Fabrication of finely structured silicon-supported SOFC with anode deposited by multi-phase plasma spraying

The mechanically mixed NiO/YSZ powder was usually used as the anode material of atmospheric plasma sprayed (APS) solid oxide fuel cells (SOFC). Big particles and the non-uniform distribution of the pores were observed in the resultant anode layer. To overcome the limitations, a method of fabricating anode layer by multi-phase plasma spraying (MPS) was proposed in this paper. The NiO and YSZ powders were delivered into plasma jet by a separate injection, where nitrogen carrier was employed to feed micrometer-sized NiO powder and liquid carrier was to feed submicrometer-sized YSZ powder. Suspension plasma spraying (SPS) was applied to fabricate dense electrolyte layer. The microstructure and composition of coatings were characterized by SEM and EDS. The results showed that finely structured anode layer with small particle size (d ∼ 2 μm) was achieved by the MPS method. The MPS anode layer was porous with the porosity of 32.1% while the APS anode layer was 22.6%. Three kinds of elements (Ni, Y, Zr) were observed in the MPS anode layer and the NiO content was calculated to be 49.6 wt%. In the SPS process, the suspension flow rate was matched to the plasma gas flow rate to obtain proper injection condition.     

Microstructure characterization and electrical conductivity of electroless nano Ni coated 8YSZ cermets

Using a common electroless bath, Ni-8YSZ (Ni-8 mol% yttria stabilized zirconia) composite nano powder have been synthesized without use of any expensive sensitizing agent. HRTEM micrographs indicated that the coating morphology of Ni nano particles on the 8YSZ showed a spotty, discontinuous distribution and the Ni nano particles appeared as a crystalline phase. The amount of Ni in the composite powders was varied from 36-51 wt.% by changing the substrate powder loading in the electroless bath. Bar type samples were prepared by uniaxial pressing and sintering at 1300 °C for 2 h with these coated powders. The cubic (c)-zirconia was found to partially dissociate into monoclinic (m)-zirconia on sintering with Ni content 41% or higher and also increases with the increase of Ni content. The microstructure of each Ni-YSZ cermet after reduction in a H₂ + Ar gas atmosphere showed dual scale porosity (micro and submicron porosity). The Ni-8YSZ cermet samples showed metallic electrical conduction behavior, proving the percolation capability of the synthesized nano composite.     

Structural investigations of oxidative behavior on nanocrystalline nickel

We have reported a comprehensive study of the structural, magnetic and electrical properties of Ni (core)/NiO (shell) particles, synthesized by control oxidation of ball milled nanocrystalline (nc-) Ni particles in air. A reaction of Ni + (1/2)O₂ → NiO is suspected to occur in the oxidation reaction at the temperature range of 300-800 °C. The phases of the Ni/NiO particles are composed of fcc-Ni and fcc-NiO. The phase compositions of the Ni/NiO particles change with annealing temperature. The Ni/NiO particles have a core-shell monomorphic flower-like microstructure with an average diameter of 20-80 nm. The size reduction and oxidation of the nc-Ni particles leads to a change in microstructure and thermal stability compared to bulk Ni. Thermogravimetric and differential scanning calorimetery analysis are applied to determine the thermal behavior of composites. The initial oxidation of nc-Ni particles is observed to occur around 325 °C (near Curie temperature). Anomalous magnetic and electric behavior is observed at room temperature for the nc-Ni and Ni/NiO particles.     

Growth and stability of CVD Ni3N and ALD NiO dual layers

Multilayers of combinations of NiO, Ni₃N and Ni have been grown by ALD and CVD techniques at 250 °C. Layers of low thermodynamical stability have been modified to reach the target structures. The Ni layers have been formed by decomposition of metastable Ni₃N layers, i.e., the Ni₃N layers act as precursor for Ni film growth. This new reaction route enables production of Ni/NiO layer structures by chemical means for the first time. By choosing suitable low temperature annealing conditions like 180 °C in a 1 Torr hydrogen atmosphere, good control of the interfaces is obtained.It has also been shown that it is possible to grow multilayers which are ordered both with respect to each other, the substrate and the Ni films. For instance the following structure Ni (111)/NiO (111)/α-Al₂O₃ (00l) has been grown. Moreover, another new reaction route is deposition of thin epitaxial seed layers of NiO (111) for subsequent growth of Ni₃N at a high rate. Single phase Ni (111) films could then be obtained by decomposition at 350 °C of the Ni₃N layers. The demonstrated reaction routes for film growth in the Ni-O-N system can also be applied in several similar systems.     

Manufacturing of high performance solid oxide fuel cells (SOFCs) with atmospheric plasma spraying (APS)

The potential of atmospheric plasma spraying (APS) technology has been investigated for the manufacture of anode, electrolyte and cathode of a solid oxide fuel cell. As the substrate a tape-casted FeCr alloy was used. It turned out that all layers can be applied by this technique, however, the APS cathode layer, although applied by suspension plasma spraying led to cells with rather low performance. Much better cell characteristics could be obtained by using screen-printed LSCF cathodes, which do not need any additional thermal treatment.Anode layers with high electrochemical activity were produced by separate injection of NiO and YSZ powders. The manufacturing of gastight electrolyte layers was a key-issue of the present development. As APS ceramic coatings typically contain microcracks and pores their leakage rate is not sufficiently low for SOFC applications.Based on the understanding of the formation of defects during spraying an optimized spraying process was developed which led to highly dense coatings with the appearance of a bulk, sintered ceramic. Open cell voltages above 1 V proofed the low leakage rates of the rather thin (< 50 μm) coatings. With these cells having a screen-printed cathode an output power of 500 mW/cm² could be achieved at 800 °C.It turned out that the long-term stability of the metal substrate based APS SOFCs was rather poor. The aging of the cells was probably due to interdiffusion of anode and substrate material. Hence, diffusion barrier was applied by APS between substrate and anode. These layers were very effective in reducing the degradation rate. For these cells the output power reached 800 mW/cm².     

Catalysts characteristics of Ni/YSZ core-shell according to plating conditions using electroless plating

This study aims to develop an anode catalyst for a solid oxide fuel cell (SOFC) using electroless nickel plating. We have proposed a new method for electroless plating of Ni metal on yttria-stabilized zirconia (YSZ) particles. We examine the uniformity of the Ni layer on the plated core-shell powder, in addition to the content of Ni and the reproducibility of the plating. We have also evaluated the carbon deposition rate and characteristics of the SOFC anode catalyst. To synthesize Ni-plated YSZ particles, the plated powder is heat-treated at 1200 °C. The resultant particles, which have an average size of 50 μm, were subsequently used in the experiment. The size of the Ni particles and the Ni content both increase with increasing plating temperature and plating time. The X-ray diffraction pattern reveals the growth of Ni particles. After heat-treatment, Ni is oxidized to NiO, leading to the co-existence of Ni and NiO; Ni₃P is also observed due to the presence of phosphorous in the plating solution. Following heat treatment for 1 h at 1200 °C, Ni is mostly oxidized to NiO. The carbon deposition rate of the reference YSZ powder is ~135%, while that of the Ni-plated YSZ is 1%-6%.     

Surface morphology and structure of Ni-P, Ni-P-ZrO2, Ni-W-P, Ni-W-P-ZrO2 coatings deposited by electroless method

Electroless binary Ni-P and ternary Ni-W-P alloy coatings and electroless composite (Ni-P-ZrO₂ and Ni-P-W-ZrO₂) nickel coatings were deposited. Baths with aminoacetic acid as the complexing agent were used. ICP measurements showed that the P content depending on the type of coating is in a range of 4.7-6.3 wt.% (at pH = 6, t = 75 °C). The tungsten content is around 1-2 wt.%. SEM examinations show that the electroless Ni-P coating has the most fine-grained structure. Grains in the form of microspheroids 20 μm in size are characteristic of the Ni-P-ZrO₂ coating. X-ray diffraction patterns show that for all the obtained coatings peak Ni(111) located around 2θ = 44° is the most intensive. After the coatings are heat treated at 400 °C for 1 h the peak becomes even sharper. The heat treatment results in a nearly double increase in crystallite size. The quaternary coatings' abrasion resistance is determined by the second-phase (ZrO₂) particles present in them.     

Analysis of macro segregation in twin-roll cast aluminium strips via solidification curves

A porous NiO/yttria-stabilized zirconia (YSZ) anode substrate for zirconia-based tubular solid oxide fuel cells (SOFCs) was prepared by the gelcasting. The effect of the impregnation of SDC in the substrate was studied. Electrochemical impedance spectroscopy and I–V and I–P curves of the cells were measured. Scanning electron microscopy (SEM) was used to observe the microstructures. The results indicate that the performance of the cell can be significantly improved by incorporating the nano-structured SDC particles in the substrate. The peak power density of the cell is increased by about 60% and the area specific resistance (ASR) decreased by about 47% at 700 °C, compared with the unmodified cells. It is explained as the extended triple-phase boundary (TPB) in the anode substrate and the excellent electrocatalytic property of SDC. It is also found that the nano-scale SDC particles change a lot during the reduction of the anode substrate, and the morphology of the resultant SDC particles on the metal Ni is significantly different from that on the YSZ. After the long-term operation, the morphology of the SDC particles on the Ni changes again, but that on the YSZ keeps almost unchanged.     

Structural evaluation of brushite/gelatine coatings on graphite substrate

Brushite is one of the most frequently formed products of the electrochemical deposition. It has shown excellent biological behaviour of calcium phosphate coatings on carbon composites. Calcium phosphate coatings were obtained by the electrochemical deposition from the solution of calcium and phosphate ions at pH = 2.4 and with 0.2 or 1 wt.% gelatine addition. Graphite substrate was used as cathode and Pt basket as anode. Electrochemical deposition of brushite/gelatine composite layer was carried out at current densities from 5 to 20 mA/cm². Coatings were examined before and after annealing at 850 °C in Ar. The large channels were observed in coatings at higher concentrations of gelatine and high current densities in microstructure. The adhesive strength of thin brushite/gelatine coating was around 7 MPa. Linear dependence of deposit weight increase with electrolysis time was observed. Similarly, the gelatine content in coating rose linearly with gelatine concentration in electrolyte. After annealing of coatings at 850 °C in argon, the brushite was transformed to hydroxyapatite and CaO, the size of the needle-like brushite particles decreased and small spherical or regular shaped particles of CaO were formed. The weak bonding of thermal treated brushite/gelatine deposits to graphite was found.     

Development and microstructure optimization of atmospheric plasma-sprayed NiO/YSZ anode coatings for SOFCs

In this paper, preparation and characterization of porous anode layers with uniform phase distribution are discussed for solid oxide fuel cell (SOFC) application. The Ni/8YSZ cermet coatings were fabricated by atmospheric plasma spray (APS) process using oxidized nickel coated graphite (Ni-graphite) and 8 mol% yittria — stabilized zirconia (8YSZ) blend as feedstock. To control the microstructure of the coating, the nickel coated graphite with low density was used as a starting feedstock instead of conventional pure nickel (Ni) powder. To balance the conductivity, uniform porosity, and structural stability of the coatings, the effects of process parameters such as hydrogen gas flow rate, stand off distance and pore formation precursor (graphite) addition on the microstructures of the resulting coatings are investigated. The results show that the anode coatings with high conductivity, structural stability and porosity could be deposited with moderate hydrogen gas flow rate and short stand off distance.     

Preparation of YSZ coatings by thermal pressure and filtration of sol-gel paint (TPFSP) for thermal barrier application

Thick YSZ ceramic coatings were prepared by thermal pressure and filtration of sol-gel paint (TPFSP), a modified sol-gel composite coating technique. SEM results show that the coatings were dense and crack-free by using paints of high mass ratios of YSZ powder to Zr-Y oxide in sol and high pressures. And the cross-sectional detail of coatings exhibited that the microstructure was consisted of micro/nano-size ceramic particles and micro-pores. The thermal insulation tests indicated that mass ratio of YSZ powder to Zr-Y oxide in sol was in inversely linear relationship with temperature drop per micron thickness. The coating showed good adherence with alloy substrate and maintained structural integrity when exposed at 1050 °C for 200 h. The cyclic oxidation test also indicated that both of oxidation resistance and spallation resistance for YSZ coated specimens were greatly improved. The TPFSP process could be a promising method to prepare TBCs for wide applications.     

Characteristics of the nanostructures in thermal sprayed hydroxyapatite coatings and their influence on coating properties

There are generally two methods for depositing nanostructured coatings, retaining the nanostructures from starting feedstock and forming novel nanostructures through quenching. The present study utilized spray-dried nanostructured hydroxyapatite (nSD-HA) feedstock for coating/splat deposition. The nanostructures were characterized by transmission electron microscopy (TEM) and field emission scanning electron microscopy (FESEM). Results revealed that the rod-shaped nano-grains in the starting HA particles (< 500 nm in length and 40-70 nm in diameter) encountered two major experiences: enlargement due to unmelt state and reorganization due to melting-solidification. The molten part of the particles results in formation of spherical nanosized particles with grain sizes of 30-110 nm. TEM observation of the HA splats demonstrates consistent nanostructures. The unmelted part of individual nSD-HA particles showed significantly enlarged grains along radial direction (< 550 nm in length and < 400 nm in diameter). In addition, individual hexagonal grains were observed in the HVOF coating made from 30 ± 10 μm powder. The grains have the size of < 250 nm in height and < 50 nm in side length and are perpendicular to the coating/substrate interface. The nanostructures within the coatings contribute to an increased Young's modulus with up to 60.11 GPa, however, they showed detrimental effect on adhesion of the coatings. In vitro cell culturing revealed marked attachment and proliferation of the osteoblast cells on the nanostructured coatings. However, the results suggest that the nanostructures possess less importance than the phases (preferably high content of crystalline HA) on enhancing the cell proliferation.     

Cyclic oxidation behavior and thermal barrier effect of YSZ-(Al2O3/YAG) double-layer TBCs prepared by the composite sol-gel method

Novel YSZ (6 wt.% yttria partially stabilized zirconia)-(Al₂O₃/YAG) (alumina-yttrium aluminum garnet, Y₃Al₅O₁₂) double-layer ceramic coatings were fabricated using the composite sol-gel and pressure filtration microwave sintering (PFMS) technologies. The thin Al₂O₃/YAG layer had good adherence with substrate and thick YSZ top layer, which presented the structure of micro-sized YAG particles embedded in nano-sized α-Al₂O₃ film. Cyclic oxidation tests at 1000 °C indicated that they possessed superior properties to resist oxidation of alloy and improve the spallation resistance. The thermal insulation capability tests at 1000 °C and 1100 °C indicate that the 250 μm coating had better thermal barrier effect than that of the 150 μm coating at different cooling gas rates. These beneficial effects should be mainly attributed to that, the oxidation rate of thermal grown oxides (TGO) scale is decreased by the “sealing effect” of α-Al₂O₃, the “reactive element effect”, and the reduced thermal stresses by means of nano/micro composite structure. This double-layer coating can be considered as a promising TBC.     

Suspension Plasma Spray and Performance Characterization of Half Cells with NiO/YSZ Anode and YSZ Electrolyte

The use of a liquid feedstock carrier in suspension plasma spray (SPS) permits injection of fine powders, providing the possibility of producing sprayed coatings that are both thin and dense and have fine microstructures. These characteristics make SPS an attractive process for depositing highly efficient electrodes and electrolytes for solid oxide fuel cell (SOFC) applications. In this study, NiO-yttria stabilized zirconia (YSZ) anode and YSZ electrolyte half cells were successfully deposited on porous Hastelloy X substrates by SPS. The NiO-YSZ anode deposition process was optimized by design of experiment. The YSZ electrolyte spray process was examined by changing one parameter at a time. The results from the design-of-experiment trials indicated that the porosity of the as-deposited coatings increased with an increase of suspension feed rate while it decreased with an increase of total plasma gas flow rate and standoff distance. The deposition rate increased with an increase of total plasma gas flow rate, suspension feed rate, and standoff distance. The microstructure examination by SEM showed that the NiO and YSZ phases were homogeneously distributed and that the YSZ phase had a lamellar structure. It was observed that the density of the YSZ electrolyte layer increased as input power of the plasma torch increased. Electrochemical characterization of the fabricated cells indicated that an open cell voltage of 0.989 V at 500 °C and a peak power of 0.610 W/cm² at 750 °C were reached.     

La2O3-modified YSZ coatings: High-temperature stability and improved thermal barrier properties

Lanthana precursor was coated on yttria-stabilized-zirconia (YSZ) powders by wet chemical infiltration, and was introduced to the crystalline structure and grain boundaries of YSZ after plasma spraying of thermal barrier coatings (TBCs). The microstructural stability and thermal barrier properties of this new kind of TBCs were studied under different annealing conditions. It demonstrates that the La₂O₃ surface coating restrains grain growth of YSZ during both deposition and post-annealing processes, compared to a TBC obtained from commercially available unmodified YSZ powders. According to the composition analysis, lanthana partially dissolved in the zirconia matrix after heat treatment. The thermal diffusivity of YSZ coating significantly decreased after lanthana modification, typically from 0.354 mm² s^− 1 for an unmodified sample to 0.243 mm² s^− 1, reflecting a decrease of 31%. Even after annealed at 1200 °C for 50 h, the thermal diffusivity of modified coatings still shows a reduction of 25% than unmodified samples.     

Reaction, transformation and delamination of samarium zirconate thermal barrier coatings

The rare earth zirconates have attracted interest for thermal barrier coatings (TBCs) because they have very low intrinsic thermal conductivities, are stable above 1200 °C and are more resistant to sintering than yttria-stabilized zirconia (YSZ). Samarium zirconate (SZO) has the lowest thermal conductivity of the rare earth zirconates and its pyrochore structure is stable to 2200 °C but little is known about its response to thermal cycling. Here, columnar morphology SZO coatings have been deposited on bond coated superalloy substrates using a directed vapor deposition method that facilitated the incorporation of pore volume fractions of 25 to 45%. The as-deposited coatings had a fluorite structure which transformed to the pyrochlore phase upon thermal cycling between 100 and 1100 °C. This cycling eventually led to delamination of the coatings, with failure occurring at the interface between the TGO and a “mixed zone” that formed between the thermally grown alumina oxide (TGO) and the SZO. While the delamination lifetime increased with coating porosity (reduction in coating modulus), it was significantly less than that of similar YSZ coatings applied to the same substrates. The reduced life resulted from a reaction between the rare earth zirconate and the alumina-rich bond coat TGO, leading to the formation of a mixed zone consisting of SZO and SmAlO₃. Thermal strain energy calculations show that the delamination driving force increases with TGO and mixed layer thicknesses and with coating modulus. The placement of a 10 μm thick YSZ layer between the TGO and SZO layers eliminated the mixed zone and restored the thermal cyclic life to that of YSZ structures.     

Microstructural evolution of 7 wt.% Y2O3-ZrO2 thermal barrier coatings due to stress relaxation at elevated temperatures and the concomitant changes in thermal conductivity

The purpose of this study was to evaluate the combined effect of stress and temperature on the microstructure of air plasma-sprayed 7 wt.% Y₂O₃-ZrO₂ thermal barrier coatings, and relate microstructural changes to the thermal conductivity, k_th. To simulate TBC service conditions, stand-alone tubes of YSZ were stress relaxed, starting from a compressive stress of 60 MPa, at temperatures of 1000 °C or 1200 °C. The duration of the stress relaxation test was either 5 min or 3 h. Detailed scanning electron microscopy (SEM) and Porod's specific surface area (SSA) analysis of small angle neutron scattering (SANS) results were used to determine which void systems, either interlamellar pores or intralamellar cracks, contributed to the observed relaxation of stress in the coatings. SEM investigations revealed closure of intralamellar cracks located perpendicular to the stress direction. For thinner YSZ coatings, SANS measurements indicated a statistically significant reduction in the total SSA and SSA associated with intralamellar cracks after stress relaxation at the times, temperatures, and stress investigated compared to those samples that were exposed to identical times and temperatures, but no stress. The SSA associated with the interlamellar pores was not significantly smaller in YSZ coatings stress relaxed from 60 MPa at 1200 °C for 3 h compared to as-sprayed coatings. The thermal conductivity of the coatings was strongly influenced by stress, with increases in k_th observed after only 5 min at 60 MPa and 1200 °C. Reductions in the total SSA were directly linked to increases in k_th.     

Thermal shock behavior of nanostructured and conventional Al2O3/13 wt%TiO2 coatings fabricated by plasma spraying

The thermal shock behavior of three kinds of Al₂O₃/13 wt%TiO₂ coatings fabricated by plasma spraying was studied in this paper. One kind of those coatings was derived from conventional fused and crushed feedstock powder available commercially; the other two kinds of coatings were derived from nanostructured agglomerated feedstock powders. These two nano coatings possess moderate pores and pre-existing microcracks, they were composed of fused structure and three-dimensional net or skeleton-like structure. For conventional coatings, the pores and pre-existing cracks were bigger, sharp-point and mostly distributed between splats. Thermal shock tests for the three coatings were performed by water quenching method. Testing result showed the two kinds of nano coatings had much higher thermal shock resistance than the conventional coatings. The improved thermal shock resistance for nano coatings could attribute to their improved microstructure and crack propagation mode. The damage evolution and failure mechanism of coatings was quite different at thermal shock temperature of 650 °C and 850 °C, which was explained by a simple model. Different crack propagating modes in nanostructured and conventional coatings during thermal shock tests were due to their different microstructures in these two kinds coatings. The stress state of coating surfaces during the thermal cycles was also discussed in this paper.     

Microstructural evolution of CoCrAlY bond coat on Ni-based superalloy DZ 125 at 1050 °C

CoCrAlY alloy has been widely used as metallic protective coatings or the bond coats in thermal barrier coatings (TBCs) to protect the underlying superalloy from oxidation and hot-corrosion. In this paper, the TBC consisting of yttria stabilized zirconia (7YSZ) ceramic top coat and CoCrAlY bond coat was deposited onto directionally solidified nickel based superalloy DZ 125 by electron beam physical vapor deposition (EB-PVD). The microstructural evolution of the bond coat on this superalloy was investigated after thermal exposure for 100 h at 1050 °C. Due to a significant inward diffusion of Al, Co and Cr from the coating and outward diffusion of Ni, Hf, W and Ti from the substrate, the phase transformation from the Co-based Al-rich β-CoAl phase to the Al-deficient γ-CoNi solid solution phase occurred in the bond coat. Simultaneously, a large amount of Ni-based β-NiCoAl phase was present in the bond coat. In addition, the particles containing substrate strengthening elements Hf and/or W are abundant in the thermally grown oxides (TGO) and within the bond coat. The mechanism for the microstructural evolution is discussed.     

Effect of heat-treatment on stress relaxation behavior of plasma-sprayed 7 wt.% Y2O3-ZrO2 stand-alone coatings

The present work studied the effect of heat-treatment temperature (1000 °C and 1200 °C) and time (10, 50, and 100 h) on the compressive stress relaxation behavior of plasma-sprayed stand-alone 7 wt.% Y₂O₃-ZrO₂ (YSZ) coatings at test temperatures of 1000 °C, 1100 °C, and 1200 °C, from stresses of 60 and 20 MPa. As-sprayed coatings were also stress relaxed in the baseline condition at room and elevated temperatures. All coatings demonstrated a two-stage relaxation behavior: fast relaxation (stage I) in the first 10 min and much slower relaxation in the final 170 min of the test (stage II). Stage I relaxation, as measured by percentage of the original stress relaxed, accounts for at least 50% of the total stress relaxed despite occurring in only 5-10 min and was attributed to lamella sliding and compaction, and permanent intralamellar crack closure (for tests conducted at higher temperatures). Stage II relaxation behavior is dominated by diffusion creep mechanisms, where prior densification at 1200 °C resulted in reduced relaxation rates compared to coatings heat treated at 1000 °C and in the as-sprayed condition. The 1200 °C test temperature greatly influenced the percentage of relaxation in the coating, more so than the prior coating heat-treatment conditions.