Fabrication of BSCF-based mixed ionic-electronic conducting membrane by electrophoretic deposition for oxygen separation application

Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3-δ (BSCF), which exhibits a high mixed oxide ionic-electronic conduction, was used for the fabrication of an oxygen separation membrane. An asymmetric structure, which was a thin and dense BSCF membrane layer supported on a porous BSCF substrate, was fabricated by the electrophoretic deposition method (EPD). Porous BSCF supports were prepared by the uniaxial pressing method using a powder mixture with BSCF and starch as the pore-forming agent (0–50 wt.%). The sintering behaviors of the porous support and the thin layer were separately characterized by dilatometry to determine the co-fired temperature at which cracking did not occur. A crack-free and thin dense membrane layer, which had about a 15 μm thickness and >95% relative density, was obtained after optimizing the processes of EPD and sintering. The dense/porous interface was well-bonded and the oxygen permeation flux was 2.5 ml (STP) min⁻¹ cm^-2 at 850 °C.     

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.     

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.     

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.     

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.     

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.     

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.     

In-situ study of electrophoretic deposition of zinc oxide nanosheets and nanorods

In the present work, the effects of two different morphologies of zinc oxide nanoparticles (nanosheets and nanorods) were investigated by in-situ measurement of deposition weight, and current density. ZnO nanosheets and nanorods were synthesized by microwave-assisted method using co-surfactant route. The average thickness of obtained nanosheets, and the average diameter of nanorods were measured to be about 26 nm and 139 nm, respectively. ZnO films were obtained by electrophoretic deposition from suspension of nanoparticles in ethanol under different voltages. Results indicated that ZnO nanosheets tend to have greater deposition rate than ZnO nanorods under similar conditions. The compactness of the film obtained from nanosheet suspension was higher than the one obtained from nanorod suspension. However, the film obtained from ZnO nanorods displayed more uniformity at different voltages in comparison to the film obtained from ZnO nanosheets, which can be due to different active surface area, and also different way of motion under hydrodynamic forces in the suspension.     

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.     

In-situ study of mass and current density for electrophoretic deposition of zinc oxide nanoparticles

In this study, zinc oxide nanoparticles were synthesized by the hydrothermal microwave-assisted method, followed by its deposition using electrophoretic deposition (EPD) method. An investigation of the characteristics of the synthesized nanoparticles was carried out using X-Ray Diffraction (XRD) and Fourier Transform Infrared Spectroscopy (FTIR). The morphology and size distribution of the nanoparticles were examined by the images obtained from Transmission Electron Microscope (TEM). The in-situ variations of mass and current density were investigated during the EPD. The effect of different parameters such as the solvent type at various voltages (20 and 40 V) was investigated on EPD kinetics. By increasing the voltage from 20 to 40 V in the methanol, the mass of the deposited film was increased up to about 38%. Similarly, in the ethanol, an increase equal to 39% was observed. The morphology and porosity of deposited nanoparticles were studied by analyzing the images of the Scanning Electron Microscope (SEM). It was observed that the porosity of the film in the ethanol was more than the methanol, at similar potentials. The increase in porosity at the voltage of 20 V was almost 3.1% and at 40 V, it was approximately 4.4% with respect to methanol. Initial current densities in methanol at 20 and 40 V were about 18 and 29% more than ethanol, respectively.     

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.     

Fabrication of alumina parts by electrophoretic deposition from ethanol and aqueous suspensions

This paper discusses the effect of the properties of alumina suspensions in ethanol and in water, on green and sintered ceramic parts formed by electrophoretic deposition. The results of the study demonstrate that a small amount of water present in ethanol suspensions as a hidden additive due to the hygroscopicity of alumina powder and ethanol can detrimentally affect the behaviour of the suspension, thus lowering the reliability of the process. Electrophoretic deposition from aqueous suspensions appears to be advantageous over ethanol, from a reliability standpoint, and due to higher achievable green and sintered densities of the deposits and higher deposition rates. Dolapix CE64 appears to be superior surfactant in water as it results in deposits with the lowest green and sintered porosities.     

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.     

Fabrication of SiC/diamond composite coatings by electrophoretic deposition and chemical vapor deposition

In this research, SiC/diamond composite coatings were fabricated by a novel procedure that consisted of the electrophoretic deposition (EPD) of diamond particles onto graphite substrates followed by chemical vapor deposition (CVD) of SiC. Various concentrations of MgCl₂ were employed to increase the deposition rate and uniformity of the deposits during the EPD process by giving a positive charge to diamond particles. The CVD of SiC was found to have a tightly connected diamond‐graphite interface and spherical texture. With higher weight fraction of diamond particles deposits, the wear of steel ball increased, while the wear of SiC coating decreased.     

Li-intercalation electrochemical/electrochromic properties of vanadium pentoxide films by sol electrophoretic deposition

Thin films of orthorhombic V₂O₅ have been prepared by sol electrophoretic deposition (EPD) followed by post-treatment at 500 °C. Their electrochemical and optical performances have been investigated for possible applications in electrochemical/electrochromic devices. Li⁺-intercalation properties of the films have been explored in two voltage ranges: 0.4 to −1.1 V and 0.4 to −1.6 V versus Ag/Ag⁺, respectively. High capacities of over 300 mAh/g are acquired in the wider voltage range at a current density of 50 μA/cm² and moderate capacities of 140 and 110 mAh/g are obtained in the narrower voltage range at a current density of 25 and 50 μA/cm², respectively. Electrochemical measurements have shown that the films demonstrate good cyclability in both voltage ranges. X-ray diffraction, scanning electron microscopy and optical spectra have been used to examine the changes in crystallinity, microstructure, morphology and transmittance of the films during cycling. Films cycled to a deeper voltage of −1.6 V versus Ag/Ag⁺ deliver higher capacity with appreciable morphological change, while films cycled in the narrower voltage range show moderate capacity and maintain the morphology, optical responses and crystalline structure. Voltage range can be optimized in between to acquire both high capacity and stability in structure, electrochemical and optical properties. High Li⁺-intercalation capacity and good cyclic stability are attributed to the porous structure of V₂O₅ films prepared by EPD.     

Controlling the degradation rate of bioactive magnesium implants by electrophoretic deposition of akermanite coating

In order to improve the corrosion resistance and the surface bioactivity of biodegradable magnesium alloys, a nanostructured akermanite (Ca₂MgSi₂O₇) coating was grown on AZ91 magnesium alloy through electrophoretic deposition (EPD) assisted with micro arc oxidation (MAO) method. The crystalline structures, morphologies and compositions of samples were characterized by X–ray diffraction, scanning electron microscopy and energy dispersive spectroscopy. The in vitro bio–corrosion (biodegradability) and bioactivity behaviors of samples were investigated by electrochemical and immersion tests. The experimental results indicated that the nanostructured akermanite coating could slow down the corrosion rate and improve the in vitro bioactivity of biodegradable magnesium alloy. Thus, magnesium alloy coated with nanostructured akermanite may be a promising candidate to be used as biodegradable bone implants.     

Texturing of 3Y-TZP zirconia by electrophoretic deposition in a high magnetic field of 17.4 T

Ceramics can be textured during colloidal processing by aligning the suspended particles in a strong magnetic field and retaining this alignment in the green body. Attempts to align tetragonal zirconia particles however were not successful, not even in 12 T magnetic fields. In the current work, monoclinic zirconia was successfully aligned with its (1 0 0) plane perpendicular to the magnetic field direction by electrophoretic deposition (EPD) in a 17.4 T field. Moreover, textured tetragonal zirconia was developed by reactive sintering of undoped pure monoclinic zirconia and co-precipitated 8 mol% yttria-stabilized zirconia. The sintered tetragonal zirconia inherited the alignment of the monoclinic zirconia particle precursor and aligned with its (0 0 1) plane perpendicular to the magnetic field direction. The toughness of the (0 0 1)-oriented 3Y-TZP along the [0 0 1] direction of the textured zirconia was 65% higher than normal to it and 48% higher than the randomly oriented material.     

Oxygen permeation through a CO2‐tolerant mixed conducting oxide (Pr0.9La0.1)2(Ni0.74Cu0.21Ga0.05)O4+δ

A novel K₂NiF₄‐type oxide based on (Pr_0.9La_0.1)₂(Ni_0.74Cu_0.21Ga_0.05)O_4+δ (PLNCG) dense mixed conducting ceramic membrane was successfully prepared through a sol–gel route. The oxygen permeation flux through the membrane swept by pure CO₂ was comparative to that swept by He. The oxygen permeation and the stability of PLNCG under pure CO₂ were investigated in detail. A membrane with a thickness of 0.8 mm was steadily operated for 230 h with a constant oxygen permeation flux of 0.32 mL/(min cm²) at 975^°C using pure CO₂ as sweep gas. X‐ray diffraction shows that PLNCG can maintain its fluorite phase, and no carbonates were observed, even when it was exposed to pure CO₂ for a long time. © 2011 American Institute of Chemical Engineers AIChE J, 58: 2473–2478, 2012