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.     

Photocatalytic enamel/TiO2 coatings developed by electrophoretic deposition for methyl orange decomposition

The aim of this study was to obtain photocatalytic coatings, capable to decompose organic pollutants, through Electrophoretic Deposition (EPD) of enamels containing respectively 0%, 5%, 10%, 15% (in wt%) of TiO₂ onto carbon steel substrates. High quality and homogeneous coatings were obtained by applying 12.5?V during 10?s, as the best EPD conditions. The layers were subsequently heat treated at 740?°C for 10?min, in order to obtain dense glazes.Rietveld refinement of XRD patterns and Raman results show that, after the heat treatment at 740?°C, TiO₂ mostly exists as anatase, responsible of the photocatalytic effect. Semi-quantitative chemical analysis indicate segregation of TiO₂ on the coatings surface, reaching saturation in the sample with 10?wt% TiO₂. FEG-SEM observations reveal rod-like and spherical Ti-rich phases along the cross section of the coatings; some Ti was also dissolved into the enamel. 3D topographical mapping shows that, by adding TiO₂, surface roughness increases significantly.Photocatalytic tests were carried out using a 2?×?10^?5 M aqueous solution of Methyl Orange (MO) as an organic pollutant. By comparing the decomposition rate of MO achieved with the pure enamel (0% of TiO₂) and with the sample with 10% of TiO₂, it was shown that the addition of 10% of TiO₂ results in 90% photocatalytic efficiency.Moreover, the permeation of organic compounds and their UV degradation were studied by measuring the water contact angle onto the enamel surface directly after dipping into oleic acid and after various UV irradiation times. The longer the UV irradiation time, the lower the contact angle, down to a minimum of 14.54° after 8?h of UV irradiation. This means, the compound was initially adsorbed on the enamel/TiO₂ coating surface (10?wt% TiO₂) but was efficiently decomposed upon UV irradiation.     

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.     

在钛基上电泳沉积羟基磷灰石生物陶瓷涂层的研究

将羟基磷灰石(HAP)电泳沉积在钛基材上，得到了结构稳定的HAP生物陶瓷涂层。研究了电场强度、悬浮液温度、电泳时间、分散介质及HAP浓度对涂层形貌的影响。通过红外光谱仪(FTIR)和X射线衍射仪(XRD)对涂层的组成及结构进行了分析，并采用扫描电镜(SEM)对涂层煅烧前后的微观形貌进行了观察。结果表明：在正丁醇作为分散剂、悬浮液温度30℃、电场强度250V／cm、电泳时间300s以及HAP浓度5．0g／L的条件下可制得形貌较好的HAP生物陶瓷涂层；经二次电泳沉积及煅烧后得到的HAP生物陶瓷涂层均匀致密．     

Microstructure and mechanical properties of continuous carbon fiber-reinforced ZrB2-based composites via combined electrophoretic deposition and sintering

A process combining electrophoretic deposition (EPD) with hot pressing (HP) was developed to fabricate continuous carbon fiber-reinforced ZrB₂-based composites (C_f/ZrB₂-based composites). ZrB₂-based ultra-high temperature ceramic (UHTC) particles were uniformly pre-coated on continuous carbon fibers via EPD. Then, the UHTC-coated carbon fibers were stacked and hot pressed to prepare the C_f/ZrB₂-based composites. Microstructure observations revealed that almost no micro-pores were found in the inter-bundle and intra-bundle regions of fibers after HP. The flexural strength, fracture toughness and the work of fracture of the C_f/ZrB₂-based composite were measured as 199 ± 26 MPa, 6.71 ± 1.29 MPa·m^1/2, and 754 ± 58 J/m², respectively. Based on the observations of non-brittle fracture behavior, fractured morphology and crack propagation, the enhanced fracture properties were mainly attributed to the multiple toughening mechanisms, such as fiber pull-out, fiber bridging, crack deflection and branching along the interfaces.     

Effects of suspension properties on the fabrication of Yb2Si2O7 coatings using electrophoretic deposition

This study examines the electrophoretic deposition of Yb₂Si₂O₇ particles on SiC substrates to produce Environmental Barrier Coatings. To prepare crack-free and homogeneous green coatings, the effect of the solvent, dispersant concentration, and pH were investigated. Ethanol provided a well-dispersed suspension and crack-free coating which was shown by sedimentation tests and microstructure analysis. The effect of the dispersant concentration was investigated with zeta potential measurement and microstructure analysis with a concentration above 0.5 g/L resulting in higher ionic strength and producing cracked and uneven coatings. The ionic strength was also associated with the powder packing density with larger indentation impressions measured for loosely packed coatings. The deposition rate depended on the suspension properties influenced coating integrity with delamination evidenced by analysing the current density drop during deposition. Sintering of the green coatings having different densities and microstructure showed their importance in the preparation of uniform and dense sintered coatings.     

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.     

Effect of suspension medium on the electrophoretic deposition of hydroxyapatite nanoparticles and properties of obtained coatings

The suspensions of hydroxyapatite (HA) nanoparticles were prepared in different alcohols. The zeta potential of HA nanoparticles was the highest in butanolic suspension (65.65 mV) due to the higher adsorption of RCH₂OH₂⁺ species via hydrogen bonding with surface P3OH group of HA. Electrophoretic deposition was performed at 20 and 60 V/cm for different times. Deposition rate was faster in low molecular weight alcohols due to the higher electrophoretic mobility of HA nanoparticles in them. The coating deposited from butanolic suspension had the highest adhesion strength and corrosion resistance in SBF solution at 37.5 °C. The surface of this coating was covered by apatite after immersion in SBF solution for 1 week.     

Thermal stability and mechanical properties of HVOF/PVD duplex ceramic coatings produced by HVOF and cathodic vacuum arc

Duplex ceramic coatings, consisting of an inner NiCr-Cr₃C₂-based coating and an outmost AlCrN film, were produced on the steel substrate in succession by velocity oxygen-fuel spraying (HVOF) and cathodic vacuum arc methods, and then isochronally annealed at annealing temperatures below 900 °C for 2 h. The thermal stability and mechanical properties of the annealed samples were systematically studied by means of X-ray diffraction, Optical microscope and transmission electron microscope, in association with mechanical property measurements. The results show that the microstructure, phase evolution and mechanical properties of duplex ceramic coatings are significantly dependent on the annealing temperature. Metastable fcc-AlCrN solid solution in AlCrN film first decomposes to rich-Al and rich-Cr domains by spinodal decomposition at 700 °C, leading to a notable increase in hardness due to its smaller grain size and high elastic strain field, and then to equiaxed hcp-AlN and Cr₂N by the nucleation and growth at 900 °C, leading to a notable decrease in hardness due to the recrystallization and the formation of hcp-AlN. Meanwhile, the both decarburization of Cr₃C₂ to Cr₇C₃ occurs at 800 °C, but becomes more intensive at 900 °C, leading to a notable loss in hardness. In addition, the dissolution of Cr₃C₂ produces high density of porosity, which also reduces the hardness. The hardness tests show the following ordering of load-bearing capacity for the duplex ceramic coatings: 700 °C>As-deposited >800 °C>900 °C. Tribological property measurements demonstrate that the wear resistance of the tested duplex ceramic coatings obeys the following ordering: 700 °C>As-deposited >800 °C>900 °C. The improved wear resistance is due to high surface hardness, load-bearing capacity and thermal stability. In addition, the wear mechanisms are shown.     

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.     

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.     

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.     

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.     

Structural characterization of YSZ/Al2O3 nanostructured composite coating fabricated by electrophoretic deposition and reaction bonding

Suspension of YSZ and Al particles in acetone in presence of 1.2 g/l iodine as dispersant was used for electrophoretic deposition of green form YSZ/Al coating. Results revealed that applied voltage of 6 V and deposition time of 3 min were appropriate for deposition of green composite form coating. After deposition, a nanostructured dense YSZ/Al₂O₃ composite coating was fabricated by oxidation of Al particles at 600 °C for 2 h and subsequently sintering heat treatment at 1000 °C for 2 h. Melting and oxidation of Al particles in the green form composite coating not only caused reaction bonding between the particles but also lowered the sintering temperature of the ceramic coating about 200 °C. The EDS maps confirmed that the composition of fabricated coating was uniform and Al₂O₃ particles were dispersed homogenously in YSZ matrix.     

Thermal behaviour of multilayer and functionally-graded YSZ/Gd2Zr2O7 coatings

Zirconates with pyrochlore structure, such as Gd₂Zr₂O₇, are new promising thermal barrier coatings because of their very low thermal conductivity and good chemical resistance against molten salts. However, their coefficient of thermal expansion is low, therefore their thermal fatigue resistance is compromised. As a solution, the combination of yttria-stabilised zirconia (YSZ) and Gd₂Zr₂O₇ can reduce the thermal contraction mismatch between the thermal barrier coating parts.In the present study, two possible designs have been performed to combine YSZ/Gd₂Zr₂O₇. On the one hand, a multilayer coating was obtained where YSZ layer was deposited between a Gd₂Zr₂O₇ layer and a bond coat. On the other hand, a functionally-graded coating was designed where different layers with variable ratios of YSZ/Gd₂Zr₂O₇ were deposited such that the composition gradually changed along the coating thickness.Multilayer and functionally-graded coatings underwent isothermal and thermally-cycled treatments in order to evaluate the oxidation, sintering effects and thermal fatigue resistance of the coatings. The YSZ/Gd₂Zr₂O₇ multilayer coating displayed better thermal behaviour than the Gd₂Zr₂O₇ monolayer coating but quite less thermal fatigue resistance compared to the conventional YSZ coating. However, the functionally-graded coating displays a good thermal fatigue resistance. Hence, it can be concluded that this kind of design is ideal to optimise the behaviour of thermal barrier coatings.     

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.     

Characterization of hydroxyapatite-tantalum pentoxide nanocomposite coating applied by electrophoretic deposition on Nitinol superelastic alloy

In this study, natural hydroxyapatite (nHA) and nHA-20?wt.%Ta₂O₅ nanocomposite coatings were deposited via electrophoretic deposition (EPD) on the NiTi substrate. The suspensions of nHA and nHA-Ta₂O₅ nanoparticles were prepared in n-butanol as a medium with different contents (0, 4, 8, 12, 16, and 20?mL/L) of triethanolamine (TEA) as a dispersant. The most stable suspensions of nHA and nHA-Ta₂O₅ nanoparticles were achieved with 16?mL/L TEA according to the sedimentation test and zeta potential measurement results. The enhanced colloidal stability of nanoparticles in n-butanol by TEA addition was investigated by FTIR analysis. The highest in-situ EPD kinetics were accomplished from suspensions containing an optimum concentration of dispersant. The phase compositions and microstructures of the coatings, before and after sintering under 1.4?×?10^?6?mbar vacuum at 800?°C for 1?h, were perused using XRD and FESEM, respectively. The results of the nano-scratch analysis showed the highest critical distance of delamination (0.38?mm), normal load before failure (133?mN) as well as the critical contact pressure (7.12?GPa) for nHA-Ta₂O₅ coating on the NiTi. The concentration of the released Ni ions from passivated-NiTi with nHA coating in PBS after 30 days of immersion reduced from 45.72 to 5.62 μg/Lcm² by introducing Ta₂O₅ in nHA matrix. On the other hand, the improved corrosion behavior of passivated-NiTi with nHA-Ta₂O₅ coating in comparison to that of with nHA deposit was explained with the lower amount of open porosities in the microstructure. The biocompatibility of the nHA and nHA-Ta₂O₅ surfaces were studied by osteoblast cell attachment during 7 days of culturing.     

基于电泳沉积工艺的低粘附抗菌涂层的制备

低表面能涂层因其优异的防污自清洁能力而受到广泛关注,但现有涂层存在易被细菌和真菌等微生物破坏而导致防污效果下降的问题,因此构建防污抗菌涂层具有深远的意义。本文基于电泳沉积工艺,将乙烯基硅油改性聚丙烯酸酯和固化剂沉积到导电基底,进一步负载纳米银杀菌剂,经过交联固化后获得了兼具抗细菌粘附与杀菌功能的涂层。采用傅里叶变换红外光谱仪(FT-IR)、核磁共振波谱仪(NMR)和扫描电子显微镜(SEM)等对涂层的结构和形貌进行了系统的表征,结果表明,成功合成了兼具低粘附与杀菌功能涂层。涂层表面具有优异的防油污、细菌及血液粘附的能力,涂层对大肠杆菌和金黄色葡萄球菌的抗细菌粘附效果达到99.9%以上。即使经过强酸、强碱等极端环境以及摩擦3000次后,涂层表面仍具有优异的防液体粘附效果。     

镁基材料表面微弧氧化生物医用陶瓷涂层研究进展

利用微弧氧化技术在镁基材料表面原位生成陶瓷膜层,能显著增强镁基材料的耐磨性、耐腐性、生物相容性等表面性能,在医用镁基材料表面改性中具有广泛的应用前景.本文主要对镁基材料表面微弧氧化所用的电解液组成、陶瓷膜的结构组成、复合生物涂层及其生物相容性的研究现状进行了评述,并对今后的研究前景进行了展望.     

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.