Processing of thin film ceramic membranes for oxygen separation

Processing of dense and thin ceramic membrane layers for high temperature selective oxygen separation is addressed in this study. Mixed oxygen-ionic and electronic conducting perovskite oxide system based on La_0.2Sr_0.8Fe_0.8Ta_0.2O_3−δ composition is employed for processing of structural and functional layers. Special focus is aimed at obtaining thin layer and final microstructure with particle size in the sub-micron range. Thin layer deposition is performed by dip coating technique using stable colloidal suspension of perovskite particles dispersed within ethanol media. Two polymer based surfactants were screened for their effect on particle agglomeration and rheological response. By using optimum quantity of 2.5 wt.% addition of selected surfactant it is possible to obtain dense 15-60 μm thick functional layers. The thermal cycle applied resulted in final particle sizes within sub-micron range. By employing suspension with pore former it was possible to significantly increase the surface area of the functional layer.     

Electrophoretic Deposition (EPD): Mechanisms, Kinetics, and Application to Ceramics

The mechanisms of electrophoretic deposition (EPD) are discussed and their shortcomings identified. The kinetics of the processes involved are analyzed for constant-current and constant-voltage conditions. A method of determining the Hamaker constant of suspended particles is developed by modeling the relationship between the particle inter-action energy and the suspension stability. A three-probe dc technique is used to map the voltage profile around the depositing electrode, and the results are used to explain discrepancies between the calculated and experimentally observed voltage drops during deposition. A mechanism of deposition is proposed based on DLVO theory and particle double-layer distortion/thinning on application of a dc field to the suspension. Kinetic equations are developed for constant-current and constant-voltage EPD using mass balance conditions; these are verified by experiments. After the phenomenon is introduced and discussed, a critique of the application of EPD to the synthesis of ceramic shapes and coatings is given.     

Effect of dispersants on structural integrity of 3D printed ceramics

Ceramic 3D printing based on stereolithography is an excellent alternative to overcome drawbacks of conventional subtractive manufacturing for 3D shape control. Optimization of photocurable ceramic slurry is one of the most essential conditions to achieve favorable 3D printed structures using SL. Homogeneity of ceramic particle dispersion in photocurable resin is particularly important to optimize ceramic suspension. Dispersant plays a significant role in increasing homogeneity. Dispersant in photocurable ceramic resin has an additional effect on photocurability and integrity of 3D printed green body. We herein discuss how dispersants influence 3D printing conditions based on stereolithography using various commercially available dispersants of BYK series such as BYK103, BYK111, BYK180, BYK182, and BYK2001. Both BYK111 and BYK180 showed better performances than others because of their lower volatilities under general temperature condition during a printing process. Both solubility and decomposition temperature of dispersants largely influenced the structural quality after washing and debinding processes. This study provides worthy information to design photocurable ceramic suspension for various types of ceramic materials.     

Surface properties of new green building material after TiO2–SiO2 coatings deposition

The aim of this study was the surface functionalization of a new green ceramic material, obtained using packaging glass waste (PGW), to improve its cleanability. This objective was reached through the deposition by air-brushing of a nanostructured coating based on titania–silica sol–gel suspension. The coatings were deposited on both glazed and unglazed ceramic substrates and the thermal treatment conditions (temperature) were optimized. The obtained results suggest that the applied coatings are transparent and show a good scratch resistance and photocatalitic activity under the tested conditions. The photodegradation process and the mechanical properties are clearly affected by the thermal treatment and thus by the sample surface roughness. The best surface properties were obtained with a thermal treatment at temperature of 150 °C. These coatings do not exhibit either cracks from the substrate. All in all, the developed surface modified ceramic material is attractive as potential sustainable building material.     

Role of Ionic Depletion in Deposition during Electrophoretic Deposition

A model is developed for deposition during the electrophoretic deposition (EPD) process. It suggests that ions that move with the charged particles in suspension are depleted at the depositing electrode, locally changing the pH toward the isoelectric point (pH_iep) to give coagulation. The variation of zeta (zeta) potential is modeled via chemical-equilibrium and surface-adsorption isotherms. The model successfully fits the experimental data for Al₂O₃ particles in ethanol when the Freundlich surface-adsorption isotherm is assumed. Calculations predict the co-ion concentration gradient as a function of location within the suspension, and the deposition time and its role in the coagulatoin process during EPD.     

3D printing of CaO-based ceramic core using nanozirconia suspension as a binder

The 3D printing of a ceramic core with nanoceramic suspension as a binder was performed to investigate a novel method for the fabrication of a complex-shaped ceramic core. Green bodies were printed using CaO powder as a precursor material and nanozirconia-absolute ethyl alcohol solution suspension as a binder. The green bodies were sintered at 1300–1500 °C for 2 h. The effects of binder saturation level on the properties of the sintered bodies were investigated. Increasing the binder saturation level caused decreases in the linear shrinkage of the sintered bodies, but increases in hydration resistance and bending strength. The nanozirconia particles were deposited on the surfaces of the CaO particles and filled the pores of green bodies, and then formed a high melting temperature CaZrO₃ layer with the CaO at the surfaces of the CaO grains, which improved the hydration resistance of the CaO-based ceramic core parts.     

高磁性能铁氧体的3D打印及其应用研究

针对传统陶瓷成型方式难以甚至无法制备高性能复杂结构的不足和局限性,采用一种直写陶瓷3D打印技术,通过配制可打印的陶瓷浆料实现陶瓷结构近净尺寸成型.研究了锌含量对镍锌铁氧体微观形貌、结晶结构及磁性能的影响,结果表明,锌含量x=0.4(Ni1-xZnxFe2O4)时,由于阳离子分布效应,铁氧体饱和磁场强度(Ms)可达到76...     

Direct Writing of Dielectric Ceramics and Base Metal Electrodes

Three-dimensional structures were assembled by direct writing of colloidal gel-based inks of electro-ceramic and metal electrode compositions. The ternary mixtures of BaTiO₃, BaZrO₃, and SrTiO₃ were explored via an active mixing nozzle print strategy that allowed for rapid screening of complex oxide ceramics. In a second experiment, Ni and BaTiO₃ inks were developed from commercially available powders in the form of concentrated, aqueous colloidal gels having shear thinning with yield stress rheology. The different surface chemistry of Ni and BaTiO₃ was accommodated by adsorbing a bi-layer of oppositely charged polyelectrolytes on the BaTiO₃ particles. Alternating layers of metal and ceramic were printed to build a multilayer structure. The multilayer Ni–BaTiO₃ structures were sintered in a reducing atmosphere and the capacitance was measured. These two examples illustrate the use of discrete or graded deposition capabilities of direct writing.     

Highly loaded hydroxyapatite microsphere/ PLA porous scaffolds obtained by fused deposition modelling

The goal of the work was the manufacturing of hydroxyapatite microsphere/polylactic acid (PLA) scaffolds by means of fused deposition modelling (FDM). Micrometer-sized hydroxyapatite spheres synthesized by spray drying (sdHA), were dispersed in PLA by extrusion compounding. Composite filaments were obtained from extrusion which were used in FDM 3D printing for the production of macroporous scaffolds. The sdHA microspheres were used in the composite in order to improve the biomimicry and the bioactivity of the 3D printed scaffold to increase the bone regeneration capacity. Morphological, thermal, physical and mechanical characterizations were performed on the 3D printed composites. Pure PLA scaffolds were 3D printed and used as a reference.Thermal analyses, TGA and DSC evidenced that the glass transition temperature and the degree of crystallinity of PLA were not influenced by the presence of sdHA. Morphological analysis showed a smooth surface of the printed samples when pure PLA was used. A rough surface was found on the PLA/sdHA composites, confirming, the homogeneous dispersion of the ceramic phase in the polymeric matrix. The higher porosity of the composite samples compared to PLA ones, most likely caused a decrease of the mechanical performances of the PLA/sdHA scaffolds. Composite scaffolds displayed stiffness values compatible with that of bone tissue.     

纤维水膜极板表面颗粒沉积脱落特性

以极板表面荷电颗粒电子传递及离子定向迁移为基础,对纤维极板表面沉积颗粒粒径分布、粉尘层堆积形貌、颗粒沉积脱落过程及关键影响因素等进行了研究,并与金属极板进行对比。结果表明：静电场同一位置处（取样点15）,纤维极板表面沉积颗粒物的粒度（6.900 μm）小于金属极板（9.018 μm）,纤维水膜极板对颗粒物的捕集效率更高;与金属极板不同,纤维水膜极板表面粉尘层堆积形貌与电晕电流密度分布无明显关联性。荷电颗粒是以纤维束凸出处为沉积中心,沉积并聚集成球或链珠状,粉尘层厚薄随机且分布松散;纤维极板液体表面浸润和内部扩散,减小了纤维极板表面与粉尘层间静电力,增大了粉尘层内颗粒间黏结力;流动曳力、液桥力、静电力、重力是纤维极板控制粉尘层脱落的关键因素。     

Stereolithography process: Influence of the rheology of silica suspensions and of the medium on polymerization kinetics – Cured depth and width

UV laser stereolithography is a rather new shaping technique that makes it possible the fabrication of complex 3D ceramic structures with a high dimensional accuracy. The green part is built through layer by layer photopolymerization of a light sensitive suspension.Polymerization is thus a critical step to control in this shaping technique. Photopolymerization, with the initiation, propagation and termination reactions, involves the mobility of reactive species and is then sensible to the rheology of the media. This study investigated the influence of the rheology of suspensions of silica particles in an acrylate oligomer and of the intergranular curable organic phase on the UV polymerization. In this respect, the effects of the powder concentration, the state of dispersion and of the dilution of the reactive oligomer on polymerization, are measured.In addition, the influence of the powder loading on the cure depth and cure width, which are respectively pertinent indicators of the reactivity of the suspension and of the dimensional accuracy of the green part, is evaluated.     

Solid Freeform Fabrication of Thin-Walled Ceramic Structures Using an Electrohydrodynamic Jet

A printing device, which operates on an electrohydrodynamic principle, was used to deposit 100 layers of a 10 vol% zirconia suspension. Thus, a wall ∼100 μm in thickness was freeformed. The wall thickness achieved in this work is almost 30% less than that of similar structures built by ink-jet printing and therefore we demonstrate a novel print deposition based solid freeform fabrication method, which can be developed further for preparing fine ceramic structures.     

Electrophoretic deposition of TiO2 nanoparticles in viscous alcoholic media

In the present study, highly viscous alcoholic media, pentanol, hexanol and heptanol were used for electrophoretic deposition of ceramic (TiO₂) nanoparticles as a new approach in the EPD process. Optical and scanning electron microscopy of the obtained deposits at 50 V revealed that layers with a fairly uniform microstructure were obtained in pentanol and hexanol while the layer formed in heptanol suffered from lack of uniformity and did not cover the substrate even at higher voltages up to 200 V. It was also revealed by the atomic force microscope (AFM) studies that surface roughness of the deposited layers decreased with increasing suspension viscosity. This behavior was directly attributed to high viscosity of heptanol which strongly hinders particles movement through the media. The low dielectric constant of heptanol was also considered to decrease particle deposition.     

3D imaging and quantification of interfaces in SOFC anodes

Solid oxide fuel cells (SOFCs) are functional electrochemical conversion devices whose performance is strongly dependent on electrode microstructure. Both the performance and lifetime of these electrochemical devices can be considerably enhanced by the ability to design better electrodes. Data acquired from high resolution 3D imaging techniques were used in the quantification of two electrode structures of different compositions. The quantified nickel-based anode data through the analysis of particle sizes with their metal–metal and ceramic–ceramic neck sizes, metal–ceramic interface sizes, volume fractions, and triple-phase boundary densities, demonstrate it is possible to understand how microstructure contributes to differences observed in electrochemical and mechanical performance; facilitating optimisation of electrode micro/nano structure towards improved performance. In doing so, new insights are gained that could be used to develop better electrodes.     

Aerosol Deposition of Ceramic Thick Films at Room Temperature: Densification Mechanism of Ceramic Layers

A novel method for depositing ceramic thick films by aerosol deposition (AD) is presented. Submicron ceramics particles are accelerated by gas flow up to 100–500 m/s and then impacted on a substrate, to form a dense, uniform and hard ceramic layer at room temperature. However, actual deposition mechanism has not been clarified yet. To clarify densification mechanism during AD, a mixed aerosol of α-Al₂O₃ and Pb(Zr, Ti)O₃ powder was deposited to form a composite layer in this study. The cross-section of the layer was observed by HR-TEM to investigate the densification and bonding mechanism of ceramic particles. As a result, a plastic deformation of starting ceramic particles at room temperature was observed.     

Experimental verification of pH localization mechanism of particle consolidation at the electrode/solution interface and its application to pulsed DC electrophoretic deposition (EPD)

Experimental measurement and verification of the pH localization at the electrode/solution interface was conducted during continuous and pulsed DC electrophoretic deposition (EPD) from aqueous solution. Application of pulsed DC enabled controlling bubble incorporation and obtaining bubble-free deposits during electrophoretic deposition (EPD) from aqueous suspension. The pH localization at the electrode/solution interface on application of electric field was attributed as the underlying mechanism of particle consolidation during continuous as well as pulsed EPD. The suspension pH tends to shift towards isoelectric point (i.e.p.) leading to spontaneous coagulation of particles at the electrode. Application of continuous DC tends to attain the i.e.p. faster and closer compared to pulse DC leading to maximum deposit yield. The kinetics and closeness of attainment of pH towards i.e.p. decreased progressively with decreasing pulse size resulting in a corresponding decrease in deposit yield.     

三维有序二氧化硅胶粒膜在垂直基片上的自组装

A method for preparation of particle crystal film constructed trom monodisperse silica colloidal partices in diameter of about 300 nm is reported. The films were prepared from an ethanol suspension by vertical deposition that relies on capillary forces to assemble colloidal crystal particles on a vertical substrate. The 3D ordered films were characterized by transmission spectra and scanning electric microscope (SEM). The effect of evaporation temperature, particle concentration and sintered temperature on the quality of colloidal particle crystal film was investigated.     

Aerosol deposition of dense lead zirconate titanate thin films at room temperature

Lead zirconate titanate (Pb(Zr,Ti)O₃, PZT) films were grown on silicon 1 0 0 substrate by aerosol deposition, using solid-state reacted powder containing donor oxide Nb₂O₅, while the substrate was maintained at room temperature. The PZT films were simultaneously sintered upon deposition on a highly densified ceramic layer. Crystalline phases of the deposited films have been determined by X-ray diffractometry (XRD), and microstructures analysed by transmission electron microscopy (TEM). The cross-section microstructure consisted of several thin layers, including the PZT film and the platinum electrode and titanium-buffered layers on the substrate. High-resolution images revealed that the PZT layer contained a mixture of randomly oriented grains of nanometre size, which were embedded in an amorphous matrix. In contrast to the conventional liquid-phase sintering mechanism, sintering of the PZT films involved amorphised phases generated by pressure-induced amorphisation (PIA) from plastic deformation when the initial powder particles collided amongst one another upon reaching the silicon substrate during aerosol deposition. An analogy may be drawn to the impact of extraterrestrial meteorites in which diaplectic glass, i.e., amorphised phase, was formed and retained metastably at room temperature. The individual PZT grains were joined with the amorphised phase(s) and sintered to become a dense, thin film on the silicon substrate.     

Electrophoretic deposition of yttria-stabilised zirconia powder from aqueous suspensions for fabricating ceramics with channel-like pores

Electrophoretic deposition with simultaneous gas bubble formation by electrolysis can be used for producing ceramic green bodies, typically few millimetres in thickness, with unidirectionally aligned channel-like pores. The method is successfully applied to yttria-stabilised zirconia. Two types of aqueous suspension compositions are investigated. Suspensions with acetic acid additions are particularly suitable for forming green bodies with fine pore channels. Only small amounts of acetic acid, promoting the gas evolution, are needed for this purpose. Dissolution of yttria in the acidic range has to be considered, but the required low acid concentrations do not measurably affect the yttrium content of the deposits. Yttria dissolution can be minimised by a suspension composition containing an anionic polyelectrolyte and ammonia instead of acetic acid. The ammonia concentration influences the size of the tubular pores of the deposits formed under constant-voltage conditions. Using structured deposition electrodes, the regularity of the pore arrangement can be enhanced.     

Evaluation of the pore morphology formation of the Freeze Foaming process by in situ computed tomography

The so-called Freeze Foaming method aims at manufacturing ceramic cellular scaffolds for diverse applications. One application is dedicated to potential bone replacement material featuring open, micro and interconnected porosity. However, the main challenges of this foaming method is to achieve a homogeneous pore morphology. In a current project, the authors throw light on the bubble/pore and strut formation of this process by in situ computed tomography. This allows for evaluating varying process parameter’s effects on the growth of the ceramic foam during the foaming process. As first result and basis for CT analysis, a stable and reproducible model suspension was developed which resulted in reproducible foam structures. In dependence of selected process parameters like pressure reduction rate or air content in the ceramic suspension resulting Freeze Foams became adjustable with regard to their pore morphology. Pore size and distribution data as well as the porosity were characterized and evaluated accordingly.