Radio-Frequency Induction-Coupled Suspension Plasma Spraying of Dense Ceramic Layers On Metal Substrates

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Radio-frequency induction-coupled suspension plasma spraying of dense ceramic layers on metal substrates
Daniel L. Calabretta
Centre de recherche en nergie, plasma et lectrochimie, Dpartement de gnie chimique et de biotechnologique, Universit de Sherbrooke, Sherbrooke, Qc., Canada, J1K 2R1 Available online 29 January 2013
Abstract Results pertaining to the fabrication of seal-less, metal-supported, electrolytic reverse hydrolysis anode compartments via radio-frequency induction-coupled suspension plasma spraying (SPS) are presented herein. The glycine nitrate process (GNP) facilitated the synthesis of contemporary metal oxide powders. Variable SPS parameters include: GNP-powder tailoring, substrate material, solvent, post-heat-treatment, substrate cooling arrangement, and substrate holder type/arrangement. The latter most parameter required a new design in order to eradicate objectionable, plasma-substrate arcing. Depositions were characterized by energy dispersive x-ray spectroscopy, scanning electron microscopy, and x-ray diffraction. Optimized anode compartments having La0.7Sr0.3Ga0.7Fe0.2Mg0.1O3- as its primary electrolyte, and up to five additional functional layers, were achieved. The anode compartments may be considered for other applications, such as intermediate temperature solid oxide fuel cells, and are in the early stages of electrochemical performance testing. Keywords: Radio-frequency induction-coupled suspension plasma spraying; Intermediate temperature solid oxide fuel cell; LSGFM; Thermal spray processes; Coatings
1. Introduction
For over a decade, researchers at CREPE have been investigating the use of thermal spray processes for the relatively rapid fabrication of metal-supported, intermediate temperature (773100 K) solid oxide fuel cells (IT-SOFCs). If the anode or cathode layer is deposited onto the porous metal support prior to the deposition of the solid oxygen anion electrolyte (SOAE) layer, then the integrated component can be used as anode compartments for the hypothetical electrolytic reverse hydrolysis (ERH) or electrolytic reverse combustion processes, respectively. These hydrogen storage processes have been described elsewhere [1-3] and are of principal interest to the author. But the investigations pertaining to SPS are of interest to the IT-SOFC community, and, more generally, to those interested in thin, dense, ceramic depositions on metal substrates. Reviews [4, 5] show that double-doped LaGaO3 perovskites, doped ceria fluorites, and scandia stabilized zirconia (ScSZ) are the most relevant SOAEs for the processes under investigation. In 1994, Ishihara et al. [6] reported on the near pure oxygen anion (O2-) conducting, double-doped, LaGaO3 perovskite family. A review [7] of the first decade of international investigation of this family is available. Later, the same group reported [8-10] on the extraordinary electronic properties of La0.7Sr0.3Ga0.7Fe0.2Mg0.1O3- (LSGFM). Although hardly investigated since its discovery, LSGFM has O2conductivities that are approximately two orders of magnitude higher than the conventional yttria stabilized zirconia (YSZ) at the intermediate temperature range. Using LSGFM as their primary SOAE [8], 0.5 mm thick, electrolyte-supported IT-SOFCs were fabricated. An additional La0.9Sr0.1Ga0.8Mg0.2O3- (LSGM), SOAE interlayer was deposited on the LSGFM substrate by pulsed laser deposition (PLD) and 90wt%Ni-Fe electro-catalytic anode and Sm0.5Sr0.5CoO3- cathode layers were applied by screen-printing. *Corresponding author Tel.: +1 819 821 8000ext63238; fax: +1 819 821 7095
E-mail:danielcalabretta@gmail.com
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Despite the thickness of the LSGFM layer, their cells yielded power densities of 0.2 and 0.1 W cm-2 at 873 and 773 K, respectively. LSGFM has partial electronic conductivity and the additional LSGM layer (<1m) blocks electron flow to the anode-SOAE interface which thereby affords nearly pure O2conduction through the multi-layer assembly; furthermore, a samarium or gadolinium doped ceria (SDC or GDC) interlayer (<1m) was required between the anode and LSGM layers in order to prevent the formation of insulating, nickel lanthanate phases. Thus far, no group has attempted to fabricate metalsupported IT-SOFCs having LSGFM as its primary SOAE via TSDPes. A brief history of radio-frequency induction-coupled suspension plasma spraying (SPS) deposition technology is warranted. In the patents invention summary [11], the physical steps that the sheared suspension droplets experience upon exiting the atomization probe (into the plasma core) were described consecutively as: (a) vaporizing the carrier substance; (b) agglomerating the small particles into at least partially melted drops; (c) accelerating these drops; and (d) projecting the accelerated drops onto the substrate to form the material deposit. This is true if inert gas or O2 plasmas with aqueous solvent based suspensions are used. Consideration of the solvent-plasma interaction(s) and its effect(s) on deposition quality has been lacking. If hydrocarbons are injected into O2 rich plasmas, reactions tending towards the hydrocarbons complete oxidation will occur. These processes are generally exothermic and should therefore cause localized heating around the solid particles; hence, if compared to aqueous suspensions, an increase in the solids heating and fusion rates can be expected. No mention of this significant factor was made by Bonneau [12] who attempted to deposit conventionally sized (5dp26) electrolyte (e.g. CeO2, ZrO2, La2O3, etc.) powders as dense SOAE layers by injecting suspensions comprised of glycol-water mixtures (solvent) into an O2 rich plasma. Due to the difficulties in maintaining the powders in suspension, negative results were obtained. In Jias bibliographic review [13], other than-low torch power limits the ability to use high solid content suspensions and often requires suspensions to be alcohol based to lower the energy required to vaporize the suspending liquid-no mention of the potential effect(s) of the suspensions solvent character on the overall deposition processs energy balance were made. Schiller et al. [14] did remark on the possibility of increasing the plasmas enthalpy by combustion reactions, but this point has not been sufficiently elaborated on in the literature. A recent review [15] on the preparation of IT-SOFCs via thermal plasma processing did not discuss the possibility of harnessing exothermic, solvent-plasma interactions either. For SPS, suspension comprised of organic solvents being injected into an O2 rich plasma would more appropriately be characterized as a hybrid between the high velocity oxy-fuel and SPS technologies, and could be defined as radio-frequency induction-coupled oxygen-fuel vacuum suspension plasma spraying. Due to the lengthiness of such an acronym, however, it is more practical to use the trademark acronym, SPS. Rudimentary considerations are possible using the solvents available thermodynamic properties [16]. Assuming the complete oxidation of two solvents, where H2O and CO2 are the reactions products, at standard temperature and pressure, the exothermic heat addition per unit time divided by the power dissipation in the radio-frequency induction-coupled plasma torch, which is typically 455 % of the plate power, is here defined as the maximum power of complete oxidation to power dissipation ratio ( PCO PPD ). In Fig. 1 the ratios have been plotted as a function of the solvent flow-rate for the solvents methanol (CH3OH), and pentadecane (C15H32). The latter has been used to approximate mineral oil. Clearly the type of organic solvent and its flow-rate are significant variables in the deposition processes overall energy balance. In the studies of Bonneau [12], Schiller [14], and Jia [13], the O2 sheath gas flowrates were always well in excess of the stoichiometric amounts required for the complete oxidation of their respective solvents. More detailed considerations of the effect of the suspensions wt% solids is warranted but will not be treated here; rather, the results of a two-year experimental study of SPS of dense, ceramic layers are presented.
*Corresponding author Tel.: +1 819 821 8000ext63238; fax: +1 819 821 7095
0.5
0.4
PCO/PPD
0.3
C15H32 0.2 CH3OH 0.1
0.0 0 2 4 6 8 10 12 14 16 18
flow rate (ml min-1)

Fig. 1 Maximum power of complete oxidation to power of heat dissipation ratios dependencies on MeOH (672.14 kJ mol-1; 0.792 g ml-1) and C15H32 (9414.85 kJ mol-1; 0.769 g ml-1) flow rates; 45% overall plasma circuit efficiency operating at 50 kW plate power 1.1 Preparation of integrated, metal-supported SOFCs by TSDPes The IT-SOFCs that have achieved the highest electrochemical performances were prepared via the vaporization deposition techniques RF-magnetron sputtering [17, 18] and pulsed laser deposition [19, 20] having deposition rates of 10-4 m s-1 and 10-3 m s-1, respectively. The most exceptional IT-SOFCs were developed by Ishihara et al. and employed the SOAE La0.9Sr0.1Ga0.8Mg0.2O3-. A thin interlayer of Sm0.2Ce0.8O2- was deposited between the anode and LSGM layer in order to prevent the formation of nickel lanthanates. Despite the amount of literature related to the preparation of metal-supported SOFCs by TSDPes, there are few reports detailing the electrochemical performances of complete cells. Recent reviews [21, 22] on integrated, metal-supported SOFC preparation via TSDPes can be compared with the earlier review by Henne et al. [23]. Takenoiri et al. [24] prepared nickel felt-supported SOFCs via atmospheric plasma spraying (LaCoO3 cathode and YSZ SOAE) and high velocity oxy-fuel (anode) technologies. Ceramic-coated metal separators were used in their thirty, seal-less stack that achieved power densities of 0.3 W cm-2. Stack degradation was significant while operating at 1243 K for 2400 hrs. Tsukuda et al. [25] constructed calcia-stabilized zirconia supported, tubular IT-SOFC having a Ni-YSZ cermet anode, YSZ SOAE, and LaCoO3 cathode. Their cell performances of ~0.5 W cm-2 were similar to analogous cells fabricated by co-sintering procedures. *Corresponding author Tel.: +1 819 821 8000ext63238; fax: +1 819 821 7095
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Shiller et al. [26] and Lang et al. [27] reported on SOFCs prepared by vacuum plasma spraying (using Laval-type nozzles) the functional layers on nickel-alloy, porous, metal filters and nickel-felt substrates. Power densities were measured to be 0.3-0.4 W cm-2 between 1023-1073 K. Compared to atmospheric plasma spraying, vacuum plasma spraying can decrease the SOAEs permeability by about an order of magnitude. The high melting temperature YSZ and scandia stabilized zirconia (ScSZ) SOAEs were sprayed directly into the arc while electrode materials were injected downstream. Electrochemical characterization was later reported [28] for larger SOFCs using the same fabrication procedure. Schiller et al. [29] assembled anode-supported SOFCs and achieved similar electrochemical performances to those reported on by Lang et al. [27]. By obtaining a maximum power density of 0.5 W cm-2 at 1073 K, Stver et al. [30] set a new benchmark for mostly TSDP-prepared SOFCs that were comprised of NiO-YSZ anodes and YSZ SOAEs. In regards to TSDP for the fabrication of SOFCs having double-doped, LaGaO3 electrolytes, Ma et al. [31] reported on near theoretical open circuit voltages for their Ni-YSZ/LSM/LSM button cells. SOAE layer thicknesses of 6515m were deposited by atmospheric plasma spraying, which rendered power densities of 0.08-0.15 W cm-2 between 773-1073 K; however, in order to obtain an acceptable level of perovskite phase, a post-deposition, heat-treatment step was required. Hwang et al. [32] later reported on Ni-YSZ/LSGM/LSCF SOFCs prepared by atmospheric plasma spraying technology on nickel substrates. Compared to the cells prepared by Ma et al., they obtained superior power densities. To the authors knowledge, at the start of this project, a fully-functional, metal-supported ITSOFC had not yet been assembled and tested at CREPE. Efforts towards the development of small ITSOFCs have always been in regards to the individual cathode [33, 34] or electrolyte [11, 12, 35, 36] layers. 2.0 Experimental 2.1 The glycine nitrate process Several metal oxide powders were synthesized by the glycine nitrate process (GNP). These materials coefficients of thermal expansion (CTEs), along with those of the principal metal substrate materials, are listed in Table 1. Reagent grade starting materials having the following purities were obtained from Alfa Aesar: La(NO3)3*6H2O (99.9 wt%), Fe(NO3)3*9H2O (98.1 wt%), Sr(NO3)2 (99.9 wt%), Mg(NO3)2*6H2O (99.9 wt%), Sm(NO3)3*6H2O (99.9 wt%), Ce(NO3)3*6H2O (99.5 wt%), Ni(NO3)2*6H2O (99.5 wt%), Ga (99.999 wt%) and C2H5NO2 (98.5 wt%). Gd0.1Ce0.9O2- SOAE (Sigma Aldrich; 734667) having particle diameters (dp)0.5m was also used without further tailoring. For the synthesis of powders by the glycine nitrate process (GNP), the vessel used at CREPE for the synthesis of nano-powders [37] by radio-frequency induction-coupled solution plasma spraying was slightly modified. Fig. 2 shows the block-schematic for the set-up. Briefly, metal nitrate salts of the corresponding metal oxides are dissolved in water, or the metals, i.e. gallium, is reacted and dissolved in [HNO3]. Glycine (C2H5NO2) is then dissolved into the solution which is subsequently heated and agitated on a hot-stir-plate. After a few minutes, the majority of the solutions water is evaporated and the homogeneous, viscous fluid reacts exothermically rendering powders with sub-micron grain sizes. During the synthesis of GNP powders, best results were obtained when the double-walled vessel was placed in a horizontal position and maintained at 34310 K with a thermostatic water bath. This avoided excess condensation on the reactor walls thus making it more agreeable to collect the powders. The systems pressure was maintained at 5414 103 Pa and the reaction vessels temperature was monitored with a hand-held recorder and a 3.175 mm o.d., SS-sheathed, K-type, grounded thermocouple (Omega) that was fitted into place with a Swagelok component. As well, a 1.70.1 C2H5NO2 to metal mole ratio was used and 7525 ml volumes of GNP solution were reacted each time. The reaction vessels temperature would stagnate after several minutes of heating; shortly thereafter, simultaneous increases in the systems pressure and reaction vessels temperature indicated the initiation of the powder formation process. *Corresponding author Tel.: +1 819 821 8000ext63238; fax: +1 819 821 7095
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Typically, in order to eliminate phase impurities, following their synthesis, ~100 g samples of GNP powders were placed in MgO crucibles (Ozark Technical Ceramics, MO, USA) and heated to 1780 K at 1.50.5 K min-1 in a RHF 17/3M (Carbolite Ltd., London, UK) resistance furnace. Then, the powders were pulverized in an 8000M Mixer/Mill (Spex SamplePrep LLC, NJ, USA), and subsequently, with a Sonic Sifter (ATM Corp.; WI, USA), sieved to dp53 m.
Table 1 mean CTEs for the ERC and ERH anode compartment materials Material (mole basis) Sm0.2Ce0.8O2- La0.9Sr0.1Ga0.8Mg0.2O3- La0.8Sr0.2Ga0.8Mg0.2O3- La0.7Sr0.3Ga0.7Fe0.2Mg0.1O3- Gd0.2Ce0.8O2- Inconel 600 Hastelloy X *Ni0.9Fe0.1 CTE (10-6 m m-1 K-1 ) 12.7 11.6 12.1 13.6 11.6 14.5 15.6 13.2 Reference 45 7 46 10 5 ca.
*mass basis
filtrationvessel
double-walled powder collection-vessel
to vacuum pump
reaction vessel
thermostat
hot-plate stirrer
Fig. 2 Schematic of the arrangement used for the synthesis of GNP powders
2.2 SPS for the preparation of ERH anode compartments The SPS apparatuss cross-view schematic is shown in Fig. 3. Details on the apparatuss suspension atomizer, torch, and substrate holder, along with other relevant points on the preparation of substrates have been given elsewhere [38]. Constant SPS parameters are listed in Table 2.
Table 2 Constant SPS parameter values Parameter icentral plasma gas(Ar) flow rate (slpm) isheathe plasma gas (O2) flow-rate (slpm) atomization gas (Ar) flow-rate (slpm) deposition chamber pressure (kPa) plasma plate power (kW) suspension injection flow rate (ml min-1) spraying distance (cm) atomization gas pressure (kPa)
Value 221 611 110.5 13.36.7 501 5.51.5 73 34510
suspension stir-plate
peristaltic pump
Faraday cage torch
1 2 8 3 7 6
high-pressure water outlet high-pressure water inlet water-cooled automated arm high-pressure water outlet
deposition chamber
vacuum
Fig. 3 Cross-sectional schematic of the apparatus used for SPS-(1) electrically-grounded water-cooled mask; (2) copper plaque; (3) SS304 water-cooled substrate holder; (4) double-walled, aluminum, watercooled jacket; (5) flexible SS316 hose; (6) dielectric fitting; (7) Teflon nipple; (8) metallic adapter
Initial investigations of the character of SPS depositions were done on commercial, porous or solid, metal substrates, which were neither pre- nor post-heated by the plasma jet. While ideally the *Corresponding author Tel.: +1 819 821 8000ext63238; fax: +1 819 821 7095
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deposition rates would refer to the coatings thicknesses per unit area and unit time, and would be reported in units of m cm-2 s-1, where the coatings thicknesses-determined from their cross-sectional micrographs-, and the area and time factors- determined from the cooling masks inner diameter (Fig. 3) and the substrate-plasma jet exposure-time during each loop, which are known to be 3.834 0.001 cm and 2.5 0.1 s, respectively-, the accuracy of the time variable renders meaningless deposition rates; hence, the deposition rate are given in m loop-1 2.3 Design and preparation of ERH anode compartments Both pipe (Fig. 4(a)) and NPT (Fig. 4(b)) anode compartment designs were investigated; after several negative results, the former was discarded for the latter. It was imperative for the substrates interior and exterior walls to be intensively cooled amid SPS; this necessitated the NPT design. A 1.91 cm o.d., Inconel bar was machined, in-house, to the GKN flow-restrictor specifications (1.270.01 cm i.d.), sand-blasted, cleaned, and shipped to the manufacturer where SIKAHX-5 powders were pressed and sintered into the part. There appeared to be excellent porous-solid joint integrity, and further machining of the integrated part was done as required throughout the SPS optimization. For the final preparation of the integrated parts, its non-porous region were sand-blasted prior to washing it in alternating baths of 1 N HCl and 20 vol% H2O2 -as was deemed necessary-and placing it in an EtOH, ultra sound bath for several hours.
integrated NPT ERH anode compartment exterior water-cooling effluent water
(a)
0.16 cm OD SS316 tube 0.48 cm OD SS316 tube TIG weld 1.27 cm OD GKN-HX-5 1.91 cm OD machined Inconel bar 1.91 cm OD machined SS316 bar
(b)
influent water interior water-cooling
copper plaque
Fig. 4 Cross sectional schematics of the metal-supported, ERH anode compartments substrates (a) pipe design; (b) NPT design For the preparation of ERH anode compartments, protocols were taken from the studies of Shiller et al. [26], Lang et al. [27] and Ishihara et al. [19, 39, 40]; the deposition of a dense layer of NiO-Fe2O3 on nickel-alloy, GKN porous metal filters, followed by its H2 reduction, prior to or after the depositions of the electrolyte layers, is essentially a hybrid of the research groups designs. The selection of SPS feedstock materials coincided with those used by Ishihara et al; however, LSGFM typically took the place of LSGM as the principal electrolyte. 2.4 Analyses XRD patterns of were acquired using an XPert Pro, multi-purpose, x-ray diffractometer (Philips, Eindhoven, Netherlands); it utilized Cu K radiation (45 V; 45 mA). A model S-4700 (Hitachi, Tokyo, Japan) field-emission scanning electron microscope (SEM), equipped with an energy dispersive x-ray spectroscopy (EDS) apparatus, facilitated the micrographic and elemental analyses of the GNP synthesized powders. *Corresponding author Tel.: +1 819 821 8000ext63238; fax: +1 819 821 7095
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Prior to acquiring an SPS coatings cross-sectional, SEM micrographs with either the S-4700, a JEOL J840A (JEOL Ltd., Tokyo, Japan) or a variable pressure N-3700 (Hitachi, Tokyo, Japan) apparatus-a homogeneous mixture of epoxy resin and hardener (Precision Surfaces Int., TX USA) was poured into the sample containing molds and left to cure at ambient conditions for two days. The hardened, sample-containing epoxy was cut with an ISOMET 2000 (Buehler Co., IL, USA), diamond saw; the corresponding face was manually polished with an Ecomet 3-variable speed grinder (Buehler Co.) with 180-600 grit silica-papers, and the final polishing employed 6 m diamond suspensions (Precision Surfaces Int.). Lastly, a thin layer of 80wt%Au-Pd was applied with a Hummer IV Sputtering System (Anatech; CA, USA), which was operated at 10 mA and 9010 Pa for ~1 min. On one occasion the adherence and porosity of SPS depositions on the ERH anode compartment was investigated by measuring its open circuit voltage (OCV) using the set-up depicted in Fig. 5. Following the depositions, 9912-G silver conductor paste (ESL Electroscience; PA, USA) was applied as a cathode (SOFC) layer. Then a layer of Aremco 634-AL Pyro-paint was coated on the ERH anode compartments exterior walls with a paint brush. A nickel wire, which was inserted in an Al2O3 tube and coiled at its end, was used to make the electrical contact with the silver cathode. Electrical contact was made with the anode via a Swagelok, SS316, male, NPT fitting. The OCV measurements were taken with a hand held multi-meter. Electrical contacts were made at the exterior of the furnace at the 1.56 mm o.d., SS316, influent H2 tube and the nickel wire. 99.9 vol% H2 and 99.9 vol% O2 were passed through their respective compartments at 200 50 ml min-1. Teflon tubing and Swagelok components were used to electrically insulate the influent H2 line from its reservoir, and a grounded, k-type, Omega thermocouple was inserted in an alumina tube such that its end was in physical contact with the ERH anode compartments electrically insulating layer. The arrangement was heated at 2 K min -1 to 92310 K in a Lindberg 55035 mini mite, horizontal, tubular furnace (Lindberg/MPH; MI, USA).
tube furnace resistance coils quartz tube 634-AL pyro-paint effluent H2 influent H2 1.56 mm o.d. SS316 tube 4.76 mm o.d. SS316 tube Al2O3 tube NPT-type ERH anode sheathed k-type thermocouple Swagelok-NPT fitting Al2O3 tube O2 Ni wire
Fig. 5 Experimental arrangement used for OCV measurements
3. Results and discussion Results and discussions regarding the synthesis and characterization of the SPS feedstock powders will be given first. This will be followed by the results and commentary on the initial investigations pertaining to SPS and succeeded by the presentation of its relative, follow-up research, particularly as it relate itself to the eradication of plasma-substrate arcing. Consecutively, inquests towards the fabrication of ERH anode compartments are given.
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3.1 Characterization of GNP powders During the GNP synthesis of the supposed nickel/iron oxide mixture (NFO), there was a remarkable increase in the reaction vessels temperature (673 10 K), and, as shown by its XRD pattern in Fig. 6, the as-synthesized powder was identified as Awaruite (Ni3Fe). However, subsequent air sintering at 1773 10 K for 8 hrs rendered the desired composition, which was ferro-magnetic and tended to agglomerate which therefore made it arduous to sieve to the preferred particle sizes (dp < 32 m).
10000
Fe3O4
8000
NiO FeNi3
Relative Intensity
6000
4000
2000
20
30
40
50
60
70
80
Position (2 theta) Fig. 6 XRD patterns for GNP synthesized NFO powder before (bottom) and after air sintering at 1773 10 K for 8 hrs
The La0.8Sr0.2Ga0.8Mg0.2O3-, La0.7Sr0.3Ga0.7Fe0.2Mg0.1O3-, and Sm0.2Ce0.8O2- GNP synthesized powders that were obtained from the GNP collection vessel were ethereal. During the reaction, the reaction vessels temperature did not exceed 47310 K, over-pressurization of the collection vessel did not occur while applying the specified vacuum conditions, and about half of the materials could be collected directly from the reaction vessel (Fig. 2). Following the GNP synthesis of La0.8Sr0.2Ga0.8Mg0.2O3-, the resultant phases coincided to with what was already known [44]. As shown in Fig. 7(a), the insulating, SrLaGa3O7 compound, which was initially significant, diminished with the air-sintering temperature, and became negligible after soaking it at 174810 K for 6 hrs. Fig. 7(b) is the EDS spectrum of La0.8Sr0.2Ga0.8Mg0.2O3- following its airsintering at 174810 K. EDS does not allow for the detection of magnesium; however, the subsequent two-electrode conductivity tests affirmed its composition [41]. *Corresponding author Tel.: +1 819 821 8000ext63238; fax: +1 819 821 7095
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16000
La0.8Sr0.2Ga0.8Mg0.2O3- SrLaGa3O7
(a)
14000
?
SrLaGaO4 uknown
12000
1748 K
Relative Intensity
10000
8000
1623 K
6000
1523 K
4000
2000
? ? ? ? ? ? ?
0 20 30
40
50
60
70
Position (2 theta)
1000
(b)
O
800
La
Ga La
counts
600
La
400
Sr
Ga La
200
La La La
La
0 2 4 6 8 10
keV
Fig. 7 Analyses for GNP synthesized La0.8Sr0.2Ga0.8Mg0.2O3- powder-(a) XRD patterns before (bottom) and after air sintering for 6 hrs at 1523, 1623, and 174810 K; (b) EDS spectrum for La0.8Sr0.2Ga0.8Mg0.2O3- after air sintering at 174810 K For La0.7Sr0.3Ga0.7Fe0.2Mg0.1O3- (LSGFM), if the same sintering sequence as the one used for LSGM is employed, it was not possible to completely eliminate the SrLaGa3O7 phase. This is exemplified by LSGFMs XRD patterns that are shown Fig. 8(a). *Corresponding author Tel.: +1 819 821 8000ext63238; fax: +1 819 821 7095
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14000
La0.7Sr0.3Ga0.7Mg0.2Fe0.1O3- SrLaGa3O7 La4Ga2O9

?
(a)
12000
unknown 1773 K
Relative Intensity
10000
1743 K
8000
6000
1673 K
4000
1623 K
2000
1373 K
0 20
? ? ? ? ?
30
40
50
60
70
80
Position (2 theta)
500
O
(b)
400
Ga La
counts
300
200
Sr
La
100
Fe La La
La
La La La
Fe Ga
0 2 4 6 8 10
keV
(c)
(d)
(e)
50m
50m
5m
Fig. 8 Analyses for GNP synthesized La0.7Sr0.3Ga0.7Fe0.2Mg0.1O3- powder (a) XRD patterns after GNP synthesis (bottom) and after air sintering for 8 hrs at1373, 1623 1673, 1743, and 177310 K; (b) EDS spectrum after air sintering at 177310 K for 8 hrs; (c) SEM micrograph after GNP; (d) SEM micrograph after air sintering at 162310 K for 8 hrs; (e) SEM micrograph after air sintering at 174810 K for 8 hrs, pulverizing, and sieving to dp32m *Corresponding author Tel.: +1 819 821 8000ext63238; fax: +1 819 821 7095
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Irons presence can be found in LSGFMs EDS spectrum (Fig. 8(b)). The SEM micrographs for the as-synthesized powders (Fig. 8(c)) shows that the dp is greater than several hundred microns and that the particles are comprised of interlocking grains having sizes in the order of 0.200.05 m. Although dp had remained essentially the same after sintering at 162310 K (8 hrs), the grain sizes augmented to 0.750.25 m. It was discovered that, for SPS, it was essential to pulverize and sieve the powders such that their dp32m. The SEM micrograph shown in Fig. 8(e) exemplifies the conventional sized powders that were used for the majority of the SPS depositions. Following its GNP synthesis, Sm0.2Ce0.8O2- (SDC) was sintered at 177310 K for 8 hrs. Its XRD patterns, given in Fig. 9, shows that a purely fluorite phase was obtained.
4000
CeO2
3000
Relative Intensity
2000
1000
0 20 30 40 50 60 70 80
Position (2 theta)
Fig. 9 XRD patterns for GNP synthesized Sm0.2Ce0.8O2- powder before (bottom) and after air sintering at 177310 K for 8 hrs (top) 3.2 Initial investigations of SPS Initial attempts at SPS depositions of double-doped, LaGaO3 SOAE employed parameters that were very similar to those used by Jia and Gitzhofer [42]. Early on, however, it was found that the backpressure in the atomization probes suspension inlet-caused by the pressure exerted by the injection gas line (Fig. 3)-often prevented the EtOH-based suspension from flowing altogether. Furthermore, EtOH, GNP powder suspensions were not uniform; thus, at the time of the depositions, EtOH flowed faster than the solids while the latter obviously settled in the peristaltic tube; therefore, it was impossible to know, even approximately, what the suspensions wt% solids were at the atomization probes exit. This *Corresponding author Tel.: +1 819 821 8000ext63238; fax: +1 819 821 7095
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occurred if solid GNP powders were added to the solvent either directly following their synthesis or following their sintering and subsequent placement in an ultrasound bath. The problem was particularly severe using the former arrangement. The effect of the addition of dispersant(s) on EtOH suspensions stabilities and fluidities was not investigated as white mineral oil was discovered to be a far superior solvent. For the flow-rates used in this study (2.5-8.0 ml min-1), mineral oil suspensions were uniform; this stems from mineral oils kinematic viscosity (34.5 cSt), which is high compared to EtOHs (1.5 cSt). Furthermore, as shown in Fig. 1, mineral oil has a higher volumetric power density. All of the SPS results given here are in regards to mineral oil suspensions. A summary of the SPS (i-xi) parameters are given in Table 3. The corresponding samples analyses were done using the given protocols (2.3). For this preliminary study, 7 wt% solid suspensions were used. As well, the substrate type and the GNP powders post-synthesis manipulations varied for this portion of the optimization. Either a mortar and pestle (MP) or a miniature ball-mill (MBM) was used to pulverize (~ 1 g) the sintered, GNP powders. Table 3 Summary of the varied parameters values during the initial SPS investigations Analyses PT ST FR (ml min-1) SOAE SD NL Ti 4 LSGFM 10 55 SEM, EDS MBM SEM, EDS MBM Ti 4 LSGM 10 20 SEM MBM Ti 4 LSGMF 10.5 20 SEM, EDS MBM Ti 4 LSGM 10 23 Ti 4 LSGMF 14 15 SEM, EDS MBM SEM, EDS MBM Ti 8 LSGM 20 4 SEM MP SIKA-SS-10 4 LSGMF 10 20 SEM, EDS MP SIKA-HX-10 4.5 LSGMF 10 10 SIKA-HX-1 4 LSGFM 11 7 SEM 2.1 SEM 2.1 SIKA-HX-1 4 LSGFM 11 60 SEM 2.1 SIKA-HX-1 4 LSGFM 11 55 ST substrate type; FR flow rate; SD spraying distance; NL number of deposition loops; PT powder tailoring.
Deposition Ii iii iii iiv iv ivi ivii iviii iix ix ixi
Figs 10(a)-(c) shows that the coating suffers from a high level of open porosity; despite the number of passes, its EDS, elemental spectrum indicated the presence of titanium. The distribution of elements, however, was similar to the feedstocks (Fig. 8(b)).
14
LSGFM
(a)
LSGFM
(b)
10 m
10 m
LSGFM
I(c)
1 m
Fig. 10 Analyses for deposition i (Table 3) (a)-(c) SEM micrographs (top section)
Deposition iis cross sectional, SEM micrographs are shown in Fig.s 11 (a)-(b). The LSGFM layer is well adhered to the Ti substrate, but there is significant variation in its thickness. Furthermore, the coating is not homogeneous. Regions with significant open porosity abruptly become dense. Copper, which assuredly came from the fusion of the copper, cooling insert that Jia [13] used for his SPS depositions, was present in the EDS, elemental spectrum; hence, Jias claim that the copper cooling mask rendered superior coatings could not be substantiated.
15
(a)
(b)
LSGFM 29.4 m 10 m Ti 23. m
LSGFM
10 m
Ti
LSGFM
(c)
1 m
Fig. 11 Analyses for deposition ii (Table 3) (a)-(b) SEM micrographs (cross section); (c) SEM micrograph (top section)
The global, SEM micrograph of deposition iiis top-section is given in Fig. 12(a). Although the coating has a high surface density of caverns, their characters do not correspond well with those stemming from the discovered, plasma-substrate arcing. In addition, the coatings microstructure is highly porous and it appears as though the powders were heated to a quasi-vapour state amid SPS. The effect may be a result of the amount of time the post-sintered, GNP powders were subjected to ball-milling-which, for this portion of the optimization, varied between several minutes to several hours. A substantial portion of the powders were lost during the ball-milling. Powders having an excessively small particle size distribution would be more susceptible to vaporization; hence, careful control over the powders post-tailoring process is critical. The SEM micrograph of the depositions cross section (Fig. 12(c)) shows that the rate of deposition was in the order of 1.0 0.1m loop-1. However, the coating did not adhere to the titanium substrate and suffers from a significant level of open porosity.
16
LSGM
(a)
LSGM
(b)
100 m
10 m
epoxy LSGM
(c)
18 m
1 m
Fig. 12 Analyses for deposition iii (Table 3) (a)-(b) SEM micrographs (top section); (c) SEM micrograph (cross section) As shown in Figs. 13(a)-(c), deposition ivs top global and micro characteristics are similar to those of deposition iiis. The layers thickness, which is approximately half of the previous two depositions, indicates that either its density is significantly higher or that a significant portion of the in-flight particles were rebounded upon contacting the substrate. Again, the coating has poor adherence to the titanium substrate and its non-homogeneity is presumably due to the powders post-tailoring sequence. As well, the top-sections EDS, elemental spectrum was similar to the feedstocks (Fig. 8(b)).
17
LSGFM
(a)
LSGFM
(b)
100 m
10 m
LSGFM
(c)
Ti epoxy 9.7 m
(d)
1 m
1 m
Fig. 13 Analyses for deposition iv (Table 3) (a)-(b) SEM micrographs (top section); (d) SEM micrograph (cross section) In comparison to the previous depositions, the only remarkable parameter change for deposition v was the greater stand-off spraying distance. Two different types of microstructures can be observed. On the one hand, as shown in Fig. 14(a), there are regions in which splats having diameters ranging from a tenth to several tens of microns are deposited upon seemingly larger particle deposits that had reached a quasi-liquid state. A vertical crack is also present in the top left hand side of the micrograph. On the other hand, as shown in Fig. 14(b), there are regions that correspond to the previous depositions where the material attained a quasi-vaporized state prior to being deposited. There is substantial variation in the depositions thickness and the cross-section micrographs (Figs. 14(c)-(d)) shows that, along with open porosity, the deposition suffers from both vertical and horizontal cracking. In addition, either during or after the deposition, portions of the coating having lengths and widths in the order of several microns broke away from the rest of the deposition. The initial layer of the deposit, however, is well adhered to the titanium substrate. Finally, other than the presence of titanium, the depositions top-section, EDS spectrum coincided with the feedstocks.
18
LSGFM
(a)
LSGFM
(b)
1 m
1 m
Ti
(c)
Ti LSGFM
(d)
LSGFM
8.2 m
1 m
1 m
Fig. 14 Analyses for deposition v (Table 3) (a)-(b) SEM micrographs (top section); (c)-(d) SEM micrograph (cross section) During deposition vi, the suspensions flow-rate, the SPS stand-off distance, and the number of deposition loops differed. High-resolution, SEM micrographs of the coatings cross-view are shown in Fig.s 15(a)-(c); it can be seen that the well-adhered deposit suffers from a significant level of open porosity. Additionally, the substrate was not well centered amid the deposition; hence, the coatings thickness varies greatly (7.9 6.9 m). Other than the presence of titanium, the depositions crosssectional, EDS, elemental spectrum corresponded to its feedstock (Fig. 7(b)).
--
19
(a)
(b)
14.7 m
LSGM
LSGM Ti 10 m 1 m Ti
(c) LSGM
Ti
10 m
Fig. 15 Analyses for deposition vi (Table 3) (a-c) SEM micrographs (cross section);
Due to the substantial powder loss that was experienced while pulverizing the post-sintered, GNP powders in the miniature ball-mill, attempts were made to reduce the powders particle sizes with a mortar and pestle. As well, commercial GKN porous metal filters made from both SS316 (SIKA-SS10) and Hastelloy X (SIKA-HX-10 and SIKA-HX-1) were used throughout the remainder of the initial optimization procedure. Deposition viis global top-view, SEM micrograph, given in Fig. 16(a), shows that the powder sizes are excessively large; hence, they are insufficiently melted in the plasma core, which gives rise to discontinuous coatings. The high-resolution, top-sectional, SEM micrograph (Fig. 16(b)) suggests that particle splat formation did not occur and that the particles were slightly liquefied in the plasmas core. The global, cross section, SEM micrograph (Fig. 16(c)) infers that the SS316 substrates pore size is excessive and that the coating is poorly adhered to the substrate. As well, its thickness (Fig. 16(d)) is less than what was achieved while spraying the ball-milled powders under the same operating conditions. This indicates that solid particles were rebounded off of the substrate.
20
LSGM
(a)
LSGM
(c)
100 m
1 m
SIKA-SS-10 LSGM
SIKA-SS-10
6.4 m
7 m
10 m
1 m
Fig. 16 Analyses for deposition vii (Table 3) (a)-(b) SEM micrographs (top section); (c)-(d) SEM micrographs (cross section)
Fig. 17 contains the analyses for deposition viii. While operating with the specified parameters, it can be seen that a large percentage of the solid particles, especially those having diameters in excess of 30 m, are not sufficiently fused in-flight, and therefore the coating is not dense. That is to say that only the particles exterior surfaces attain the liquid state as the heat transfer rate was insufficient to liquefy their cores. However, as indicated by Fig. 17(d), the larger particles fuse together during the quenching process. Clearly, the suspensions large particle size distribution results in irregular depositions hence further tailoring of the synthesized powders is required.
21
LSGFM
(a)
LSGFM
(b)
300 m
20 m
(c) LSGFM LSGFM
(d)
SIKA-HX-10 50 m SIKA-HX-10 50 m
Fig. 17 Analyses for deposition viii (Table 3) (a)-(b) SEM micrographs (top section); (c)-(d) SEM micrographs (cross section) Other than the severe plasma-substrate arcing, which results in micro-lunar surfaces, SPS of post-sintered, GNP-synthesized, LSGFM powders, tailored to dp32m, on SIKA-HX-1 substrates renders depositions of uniform thicknesses (Fig. 18). The author is unable to specify the reason(s) for the seemingly absence of the arcing in the prior depositions. In the plasma core, the outer volumes of the feedstock powders with 32 m < dp < 10 m attain a majority liquid state in their outer volumes, while smaller particles are completely liquefied. The quenched mixture results in depositions having minor amounts of open porosity (e.g. Fig. 18(e)).
22
LSGFM
(a)
LSGFM
(b)
500 m
50 m
(c)
(d)
50 m
100 m
(e)
1 m
Fig. 18 Analyses for deposition ix (Table 3) (a)-(f) SEM micrographs (top sections) The SEM micrograph of deposition ixs global top-view (Fig. 18(a)) indicates that the arc rate density is 1.5 0.25 arcs loop-1 mm-2. Microstructures for three of the depositions craters are displayed in Figs. 18(b)-(d); the arcs penetrate the depth of the ceramic layer leaving craters with diameters of 45 15 m. Two types of craters are noted. One type, which is exemplified by Figs. 18(b)-(c), is where only the removal of material occurs during the arcing. The other type is where the arc results in both the removal of material in combination with its vaporization, which, upon quenching, results in ceramic bubble formation in the craters exterior ring (Fig. 18 (d)). *Corresponding author Tel.: +1 819 821 8000ext63238; fax: +1 819 821 7095
23
Deposition xs global, top section SEM micrograph (Fig. 19(a)) shows the augmentation in crater density, compared to deposition ixs, because of the greater number of deposition passes. The severe environment also renders a high density of vertical cracks (Fig. 19(b)).
LSGFM (a) LSGFM (b)
500 m
200 m
LSGFM
(c)
LSGFM
(d)
100 m
50 m
Fig. 19 Analyses for deposition x (Table 3) (a)-(d) SEM micrographs (top section) Cross-view, SEM micrographs for a 55 loop, LSGFM deposition are given in Fig. 20. The operating conditions allow for a deposition rate of 0.80.1 m loop-1 and the use of SIKA-HX-1 substrates largely eliminates the coating discontinuities and depressions that occur on SIKA-HX-10 substrates. Although the level of open porosity is very minor and the LSGFM coating adheres well to Hastelloy X, the presence of vertical cracks-caused by either the arcs or the mismatch of the materials CTEs, or a combination of the two effects-are highly objectionable.
24
(a)
(b)
LSGFM
LSGFM
100 m SIKA-HX-1 SIKA-HX-1 (c) LSGFM
100 m
20 m SIKA-HX-1
Fig. 20 Analyses for deposition xi (Table 3) (a)-(c) SEM micrographs (cross section)
In summary, as it pertains to obtaining dense ceramic coatings by SPS, despite what was reported [42], major parameter adjustments were required. Firstly, GNP powder-EtOH suspensions are not homogeneous. Rather, viscous solvents that can be pumped at greater than 4 ml min -1, such as mineral oil, are required. Secondly, to obtain coatings of uniform thicknesses, post-air-sintered, GNP synthesized powders must be pulverized and sieved to dp32 m, and commercial substrates having low pore sizes, such as SIKA-HX-1, are required. Thirdly, the plasma-substrate arcing, which produces craters at a rate 1.50.5 arcs loop-1 mm-2, is highly objectionable as it is responsible for significant amounts of coating loss and crackingboth horizontal and vertical. The results from the secondary investigations of SPS of dense ceramic layers on commercial, porous, metal substrates, particularly as it relates to the eradication of the plasma-substrate arcing, is presented in the following sub-section. 3.3 SPS on GKN porous, metal filter substrates Although several problems associated with SPS of dense ceramic layers on metal substrates were exposed and resolved in the previous sub-section, several issues still need to be addressed before the fabrication of metal-supported, ERH anode compartments can be considered. In this sub-section, findings from the optimization of dense ceramic coatings on GKN porous metal filters by SPS are elaborated. This particularly relates itself to material compatibility issues, the eradications of the discovered plasmasubstrate arcing, and multi-layer depositions.
25
Table 4 Summary of the varied parameters values for the SPS of dense, ceramic layers on GKN porous metal filters
Deposition Powder Ii NFO SDC LSGM LSGFM Iii NFO SDC LSGM LSGFM Iiii NFO LSGM LSGFM Iiv NFO SDC LSGM LSGFM Iv NFO LSGFM Vi NFO GDC LSGM LSGFM
Wt% solids 10.6 10 10 10.1 10.6 10 10 10.1 10.6 10 10.1 9.7 10 10 10.1 6.9 8 8 7.4 7.4 8
iNo. loops 50 3 3 60 50 3 3 60 50 3 80 60 2 2 60 25 25 20 2 2 70
Analyses
SEM, EDS
SEM
SEM, EDS
SEM SEM
SEM, EDS, XRD
The remainder SPS results presented in this text involves the use of sintered, GNP synthesized powders that were tailored to dp<53 m (NFO) and dp<32 m (LSGM, SDC, LSGFM) using the protocol given in 2.1. Depositions i-iv and v-vi were done using the electrically-non-insulated (old) and electrically-insulated (Fig. 3) substrate holders, respectively. During every deposition, the cooling mask was electrically grounded and neither the pre-heating of the metal substrates nor the post heating of the coatings was done. As well, the spraying distance (nozzle tip to substrate) was 5.51.5 cm, and the suspension flow-rate was 4.00.1 ml min-1. A summary of the varied parameters values for the SPS of dense, ceramic layers on GKN porous metal filters are listed in Table 4. SEM micrograph of deposition is cross-sectional view, shown in Fig. 21(a), does not focus on the craters that were still present to a minor degree. For the NFO, SDC, and LSGFM deposits, respective deposition rates of 0.720.02, 1.00.02, and 1.450.02 m loop-1 were obtained. Although the NFO layer does not adhere to the SIKA-SS-5 substrate, there is excellent adherence at the three ceramic interfaces. Other than the LSGM/LSGFM interface, it is possible to visually distinguish the distinct layers by the abrupt colour variations. While the level of open porosity is low, the vertical crack that extends itself across the SOAE layer is objectionable.
26
SIKA-SS-5
LSGFM SDC
(a)
NFO
LSGM
50m
epoxy
Fig. 21 Analyses for deposition i (Table 4) (a) SEM micrographs (cross section) Deposition ii was done on a SIKA-HX-1 substrate. The SEM micrographs of its top section are shown in Fig. 22. A crater formation rate of 0.060.01 craters loop-1 mm-2 is low compared to the ones obtained while performing depositions with an ungrounded, cooling mask. Note that the calculation was made using the number of LSGFM passes as it is believed that craters in the previous layers were undetectable. The high resolution micrographs (Figs. 22(b)-(c)) indicate that the vast majority of the feedstock is liquefied in the plasmas core and that the coating is essentially free of vertical cracks.
LSGFM
(a)
LSGFM
(b)
1000m
50m (c)
LSGFM
50m
Fig. 22 Analyses for deposition ii (Table 4) (a)-(c) SEM micrographs (top-section)
27
Deposition iii was done on a SIKA-HX-1 substrate. From its cross-sectional, SEM micrograph, shown in Fig. 23(b), deposition rates of LSGM/LSGFM and NFO are 1.340.14 and 0.920.10 m loop-1, respectively, have been determined. The contrasting layers are firmly attached to one another and there are no signs of discontinuities along their interfaces. Additionally, the EDS, elemental mapping of the individual elements, which are shown in the bottom inserts, affirms that excellent phase separation is achieved. Furthermore, the EDS spectrum (Fig. 23(a)) of the LSGFM layer coincided with its feedstock. However, unwanted vertical cracks, which are only present in the SOAE layer(s), exist at intervals of one for every 10020 m and extend themselves through the layers thickness, appear to have initiated themselves at the top surface of the coating.
(a)
LSGFM
(b)
NFO
100m SIKA-HX-1
Fe (Ka1)
Ni (Ka1)
La (La1)
Ga (La1_2)
Sr (La1)
O (Ka1)
Fig. 23 Analyses for deposition iii (Table 4) (a) EDS, elemental spectrum of the LSGFM layer (cross section); (b) SEM micrograph (cross section); EDS, elemental mapping of the elements Fe (Ka1), Ga (La1,2), Ni (Ka1), O (La1), and Sr (La1) Deposition ivs top section, SEM micrographs are shown in Figs 24(a)-(f). Again, while operating with the grounded, cooling mask, and assuming 60 deposition loops (LSGFM), the crater formation rate is 0.060.01 craters loop-1 mm-2. The high resolution micrographs shows that not all of the feedstock powders attain a purely fused state in the plasma core, particularly those having dp>20 m. *Corresponding author Tel.: +1 819 821 8000ext63238; fax: +1 819 821 7095
28
LSGFM
(a)
LSGFM
(b)
1000m
200m
LSGFM
(c)
LSGFM
(d)
50m
20m
LSGFM
(e)
LSGFM
(f)
10m
20m
Fig. 24 Analyses for deposition iv (Table 4) (a)-(f) SEM micrographs (top section) For deposition v, to investigate the possibility of liquefying a greater portion of the feedstocks particles, the suspensions solid wt% was lowered. Furthermore, this was the first trial that employed the electrically insulated sample holder (Fig. 3). Numerous depressions are shown by the global SEM micrographs of their top sections (Fig.s 25(a)-(c)). The cavernous character differs from the craters that result from the plasma-substrate arcing and it can be concluded that they are a corollary of the larger pore size of the SIKA-SS-10 substrates. Ostensibly, the plasma-substrate arcing can be eliminated by operating with the new sample holder in combination with the grounded, cooling mask. As well, as anticipated and exemplified by the high-resolution micrographs given in Figs 24(c)-(d), the percentage of *Corresponding author Tel.: +1 819 821 8000ext63238; fax: +1 819 821 7095
29
the feedstock that is liquefied in the plasma core is augmented when operating with suspensions comprised of lower wt% solids.
LSGFM (a) LSGFM (b)
500m
500m
LSGFM
(c)
LSGFM
(d)
10m
50m
Fig. 25 Analyses for deposition v (Table 4) (a)-(d) SEM micrographs (top section) Deposition vis top-sectional, XRD pattern coincides with the feedstocks (Fig. 8(a)). Figs. 26(a)-(f) are its top- and cross- sectional, SEM micrographs of varying resolutions. Because a SIKA-HX1 substrate was used, the deposition is devoid of the caverns previously found (i.e. deposition v). Judging by the quantity of splat formations (Figs. 26(c)-(d)), presumably, the vast majority of the feedstock powders were liquefied in the plasma core. The deposition rates for the NFO, GDC, and LSGFM/LSGM layers were 0.990.15, 0.650.30, 1.000.50 m loop-1, respectively. While there is some slight open porosity at the GDC-LSGM interface, the deposition is dense. Only one vertical crack-which again appears to have commenced at the top of the coating-can be found along the depositions cross-section; but, to a lesser extent, horizontal cracks are also present. The EDS, elemental line-scans, which are shown in the bottom panels of Fig. 27, demonstrate the excellent separation between the material deposits. Using these optimized SPS parameters, similar results were achieved (i.e. reproducible); multilayer, anodic, IT-SOFC half-cells of varying LSGFM thicknesses were prepared for further investigations [37]. Notably, for these coatings, the coating thicknesses were an order of magnitude less than those presented here and they did not suffer from vertical or horizontal cracks.
30
LSGFM
(a)
LSGFM
(b)
500m
100m
LSGFM
(c)
LSGFM
(d)
50m
5m
(e) LSGFM LSGFM
(f)
100m
50m
Fig. 26 Analyses for deposition vi (Table 4) (a)-(d) SEM micrographs (top sections); (e)-(f) SEM micrographs (cross sections)
31
LSGFM GDC
(a)
600 (b) LSGFM SrLaGa3O7
500
Relative Intensity
400
300
NFO 20m SIKA-HX-1
200
100
0 20 30 40 50 60 70 80
Position (2 theta)
Fe (La1)
Ce (La1)
Gd (La1)
Ni (Ka1)
Sr (La1)
Ga (La1_2)
La (La1)
O (Ka1)
Fig. 27 Analyses for deposition vi (Table 4) (a) SEM micrographs (cross section); (b) XRD pattern (top section); EDS, elemental line-scans for the composition line shown in (a) are given in the bottom panels The experimental findings from this sub-section can be summarized as follows: grounding the cooling mask drastically diminishes the rate of crater formation; grounding the cooling mask in combination with the electrically-insulated sample-holder eliminates the plasma-substrate arcing; depositions on SIKA-HX-10 substrates results in cavernous coatings; depositions on SIKA-HX-1 substrates renders coatings having uniform depths; feedstock liquefaction in the plasma core is largely dependent on the suspensions solid content; compared to the relevant TSDP literature pertaining to dense, ceramic coatings, the optimized, multi-layer depositions (e.g vii) are of very high quality.
At this juncture, there are several recent claims that have been made by CREPE researchers that need to be addressed. Jia and Gitzhofer [42] stated that the lowest viscosity suspensions were ideal for SPS, which contradicts this investigations findings. In regards to their high resolution, 79 m2 micrographs of the SPS deposition of GDC, they claimed that negligible gas permeability along with low coating porosity (1.4%) was attainable while using both induction coupled plasma and GNP synthesized powders, which indicates that they did not observe the
32 plasma-substrate arcing. However, this does not correspond to the authors understanding of matters. In their description of the test rig they used for the measurement of gas permeability, no mention of how their coated substrates were fixed into the test rigs enclosure was given. The author deemed that open circuit voltage readings would be more accurately allow for the determination of gas permeability and coating porosity hence their test rig was not used. Moreover, despite claiming that powder synthesis was achieved by two different methods, the high-resolution SPS micrograph that were presented in the separate articles [42, 43] were the same, and no low-resolution micrographs were presented. Lastly, the SPS apparatus set-up for the coatings that were presented in the Gitzhofer et al.s follow-up article [37] did not correspond to reality; rather, in order to eradicate plasma-substrate arcing, the set-up shown in Fig. 3 was used. Attempts at extending these promising results to ERH anode compartments will now be elaborated.
3.4 SPS for the fabrication of ERH anode compartments Table 5 lists the parameters/post-deposition analyses used in the investigations of, ERH anode compartment (2.3) prepared by SPS. For these investigations, the SPS stand-off distance was 4.5 0.5 cm and, unless stated otherwise, the suspension flow-rate was 4.0 0.1 ml min-1. Furthermore, in order to achieve a denser GDC interlayer, its suspensions solid content was diminished from 8 to 3 wt%. GDC has a significantly higher fusion temperature (~3000 K) compared to those of NFO and the double-doped LaGaO3 (~1800 K). All other suspensions were comprised of 8 wt% solids. Finally, as will be discussed in more depth below, the sequencing of the post-deposition, H2 reduction (H2R in Table 4) plays an important role in the successful fabrication of the ERH anode compartments. Components were placed under a flowing (100 25 ml min-1) H2 (99.9 vol%) atmosphere at 923 10 K for 6 hrs. In order to determine if the reduction of the anode layer(s) had indeed taken place in the allotted time-frame, electrical resistance measurements were taken before and after their depositions. Similar tests proved that the incorporated Fe 2O3, in LSGFM is not reduced by H2 to its metallic state under the aforementioned conditions. At the time of this writing, Ishihara et al.[19] had obtained the highest power densities in the ITSOFC literature. This was achieved by the in-situ reduction of the NiO-Fe2O3 substrate after the deposition of the SOAE layers were deposited by pulsed laser deposition. Being that the ERH process to be tested was to be done with a metal-supported, anode compartment fabricated by TSDP, which are susceptible to vertical cracks, relatively thick ( 100 m) SOAE layers were deposited so to lessen the possibility of catholyte cross-over. The SEM micrographs of deposition is top-section are shown in Fig. 28. Judging by the coatings surface, ostensibly, while in the plasma core, the feedstock had reached a quasi-vaporized state. The post-deposition measurement of the suspensions flow-rate rendered an unexpected value of 2.5 0.1 ml min-1 due to a worn out tube.
33
Table 5 Summary of the varied parameters values during the SPS on ERH anode compartments having the NPT design Deposition Ii Iii Iiii Powder no. loops H2R NFO 15 LSGFM 20 NFO 35 R LSGFM 99 R NFO 35 GDC 4 LSGM 3 LSGFM 110 R NFO 35 GDC 4 LSGM 3 R LSGFM 99 NFO 35 GDC 4 LSGM 3 R LSGFM 99 R NFO 35 *7NFO3SDC 3 R **3NFO7SDC 3 GDC 4 LSGM 3 R LSGFM 150 NFO 30 *7NFO3SDC 3 R **3NFO7SDC 3 GDC 3 LSGM 3 R LSGFM 99 NFO 30 *7NFO3SDC 3 R **3NFO7SDC 3 GDC 3 LSGM 3 LSGFM 70
Iiv
Iv
Ivi
Ivii
Iviii
**3NFO7SDC-30wt%NFO-SDC; *7NFO3SDC-70wt%NFO-S
34
LSGFM
(a)
LSGFM
(b)
200m
50m
LSGFM
(c)
LSGFM
(d)
20m
5m
Fig. 28 Analyses for deposition i (Table 5) (a)-(d) SEM micrographs (top section)
To test the functionality of the ERH anode compartment that resulted from deposition ii, OCV measurements were taken using the arrangement depicted in Fig. 5. As the systems temperature was augmented between 87310 and 92310 K, the OCV increased from 0.3850.003 and 0.6450.003 V. Thereafter, it diminished rapidly (~3 mV min-1) until a zero voltage reading was obtained. The measured value at 92310 K is in reasonable accordance with the one obtained by Ishihara et al. [19]. This was the only ERH anode compartment that was characterized in this way. The subsequent SEM analysis of the samples cross-section (Figs. 29(a)-(e)) shows that, during the examination period, other than the far left portion of the coating (Fig. 29(a)), the LSGFM layer had completely delaminated itself from the quasi-dense, 305 m thick, 90wt%Ni-Fe, anode layer. The latter material remained flush and fully adhered to the well adjoined SIKA-HX-1 and Inconel materials that constitute the integral, flow-restrictor substrate. Five minor vertical cracks of variable spacing between each (50-400 m) can be observed along the 10010 m thick, LSGFM layer (Fig. 29(c)), which was therefore deposited at a rate of 1.010.10 m loop-1. From these analyses it can be concluded that the custom cooling arrangement can achieve the goal of substrate temperature management but a protocol that allows for an adherent, multilayer deposition following the H2 reduction of NFO is still required.
35
(a)
(b)
Ag LSGFM SIKA-HX-1 90wt%Ni-Fe Inconel 500m Inconel SIKA-HX-1 500m Ag LSGFM 90wt%Ni-Fe
(c)
(d)
Ag LSGFM 500m 90wt%Ni-Fe SIKA-HX-1 LSGFM (f)
Ag LSGFM Inconel 90wt%Ni-Fe SIKA-HX-1 (e) Ag 500m
LSGFM 90wt%Ni-Fe Inconel SIKA-HX-1 100m 90wt%Ni-Fe SIKA-HX-1 200m Inconel
Fig. 29 Analyses for deposition ii (Table 5) following the OCV testing (a)-(d) SEM micrographs (cross sections) Deposition iiis H2 reduction sequence allows for the investigation of the cohesion of the SOAE layer(s) on the 90wt%Ni-Fe anode layer. So to conform, as much as possible, to the desired final product, GDC and LSGM inter-layers were included. The SEM micrographs of its cross sections are displayed in Figs. 30(a)-(f). The apparent LSGFM/LSGM and GDC deposition rates are 1.190.18 and 0.190.06 m loop-1, respectively. As the deposition of the NFO layer was succeeded by its H2 reduction, a corresponding value cannot be assigned; hence, only a superficial (i.e. 90wt%Ni-Fe) deposition rate of 0.740.12 m loop-1 can be given. The anodes sub-micron porosity is particularly notable (Fig. 30(f)). Although there is excellent coherence between the various layers, it can be seen that, in comparison with the previous *Corresponding author Tel.: +1 819 821 8000ext63238; fax: +1 819 821 7095
36
depositions of simple substrates, the number of vertical and horizontal cracks is extensive; a significant percentage of the former type, which occur at a frequency of 5-6 cracks mm-1, penetrate the multi-layer coating all the way up to the substrate; the latter type, which often but not always span themselves between two neighbouring vertical cracks, appear to coincide with an individual layer resulting from a single, deposition pass. Speculative reasons for the formation of these macro-fissures include: (a) insufficient substrate cooling at the time of the deposition which results in the coatings subsequent, rapid, post-deposition cooling; (b) abrasive, post-deposition handling of the component during its removal from the cooling apparatus; (c) CTE mismatch between the substrate and deposited layers; and (d) the inherent vibrations that the robotic arm perpetuates during the deposition. A Swagelok, SS316, bottom ferrule was used to make the thermal contact between the underside of the substrate and the interior cooling apparatus. The ferrules thermal conductivity (16.3 W m-1 K-1), in combination with its irregular shape, lends credence to (a). Moreover, the obnoxious macrofissures are more probably a consequence of reasons (a) and (b) together. Because of coppers excellent ductility and high thermal conductivity (386.0 W m-1 K-1), it is a preferable thermal contact material; hence, copper foil was used for depositions iv, v, vii, and viii. The remaining aforementioned reasons are regarded with less confidence but are worthy of mention for future researchers. Prior to depositing its three SOAE layers, deposition ivs NFO layer was H2 reduced to its metallic state. The completed deposition was then exposed to a H2 environment; thereafter, the SEM micrographs for both the coatings top (Figs 31(a)-(d)) and cross (Figs 31(e)-(h)) section were taken. Due to the cross-sectional micrographs poor colour resolution it is not possible to ascertain the GDC layers thickness. However, the LSGFM/LSGM and superficial anode deposition rates are 1.040.07 and 0.790.07 m loop-1, respectively. The anode layers sub-micron porosity is visible in Figs 31(e)-(f).
37
(a) LSGFM LSGM GDC 90wt%Ni-Fe Inconel SIKA-HX-1 500m GDC 90wt%Ni-Fe 300m LSGFM
LSGM
(b)
SIKA-HX-1
(c)
(d)
LSGFM
LSGM
LSGFM
LSGM
GDC
90wt%Ni-Fe 300m
GDC
90wt%Ni-Fe 300m
SIKA-HX-1
SIKA-HX-1
(e)
90wt%Ni-Fe GDC
LSGFM
LSGM
(f)
LSGFM
LSGM
Inconel SIKA-HX-1
GDC
90wt%Ni-Fe 300m 50m
SIKA-HX-1
Fig 30 Analyses for deposition iii (Table 5) (a)-(f) SEM micrographs (cross sections)
38
LSGFM
(a)
LSGFM
(b)
1000m
200m
LSGFM
(c)
LSGFM
(d)
200m
50m
(e) LSGFM
LSGM
(f)
LSGFM
LSGM
GDC 90wt%Ni-Fe Inconel SIKA-HX-1 500m (g)
GDC 90wt%Ni-Fe SIKA-HX-1 Inconel 500m
(h)
LSGFM
LSGM
LSGFM
LSGM
90wt%Ni-Fe SIKA-HX-1
GDC 500m
GDC SIKA-HX-1
90wt%Ni-Fe 500m
Fig 31 Analyses for deposition iv (Table 5) (a)-(d) SEM micrographs (top section); (e)-(h) SEM o micrographs (cross section) *Corresponding author Tel.: +1 819 821 8000ext63238; fax: +1 819 821 7095
39
Deposition vs cross-sectional micrographs are shown in Fig. 32. The SOAE layers completely delaminate themselves from the anode, which remained adhered to the integral metal component. Despite the addition of the LSGM and GDC SOAE interlayers, the overall result is similar to what occurred in the case of deposition ii. Tentatively, one may conclude that it is essential to reduce the anode layers prior to the deposition of the SOAE layers as the volumetric change that the anode layer endures during the reduction step renders the undesirable result.
(a) LSGFM LSGM 90wt%Ni-Fe GDC 90wt%Ni-Fe SIKA-HX-1 Inconel SIKA-HX-1 500m Inconel LSGFM LSGM GDC
(b)
500m
(c)
(d)
LSGFM
LSGM
LSGFM LSGM GDC GDC 90wt%Ni-Fe 500m SIKA-HX-1 500m
(e) LSGFM
LSGM
(f) LSGFM
LSGM
GDC 90wt%Ni-Fe SIKA-HX-1 Inconel 200m GDC 90wt%Ni-Fe SIKA-HX-1 200m Inconel
Fig. 32 Analyses for deposition v (Table 5) (a)-(f) SEM micrographs (cross sections) Deposition vis cross-sectional SEM micrographs are shown in Fig 33. As a Swagelok, SS316, bottom ferrule was used to make thermal contact between the substrate and the interior cooling apparatus *Corresponding author Tel.: +1 819 821 8000ext63238; fax: +1 819 821 7095
40
(Fig. 4), the depositions character resembles deposition iiis. This is illustrated by the prevalence of horizontal (6-7 cracks mm-1) and vertical fissures that are of the particularity previously described. However, there is good coherence between the anode, cermet, and electrolyte layers; therefore, the cermet layers are effective in diminishing the interlayer tension that results from materials differing CTEs. Finally, the loss of the electrolyte layers shown in Fig. 33(b) may have occurred while removing the component from cooling apparatus following the final depositions.
(a)
(b)
LSGFM LSGFM 90wt%Ni-Fe GDC GDC

LSGM 3NFO7SDC 7NFO3SDC LSGM 3NFO7SDC 7NFO3SDC
90wt%Ni-Fe
Inconel SIKA-HX-1 500m
SIKA-HX-1
500m
(c)
(d)
LSGM 3NFO7SDC 7NFO3SDC
LSGFM
LSGFM
GDC 500m
90wt%Ni-Fe
GDC 500m
SIKA-HX-1 (e) LSGFM LSGFM

(f)
GDC 90wt%Ni-Fe
GDC Inconel
SIKA-HX-1 Inconel 200m 100m
Fig. 33 Analyses for deposition vi (Table 5) (a)-(f) SEM micrographs (cross section)
With the exception of the use of copper foil as the cooling apparatus-substrate thermal connection and the number of LSGFM deposition passes, the protocol used for deposition vi and vii were the same; *Corresponding author Tel.: +1 819 821 8000ext63238; fax: +1 819 821 7095
41
the latters cross-sectional, SEM micrographs, along with its top-sectional XRD pattern, are shown in Fig. 34. Although present, the incidence and character of the vertical and horizontal cracks was less than what was found in the previous deposition. This supports the hypothesis that: amid deposition, maximum substrate cooling increases the uniformity of the coating. The reason for the phenomenon may be because the transformation of energy that is endured during the relaxation of residual stresses in a macroquench-i.e. deposited material resulting from several deposition passes-is in excess of what would otherwise be experienced if the liquefied particles from an single pass are quenched and relieved of the their residual stresses prior to the deposition of the succeeding layer. The electrolyte layers are coherent to the anode layer. If compared with the previous depositions, the addition of the cermet layers is responsible for the positive result. Due to substrate misalignment, there is considerable variation in the electrolyte layers thickness ranges between 333 to 90 5 m, going from left to right. Other notable observations include: (I) the sub-micron porosity of the anode layer (Figs. 34(a),(c)-(d)); (II) the LSGFM, perovskite phase was present following the deposition (Fig. 34(h)); (III) the poor coherence between the porous SIKA-HX-1 and solid Inconel housing at the integrated substrates left side (Figs. 34(a)-(c)); and (IV) the detachment of the SOAE layers at the outer edge (Figs. 34(a),(d)). The latter two observations may be a direct result of the handling of the post-deposition component. Further efforts are required to resolve minor issues surrounding the custom cooling apparatus.
42
(a) LSGFM LSGM 90wt%Ni-Fe GDC

(b) LSGFM
LSGM
90wt%Ni-Fe
GDC
Inconel SIKA-HX-1
Inconel
SIKA-HX-1 100m 300m
LSGFM
LSGM
(c)
(d)
GDC LSGFM SIKA-HX-1

90wt%Ni-Fe
GDC Inconel 100m 90wt%Ni-Fe Inconel (e) (f) 100m
LSGFM LSGFM
GDC
50m
GDC 90wt%Ni-Fe SIKA-HX-1 (g)

20
50m
(h) (h) LSGFM SrLaGa3O7
15
Relative Intensity
10
LSGFM GDC 50m
0 20 30 40 50 60 70 80
Position (2 theta)
Fig. 34 Analyses for deposition vii (Table 5) (a-g) SEM micrographs (cross section); (h) XRD pattern (top section) *Corresponding author Tel.: +1 819 821 8000ext63238; fax: +1 819 821 7095
43
Points worth reiterating from the investigations pertaining to the fabrication of NPT type, ERH anode compartment via SPS include: NFO experiences a volumetric change during its H2 reduction to its corresponding sub-micron, porous metallic form which causes the SOAE layer(s) to delaminate; hence, the deposition of the electrolyte layers must succeed the reduction of the NFO layer; degrees to which substrate cooling occurs reflects upon the homogeneity of coatings, particularly as it pertains to the incidence of both horizontal and vertical cracking -where maximum cooling amid deposition renders the best result; diminishing the interlayer CTE mismatch via additional cermet layers mitigates the SOAE layer(s) from delaminating from the anode; unlike the optimal depositions in sub-section , crack-free coatings were not achieved during the course of this optimization; modifications to the SPSs cooling apparatus (Fig. 3.4) that will allow for more intensive substrate cooling during SPS and less abrasive addition and removal of the substrates are required. A TSDP coating study that unequivocally demonstrates the outright eradication of the fissuring phenomena is unknown to the author. This, of course, does not bode well for the experiments that were supposed to be at the heart of this multidisciplinary study. Only a superficial investigation of the hypothetical process was possible in the allotted time-frame. 4. Conclusions Significant gains were made in the field of SPS, multi-layered, ceramic-to-metal deposition technology. Necessarily, many of the previously stated parameters were significantly modified. This includes: (a) the suspensions solvent; (b) the post-tailoring of the GNP-synthesized powders; (c) the anodes post-deposition, H2 reduction sequence; (d) the substrate type; (e) the substrates cooling amid deposition; and (f) the substrate holder. Particularly, the undisclosed, deleterious, plasma-substrate arcing was completely eradicated via the development of an electrically-insulated substrate-holder. In regards to the TSDP literature pertaining to the deposition of dense, ceramic layers on metal substrates, the optimized depositions given in 3.3 are of the highest quality known to the author. Although the results were not fully transposed to the ERH anode compartments that were desired for a fundamental investigation of a novel electrochemical process, they could instead be considered for intermediate temperature water electrolysis, IT-SOFC, or other applications. For economic reasons, Hastelloy X could be substituted by cheaper iron substrates, and air, as opposed to O2, could be considered as the principal plasma gas. More generally, because of the increase in the volumetric power density that results when operating SPS with hydrocarbon solvents and O2 rich plasmas, this sub-family of TSDPes is very versatile. Acknowledgements The financial support received from Kingston Process Metallurgy Inc., AUTO21, and NSERC made this project possible. Along with F. Gitzhofer, CREPE technicians F. Barrette, S. Gutierrez, K. Br, B. Couture, I Kelsey-Lveque, and N. Simard were instrumental in the manifestation of this work.
References
[1] Calabretta DL (2006) Queens University (masters thesis)
44
[2] [3] Calabretta DL, Davis BR (2007) J Power Sources 164(2): 782-791 Calabretta DL (2009) Proceedings of the 2009 Hydrogen and Fuel Cells Conference (Vancouver, Canada) [4] Ivers-Tiffe E (2009) Encyclopedia of Electrochemical Power Sources: 181-187 [5] Badwal SPS, Ciacci FT (2000) Ionics 6: 1-20 [6] Ishihara T, Matsuda H, Takita Y (1994) J Am Chem Soc 116: 3801-3803 [7] Ishihara T (2006) B Chem Soc Jpn 79(8): 1155-1165 [8] Ishihara T, Enoki M, Yan J, Matsumoto H (2005) Solid Oxide Fuel Cell (SOFC), Electrochemical Society Proceedings: 1117-1126 [9] Ishihara T, Ando M, Enoki M, Takita Y (2006) J Alloy Compd 408-412: 507-511 [10] Enoki M, Yan J, Matsumoto H, Ishihara T (2006) Solid State Ionics 177: 2053-2057 [11] Gitzhofer F, Bouyer E, Boulos MI (1994) US patent 5609921 [12] Bonneau M-E (2001) Universit de Sherbrooke (masters thesis) [13] L. Jia (2010) Universit de Sherbrooke (PhD thesis) [14] Schiller G, Mller M, Gitzhofer F (1999) J Therm Spray Technol 8(3): 389-392 [15] Hui R, Wang Z, Kesler O, Rose L, Jankovic J, Yick S, Maric R, Ghosh D (2007) J Power Sources 170: 308-323 [16] FactSage 6.2 ThermFact and GTT Technologies [17] Sasaki K., Muranaka M, Suzuki A, Terai T (2008) Solid State Ionics 179: 1268-1272 [18] Yoo Y (2006) J Power Sources 160: 202-206 [19] Ishihara T, Yan J, Shinagawa M, Matsumoto H (2006) Electrochim Acta 52: 16451650 [20] Hui R, Yang D, Wang Z, Yick S, Deces-petit C, Qu W, Tuck A, Maric R, Ghosh D (2007) J Power Sources 167: 336-339 [21] Hui R, Wang Z, Kesler O, Rose L, Jankovic J, Yick S, Maric R, Ghosh D (2007) J Power Sources 170: 308-323 [22] Henne R (2007) J Therm Spray Technol 16(3): 381-403 [23] Henne R, Muller M, Prob E, Schiller G, Gitzhofer F, Boulos M (1999) J Therm Spray Technol 8(1): 110-116 [24] Takenoiri S, Kadokawa N, Koseki K (2000) J Therm Spray Technol 9(3): 360-363 [25] Tsukuda H., Notomi A, Hisatome N (2000) J Therm Spray Technol 9(3): 364-368 [26] Schiller G, Henne RH, Lang M, Ruckdaschel R, Schaper S (2000) Fuel Cells Bulletin 3(21): 7-12 [27] Lang M, Henne R, Schaper S, Schiller G (2001) J Therm Spray Technol 10(4): 618625 [28] Lang M, Franco T, Schiller G, Wagner N (2002) J Appl Electrochem 32(8): 871-874 [29] Schiller G, Henne R, Lang M, Muller M (2004) Fuel Cells 4(1-2): 56-61 [30] Stver D, Hathiramani D, Vaen R, Damani R (2006) Surf Coat Technol 201: 20022005 [31] Ma XQ, Hui S, Zhang H, Dai J, Roth J, Xiao TD, Reisner DE (2003) Thermal Spray: Advancing the Science and Applying the Science, ASM International: 163-168 [32] Hwang C, Tsai C, Lo C, Sun C (2008) J Power Sources 180: 132-142 [33] Bouchard D (2006) Universit de Sherbrooke (masters thesis) [34] Gheriani M (2008) Universit de Sherbrooke (masters thesis) [35] Mailhot K (1998) Universit de Sherbrooke (masters thesis) [36] Vallet-Renouard G (2004) Universit de Sherbrooke (PhD thesis) [37] Shan Y, Almeida VAB, Gitzhofer F (2010) J Therm Spray Technol 19(3): 566-574 [38] Calabretta D; (2012) Universit de Sherbrooke (PhD thesis) [39] Ishihara T, Yan J, Enoki M, Okada S, Matsumoto H (2008) J Fuel Cell and Technol 5: 031205 [40] Yan J, Matsumoto H, Enoki M, Ishihara T (2005) Electrochem Solid State Letters *Corresponding author Tel.: +1 819 821 8000ext63238; fax: +1 819 821 7095
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8(8): A389-A391 Bilodeau J (2012) Universit de Sherbrooke,(masters thesis) Jia L, Gitzhofer F (2010) J Therm Spray Technol 19(3): 566-574 Gitzhofer F, Jia L (2008) Int J Appl Ceramic Technol 5(6): 537-547 Cong L, He T, Ji Y, Guan P, Huang Y, Su W (2003) J Alloy Compd 348: 325-331 Wang Z, Berghaus JO, Yick S, Deces-Petit C, Qu W, Hui R, Maric R, Ghosh D (2008) J Power Sources 176: 90-95 [46] Lee D, Han J, Chun Y, Song R, Shin D (2007) J Power Sources 166: 35-40 [41] [42] [43] [44] [45]

Radio-Frequency Induction-Coupled Suspension Plasma Spraying of Dense Ceramic Layers On Metal Substrates

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Radio-Frequency Induction-Coupled Suspension Plasma Spraying of Dense Ceramic Layers On Metal Substrates

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1

C15H32 0.2 CH3OH 0.1

flow rate (ml min-1)

double-walled powder collection-vessel

Value 221 611 110.5 13.36.7 501 5.51.5 73 34510

Faraday cage torch

influent water interior water-cooling

Fig. 5 Experimental arrangement used for OCV measurements

La0.7Sr0.3Ga0.7Mg0.2Fe0.1O3- SrLaGa3O7 La4Ga2O9

Deposition Ii iii iii iiv iv ivi ivii iviii iix ix ixi

LSGFM 29.4 m 10 m Ti 23. m

(c) LSGFM LSGFM

100 m SIKA-HX-1 SIKA-HX-1 (c) LSGFM

SEM, EDS, XRD

Fig. 22 Analyses for deposition ii (Table 4) (a)-(c) SEM micrographs (top-section)

(e) LSGFM LSGFM

NFO 20m SIKA-HX-1

Ag LSGFM 500m 90wt%Ni-Fe SIKA-HX-1 LSGFM (f)

Ag LSGFM Inconel 90wt%Ni-Fe SIKA-HX-1 (e) Ag 500m

LSGFM 90wt%Ni-Fe Inconel SIKA-HX-1 100m 90wt%Ni-Fe SIKA-HX-1 200m Inconel

90wt%Ni-Fe 300m 50m

GDC 90wt%Ni-Fe Inconel SIKA-HX-1 500m (g)

GDC 90wt%Ni-Fe SIKA-HX-1 Inconel 500m

LSGFM LSGM GDC GDC 90wt%Ni-Fe 500m SIKA-HX-1 500m

LSGFM LSGFM 90wt%Ni-Fe GDC GDC

Inconel SIKA-HX-1 500m

LSGM 3NFO7SDC 7NFO3SDC

LSGM 3NFO7SDC 7NFO3SDC

SIKA-HX-1 (e) LSGFM LSGFM

SIKA-HX-1 Inconel 200m 100m

(a) LSGFM LSGM 90wt%Ni-Fe GDC

LSGM 3NFO7SDC 7NFO3SDC

SIKA-HX-1 100m 300m

LSGM 3NFO7SDC 7NFO3SDC

GDC LSGFM SIKA-HX-1

GDC Inconel 100m 90wt%Ni-Fe Inconel (e) (f) 100m

GDC 90wt%Ni-Fe SIKA-HX-1 (g)

(h) (h) LSGFM SrLaGa3O7

LSGM 3NFO7SDC 7NFO3SDC

LSGFM GDC 50m

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