rhodamine 6 G in methanol solution. Finally, the relationship between Raman signal amplification capability and GNP deposition density has been further investigated. The results of our experiment indicate that the high-density GNP film shows relatively higher signal amplification capability due to the strong LSPR effect in narrow gap regions between the neighboring particles on the film.     

Fabrication of ceramic membranes on porous ceramic supports by electrophoretic deposition

Abstract

Nanoporous alumina membrane and continuous zeolite L membrane were fabricated on the inner surface of microporous alumina tubes. In the former case, an electrophoretic deposition (EPD) technique was used for the deposition of bimodal alumina particles for the subsequent low temperature sintering. In the latter case, the EPD was used for the seeding process of zeolite L particles for the subsequent hydrothermal synthesis. A thin layer of polypyrrole was synthesised on the inside wall of the porous tubes by the chemical polymerisation of pyrrole to give the wall electric conduction for the EPD electrode. The thickness of the coating layers was controlled by altering the applied voltage and deposition time. The interfacial connection of the alumina or zeolite coated layer and the substrate was evaluated by SEM observations before and after the thermal treatment. The nanoporous structure of the alumina membrane was also characterised by a pore size analyser.     

Fabrication of aluminum nitride coatings by electrophoretic deposition: Effect of particle size on deposition and drying behavior

Electrophoretic technique was used to deposit micro- and nano-sized aluminum nitride coatings on stainless steel surfaces by using a well-dispersed stable suspension produced by addition of AlN powder plus a small amount of iodine to ethanol. Parabolic regime governed the deposition. Electrophoretic deposition for 240 s at 100 V resulted in formation of a uniformly dense film on the top, but a porous inhomogeneous layer at the bottom. This was attributed to fast deposition of coarse particles and/or agglomerates at large electric fields. After drying, micro-sized particles led to a uniform crack-free interface while nano-particles resulted in fragmented non-cohesive layers. Weight loss measurements revealed higher drying rates for micro-layer as compared to nano-cover. This seemed owing to the larger pore sizes and lower specific surfaces of the former. Stress inducement by lateral drying of small capillaries led to crack initiation from the edges and its propagation across the surfaces. This resulted in fragmentation of the samples due to their delamination. Effect of deposition rate on particles packability was also investigated.     

Effects of Al content on the oxygen permeability through dual-phase membrane 60Ce0.9Pr0.1O2-δ-40Pr0.6Sr0.4Fe1-xAlxO3-δ

Ceramic dual-phase oxygen transport membranes with the composition of 60 wt% Ce_0.9Pr_0.1O_2-δ-40 wt%Pr_0.6Sr_0.4Fe_1-xAl_xO_3-δ (x = 0.05, 0.1, 0.2, 0.3, 0.4, 0.6, 0.8, 1.0) (60CPO-40PSF_1-xA_xO) based on 60Ce_0.9Pr_0.1O_2-δ-40Pr_0.6Sr_0.4FeO_3-δ doped Al was successfully synthesized through a modified Pechini method. Crystal structure, surface microtopography and oxygen permeability are investigated systematically. The cell parameters of perovskite phase first increased and then decreased with the increase of Al content, which is related to the radius of the Al³⁺ and the formation of impurity phase. As x ranges from 0.1 to 0.8, the oxygen permeability of the materials first increases and then decreases, and the maximum value of oxygen permeation rate for 60CPO-40PSF_1-xA_xO membranes with 0.4 mm thickness at 1000 °C is 1.12 mL min⁻¹ cm⁻² when x = 0.4. XRD measurements revealed high temperature stability and CO₂-tolerant property of the dual-phase composites. The partial replacement of Fe³⁺/Fe⁴⁺ by Al³⁺ causes the material not only to exhibit good stability, but also to increase the oxygen permeability of the membranes.     

Fabrication of cylindrical SiCf/Si/SiC-based composite by electrophoretic deposition and liquid silicon infiltration

Cylindrical SiC-based composites composed of inner Si/SiC reticulated foam and outer Si-infiltrated SiC fiber-reinforced SiC (SiC_f/Si/SiC) skin were fabricated by the electrophoretic deposition of matrix particles into SiC fabrics followed by Si-infiltration for high temperature heat exchanger applications. An electrophoretic deposition combined with ultrasonication was used to fabricate a tubular SiC_f/SiC skin layer, which infiltrated SiC and carbon particles effectively into the voids of SiC fabrics by minimizing the surface sealing effect. After liquid silicon infiltration at 1550 °C, the composite revealed a density of 2.75 g/cm³ along with a well-joined interface between the inside Si/SiC foam and outer SiC_f/Si/SiC skin layer. The results also showed that the skin layer, which was composed of 81.4 wt% β-SiC, 17.2 wt% Si and 1.4 wt% SiO₂, exhibited a gastight dense microstructure and the flexural strength of 192.3 MPa.     

Influence of oxygen partial pressure on the oxygen diffusion and surface exchange coefficients in mixed conductors

The performances of mixed ionic and electronic conductors is used in many applications, such as oxygen transport membranes or electrodes in solid oxide fuel cells. The performances of these systems depend mainly on two fundamental parameters including oxygen diffusion (D_O) and the oxygen exchange coefficient (k). This work focuses on the impact of the oxygen partial pressure on oxygen diffusion and surface exchange coefficients of mixed conducting materials, as reported studies are scarce in the literature. In this way, two different mixed conducting materials are studied, namely, La_0.6Sr_0.4Fe_0.6Ga_0.4O_3-δ, a perovskite-type material, and the nickelate La₂NiO_4+δ. The D_O and k coefficients are determined by a specific oxygen permeation measurement and by the isotopic exchange depth profile method.     

Single- and dual-phase capillary membranes prepared through plastic extrusion method for oxygen permeation

Two capillary membranes, single-phase Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3-δ (BSCF) and dual-phase 75 wt% Ce_0.85Sm_0.15O_1.925 - 25 wt% Sm_0.6Sr_0.4Cr_0.3Fe_0.7O_3-δ (SDC-SSCF), with dense cross section, were successfully prepared through the plastic extrusion method. The dual-phase capillary membrane shows higher strength compared to the BSCF counterpart, while the two capillary membranes exhibit much higher fracture strength than those of hollow fiber membranes. The oxygen permeation fluxes of both membranes increase with the increase of temperature and flow rate of sweep gas at the ambient pressure, and can be greatly improved by applying high pressures to the feed side. The oxygen permeation flux of BSCF capillary membrane is up to 19.5 mL cm^?2 min^?1 when 0.5 MPa air was applied to the feed side at 900 °C, which is one order of magnitude higher than that of SDC-SSCF capillary membrane. Thus, both capillary membranes have their own advantages and meet applications under different operation conditions.     

High-flux dual-phase percolation membrane for oxygen separation

A series of composites based on (100-_x)wt.%Ce_0.9Pr_0.1O_2-δ-xwt.%Pr_0.6Ca_0.4FeO_3-δ (x = 25, 40 and 50) doped with the cheap and abundant alkaline earth metal Ca²⁺ at the A-site has been successfully designed and fabricated. The crystal structure, oxygen permeability, phase and CO2 stability were evaluated. The composition of 60wt.%Ce_0.9Pr_0.1O_2-δ-40wt.%Pr_0.6Ca_0.4FeO_3-δ(60CPO-40PCFO) possesses the highest oxygen permeability among three studied composites. At 1000 °C, the oxygen permeation fluxes through the 0.3 mm-thickness 60CPO-40PCFO membranes after porous La_0.6Sr_0.4CoO_3-δ each to 1.00 mL cm^?2 min^?1 and 0.62 mL cm^?2 min^?1 under air/He and air/CO₂ gradients, respectively. In situ XRD results demonstrated that the 60CPO-40PCFO sample displayed a perfect structural stability in air as well as CO₂-containing atmosphere. Thus, low-cost, Co-free and Sr-free 60CPO-40PCFO has high CO₂ stability and is economical and environmental friendly since the expensive and volatile element Co was replaced by Fe and Sr was waived since it easily forms carbonates.     

Preparation and characterization of polysulfone mixed matrix membrane incorporated with palladium nanoparticles in the inversed microemulsion for hydrogen separation

Polysulfone (PSf) membrane shows acceptable gas separation performance, but its application is limited by the “trade-off” between selectivity and permeability. In this study, PSf mixed matrix membranes (MMMs) incorporated with palladium (Pd) nanoparticles in the inversed microemulsion were proposed for hydrogen (H₂) separation. Pd nanoparticles can be kinetically stabilized and dispersed using electrostatic and/or steric forces of a stabilizer which is typically introduced during the formation of Pd nanoparticles in the inversed microemulsion. Pd nanoparticles were synthesized by loading (PdCl₂) into the polymeric matrix, polyethylene glycol (PEG) which acts as reducing agent and stabilizer. The dry–wet phase inversion method was applied for the preparation of asymmetric PSf MMMs. The effects of Pd (0–4 wt%) on the membrane characteristics and separation performance were studied. Experimental findings verified that the MMMs are able to achieved a high H₂/N₂ selectivity of 21.69 and a satisfactory H₂ permeance of 46.24 GPU due to the changes in membrane structure from fully developed finger-like structure to closed cell structure besides the growth of dense layer. However, the selectivity of H₂/CO₂ decreased due to the addition of PEG.     

Shaping of 3YSZ porous substrates for oxygen separation membranes

In recent years, asymmetric membranes based on mixed ionic-electronic conductors (MIEC) have gained importance in practical gas separations. MIEC ceramic materials show high-energy efficiency and high-temperature resistance, which allows direct integration in industrial processes. Thin layers are supported on porous substrates that provide mechanical strength. In the asymmetric membrane manufacture, the control of support porosity and microstructure is crucial. Colloidal processing is an interesting method that allows controlling the final microstructure in both surfaces and bulk, with high reproducibility. Here, the development of asymmetric membranes with a top functional layer made of Ce_0.8Gd_0.2O_1.9/Ni₂FeO₄ composite is presented and aims to maximize oxygen permeation and membrane robustness. The porous substrate is prepared by slip casting while the functional layers by screen-printing. The effect of pore former volume and particle morphology were studied. The combination of spherical and flake-like PMMA particles enabled to generate open porosity suitable for fast gas transport.     

Production of bulk SiC parts by electrophoretic deposition from concentrated aqueous suspension

Abstract

This paper reports on electrophoretic deposition of SiC bulk parts from highly loaded aqueous suspensions of submicron and nanosized powders. The effects of suspensions parameters (ζ-potential, conductivity, solids content) and deposition parameters (voltage, current density, time) on quality of deposits were examined. It is presented that by using well defined suspension parameters high process stability is assured. For submicron powder, relatively high density was achieved, i.e. 60% TD (±2%), while for the nanosized SiC, the highest density was 42% TD (±2%). Mixing of powders did not result in density increase. Bulk >4 cm thick deposits were proved to have homogeneous density distribution, which is one of the advantages of electrophoretic deposition (EPD) process in comparison to other ceramic shape forming processes.     

Thermal behaviour of vitreous ceramic coatings obtained by electrophoretic deposition for furnace components

In this study, three different vitreous ceramic coatings have been designed to improve radiation heat transfer and thereby increase the thermal efficiency of fired heaters or furnaces working at high temperatures. The vitreous ceramic coatings were produced through Electrophoretic Deposition technique (EPD) of ceramic suspensions. These ceramic formulations were designed based on components which increase emissivity, such as SiO₂ and a Black dye (based on chromium, copper and iron oxides), added in 25 wt%. These coatings showed emissivity values around 0.89 at room temperature and around 0.82 at 550 °C in the middle infrared (MIR) spectral range, with slight differences between them. The SiO₂ and Black dye additions provide an important protective effect on the coatings’ thermal stability as it was proved by the absorbance level at long times, higher than 85% in the near infrared (NIR) spectral range. These results were also supported by microstructural characterisation, substrate-coatings adhesion strength and thermal stability tests.     

Processing and electromechanical properties of lead zirconate titanate thick films by electrophoretic deposition

Electrophoretic deposition (EPD) was used for the fabrication of piezoelectric [lead zirconate titanate (PZT)] thick films on alumina substrates. The EPD was performed in constant current mode from an ethanol based suspension consisting of PZT and PbO particles. The influence of addition of ethyl cellulose (EC) and sintering temperature on the thickness, density, homogeneity and functional response of PZT thick films is studied. Results show that the highest electromechanical performance is obtained for the PZT thick films sintered at 900 or 950°C, with a thickness coupling factor k_t of 50%. The addition of EC influenced the thickness of the PZT thick films but had only minor effect on the porosity content for sintering temperatures over 900°C. Moreover, elastic constants of the thick films based on the suspension with EC were lower, which leads to lower acoustic impedance (15?MRa) while maintaining high (k_t) value. In this last case, a better acoustic matching can be expected with propagation media such as water or biological tissues for ultrasound medical imaging applications.     

Analysis of oxygen permeation through dense ceramic membranes with chemical reactions of finite rate

The oxygen permeation through oxygen ionic or mixed-conducting ceramic membranes under reaction conditions was examined with a model taking into account of different electrical transport mechanisms (p-type and n-type transports) and finite reaction rate. It was demonstrated that with a reaction consuming oxygen in one side of the membrane, the oxygen partial pressure in the reaction side decreases and the oxygen permeation flux increases with the increase in the reaction rate for both the p-type and the n-type transport dominated mechanism. The increase in reaction rate causes a transition of the transport mechanism from p-type to n-type. This transition leads to an increase in the permeation flux by up to 30 times. This effect offers one explanation for the large discrepancies in published permeation data for membrane reactors of partial oxidation reaction employing an oxygen permeable dense ceramic membrane. For a membrane with a specific transport mechanism, the increase in the reactant partial pressure causes an increase in the reaction rate and oxygen permeation flux. However, the increase in the inlet inert gas amount has a complicated effect on the oxygen permeation flux because it lowers both oxygen partial pressure and the reaction rate at the same time.