Hydrogen isotope permeation through yttria coatings on Eurofer in the diffusion limited regime

In fusion power plants a tritium permeation barrier is required in order to prevent the loss of the fuel. Moreover, the tritium permeation barrier is necessary to avoid that the radioactive tritium accumulates in the first wall, the cooling system, and other parts of the power plant. Oxide thin films, e.g. Al₂O₃, Er₂O₃ and Y₂O₃, are promising candidates as tritium permeation barrier layers. With regard to the application, this is especially true for yttrium due to its favorably short decay time after neutron activation compared to the other candidates. The Y₂O₃ layers with thicknesses from 100 nm to 500 nm are deposited on both sides of Eurofer substrates by RF magnetron sputter deposition. Some of the samples are additionally deposited with palladium thin films to analyse the limited regime. During the annealing in the experiments the palladium layers do not show any crack formation or delamination, verified by scanning electron microscopy. After annealing the cubic crystal structure of the Y₂O₃ layers is verified by X-ray diffraction. The cubic phase contains a small amount of a monoclinic phase, which is eliminated after the permeation measurements. The permeation reduction factors of the samples are determined in gas-driven deuterium permeation experiments. A permeation reduction of 5000 of the yttria thin film is verified. The diffusion limited regime is identified by the pressure dependence of the permeation measurement and by permeation experiments with the palladium top layers on the Y₂O₃ thin films. Furthermore, the activation energy of the permeation through the yttria thin films is determined. Pre-annealing times for more than 70 h of the Y₂O₃ thin films and permeation measurements with temperature cycles for 20 days are performed to show the stability of the permeation flux and hence the microstructure of the barrier layers. Measurement times at each constant temperature level of more than 25 h are required for the stabilization of each permeation flux to a constant value. The permeation measurement setup is enhanced to enable a continuously running equipment for these measurement times.     

Hydrogen interaction characteristics of a Cr2O3Y2O3 coating formed on stainless steel in an ultra-low oxygen environment

Ceramics are the most promising candidates for tritium permeation barriers for fusion reactors due to their high thermal and chemical stabilities and low hydrogen isotope permeation reduction factors. However, hydrogen embrittlement and a large number of defects in ceramic coatings are new challenges for first wall materials in nuclear reactors. To address this issue, a new Cr₂O₃Y₂O₃ coating with a thickness of about 100 nm was synthesized and placed in an ultra-low oxygen partial pressure (8 × 10⁻²⁰ Pa) environment, in which a compact CrY alloy coating was successfully deposited on the stainless-steel substrate by pulsed electrochemical deposition. The interactions between the coating and hydrogen plasma were comprehensively analyzed and compared via surface analysis techniques, including TEM, XPS and electrochemical impedance spectroscopy (EIS). The mechanical properties of the coating before and after hydrogen permeation were studied by tensile testing. It was found that this ceramic coating effectively reduced the defect concentration and retained a high protective performance upon hydrogen exposure. Therefore, this new Cr₂O₃Y₂O₃ coating has potential as a promising hydrogen permeation barrier.     

Atom doping in α-Fe2O3 thin films to prevent hydrogen permeation

Prevention of hydrogen (H) penetration into passive films and steels plays a vital role in lowering hydrogen damage. This work reports effects of atom (Al, Cr, or Ni) doping on hydrogen adsorption on the α-Fe₂O₃ (001) thin films and permeation into the films based on density functional theory. We found that the H₂ molecule prefers to dissociate on the surface of pure α-Fe₂O₃ thin film with adsorption energy of −1.18 eV. Doping Al or Cr atoms in the subsurface of α-Fe₂O₃ (001) films can reduce the adsorption energy by 0.03 eV (Al) or 0.09 eV (Cr) for H surface adsorption. In contrast, Ni doping substantially enhances the H adsorption energy by 1.08 eV. As H permeates into the subsurface of the film, H occupies the octahedral interstitial site and forms chemical bond with an O atom. Comparing with H subsurface absorption in the pure film, the absorption energy decreases by 0.01–0.22 eV for the Al- and Cr-doped films, whereas increases by 0.82–0.96 eV for the Ni-doped film. These results suggest that doping Al or Cr prevents H adsorption on the surface or permeation into the passive film, which effectively reduces the possibility of hydrogen embrittlement of the underlying steel.     

Preparation of Cr2O3/Al2O3 bipolar oxides as hydrogen permeation barriers by selective oxide removal on SS and atomic layer deposition

Iron-nickel based stainless steel (SS) applied in nuclear plants as a substrate material barely suppresses the permeation of hydrogen plasmas, which are mainly composed of positive and negative hydrogen ions with trace amounts of non-ionized hydrogen atoms. In this work, a new Cr₂O₃/Al₂O₃ bipolar oxide barrier was prepared using atomic layer deposition (ALD) of Al₂O₃ on a Cr₂O₃ layer that was generated by removing partial oxides with cyclic voltammetry (CV) of SS that had been pre-oxidized at 550 °C in air. We found that a small layer of α-Al₂O₃ was formed by the template effect of Cr₂O₃ at the interface of this composite film. The hydrogen permeation behavior of this bipolar oxide barrier in a fusion reactor was simulated with hydrogen-discharging plasma treatment. The results demonstrated that the hydrogen permeation resistance of this bipolar oxide was superior to the original oxide or a Cr₂O₃ film. Impressively, hydrogen plasma treatment repaired the bipolar oxide via reduction of the defective CrO₃, resulting in an improvement in the hydrogen permeation resistance. These findings demonstrate a novel method of hydrogen permeation barrier preparation on SS, providing insight into hydrogen barrier construction for future nuclear energy applications.     

Hydrogen permeation properties of CrxCy@Cr2O3/Al2O3 composite coating derived from selective oxidation of a CrC alloy and atomic layer deposition

Metal oxides and carbides are promising tritium permeation barrier coatings for fusion reactors. However, the thermomechanical mismatch between the coating and substrate poses a threat to their interface's integrity during fabrication and operation. To address this issue, a metallic interlayer coating was introduced followed by selective oxidation in which a compact and uniform CrC amorphous alloy coating was successfully deposited on the stainless steel substrate by pulsed electrochemical deposition. A new composite coating of Cr_xC_y@Cr₂O₃/Al₂O₃ was formed by subsequent controlled oxidation conversion and atomic layer deposition. The phase, morphology, chemical state and defects of the films were analyzed and compared both before and after hydrogen exposure at 300 °C. The results show that this new kind of composite coating, based on the principles of grain boundary pinning of chromic oxide with carbide and defect healing of alumina, can remarkably improve the hydrogen permeation barrier performance of these materials.     

Evaluation of pulse electroplated cobalt/yttrium oxide composite coating on the Crofer 22 APU stainless steel interconnect

Ferritic stainless steels have been evaluated as favorable materials for utilization in SOFC interconnects. However, there are difficulties in utilizing these metallic interconnects, including the quick decrease of their electrical conductivity and cathode poisoning due to the evaporation of Cr species. In this work, Co and Co/Y₂O₃ composite coatings have been deposited onto Crofer 22 APU stainless steels by the pulse current electrodeposition method and the oxidation and electrical properties of uncoated and coated steels have been evaluated. Cyclic oxidation was performed in air at 800 °C for 500 h, oxidation rates were calculated, and oxide layer microstructures were examined. SEM–EDS and XRD investigations exhibited the created oxide layer on both coated samples made up of two scale after oxidation. The internal thin scale was composed of Cr and O and the external scale comprised of Co, Mn, Cr, Fe, and O. Y₂O₃ was observed as dispersed particles in the external oxide scale after the cyclic oxidation test. The thicknesses of internal oxide scale were reduced and oxidations rates also were meaningfully decreased for Co/Y₂O₃-coated steels relative to uncoated and Co-coated steels. Finally the ASR values of coated and uncoated substrates was also tested as a function of temperature and time in air. Results showed that the ASR value of the Co/Y₂O₃-coated steel was 13.1 mΩ cm² after 500 h of cyclic oxidation at 800 °C, which was significantly lower than that of bare steel and the Co-coated sample.     

Effect of magnetron sputtered anode functional layer on the anode-supported solid oxide fuel cell performance

Nickel oxide-yttria stabilized zirconia (NiO-YSZ) thin films were reactively sputter-deposited by pulsed direct current magnetron sputtering from the Ni and ZrY targets onto heated commercial NiO-YSZ substrates. The microstructure and composition of the deposited films were investigated with regard to application as thin anode functional layers (AFLs) for solid oxide fuel cells (SOFCs). The pore size, microstructure and phase composition of both as-deposited and annealed at 1200 °C for 2 h AFLs were studied by scanning electron microscopy and X-ray diffractometry and controlled by changing the deposition process parameters. The results show that annealing in air at 1200 °C is required to improve structural homogeneity of the films. NiO-YSZ films have pores and grains of several hundred nanometers in size after reduction in hydrogen. Adhesion of deposited films was evaluated by scratch test. Anode-supported solid oxide fuel cells with the magnetron sputtered anode functional layer, YSZ electrolyte and La_0.6Sr_0.4Co_0.2Fe_0.8O₃/Ce_0.9Gd_0.1O₂ (LSCF/CGO) cathode were fabricated and tested. Influence of thin anode functional layer on performance of anode-supported SOFCs was studied. It was shown that electrochemical properties of the single fuel cells depend on the NiO volume content in the NiO-YSZ anode functional layer. Microstructural changes of NiO-YSZ layers after nickel reduction-oxidation (redox) cycling were studied. After nine redox cycles at 750 °C in partial oxidation conditions, the cell with the anode NiO-YSZ layer showed stable open circuit voltage values with the power density decrease by 11% only.     

Spontaneous dissociation of H2 and high energy barrier of H invasion on W doped Al2O3(0001) surface

In view of the wide use of tungsten in fusion experimental devices and the importance of hydrogen isotopes permeation, here we studied the adsorption, dissociation, diffusion and invasion behavior of hydrogen on W doped α-Al₂O₃ (0001) surface. Based on the first-principle approaches, we found the W substitution for a top surface Al atom is the most energetically favorable. H₂ molecule prefers to be adsorbed on the surface W and spontaneously dissociates into two H anions. Near the W defects, H atoms favor to be adsorbed at the W and Al sites rather than O sites on the surface, and within the subsurface layer H can only bond to W stably. As a result, H migration to subsurface should occur around W with an energy barrier as large as 4.22 eV which is much larger than the 1.91 eV around the O atom on undoped α-Al₂O₃ (0001) surface. These findings suggest that W surface doping is beneficial to α-Al₂O₃ as tritium permeation barrier.     

Preparation and hydrogen penetration performance of TiO2/TiCx composite coatings

Titanium carbide is a good candidate for tritium permeation barrier in a fusion reactor. However, its oxidation susceptibility and the mismatch between the ceramic coating and substrate are still a challenge. In this study, a promising candidate as a hydrogen permeation barrier, comprising a titanium-based ceramic TiO₂/TiC_x composite coating, was proposed. The preparation process of this TiO₂/TiC_x composite coating involves two steps of carbon ion implantation and oxidation under ultra-low oxygen partial pressure. According to the results, the optimal oxidation temperature for TiO₂ coating is 550 °C, with the increase of the oxidation temperature, the particles on the surface of the oxide layer become coarse and loosely arranged, and the protective performance of the oxide layer is greatly reduced. The hydrogen barrier permeation behavior of the composite coating in a fusion reactor was simulated via hydrogen plasma discharge environment, the results show that the hydrogen barrier permeation performance of the composite is significantly better than that of a single TiO₂ coating. In addition, the coatings treated with hydrogen plasma showed a certain self-repairing performance through the diffusion growth of the TiC_x layer. These findings illustrate a novel method for preparing composite coatings to restrain hydrogen permeation, providing insight into the development of hydrogen permeation barrier materials.     

Energetics and diffusion of hydrogen in hydrogen permeation barrier of α-Al2O3/FeAl with two different interfaces

To provide insights into the interface structure of hydrogen permeation barrier of α-Al₂O₃/FeAl and its effect on stability and diffusion of hydrogen isotopes, the thermodynamics and kinetics of H diffusion in α-Al₂O₃ (001)/FeAl (111) slab with Al/O and Al/Fe/O interfaces have been studied by the density functional theory. Hexagonal alumina layers above the FeAl plane in interface region are predicted. The interfacial binding involves cation–anion and metal–metal interactions. H-surface interaction on the α-Al₂O₃/FeAl slab resembles that on pure α-Al₂O₃ (001) slab, and the H interstitials in the α-Al₂O₃ part of the slab with the Al/O interface are significantly less stable than in bulk of α-Al₂O₃ slab, whereas that with the Al/Fe/O interface are slightly more stable. H diffusion into the α-Al₂O₃ part of both slabs must overcome a larger barrier of about 1.66–2.02 eV at surface-to-subsurface step, as pure α-Al₂O₃ case. For the bulk path, the migration of H atom can occur more readily in the α-Al₂O₃ part of the slab with the Al/O interface compared to that with the Al/Fe/O interface. Thus α-Al₂O₃/FeAl barrier with interface region of the Al, Fe mix-oxide is predicted to be much effective at protection against H permeation of the underlying steel.     

Stability of Y2O3 hydrogen isotope permeation barriers in hydrogen at high temperatures

Hydrogen isotope permeation barriers (HIPB) have great potential applications in the fields of hydrogen energy and thermonuclear fusion energy. Here, we report the stability of Y₂O₃ HIPB in gaseous hydrogen at high temperatures including the structures, mechanical properties and electrical properties. With increasing hydrogen treatment time at 700 °C, the high-index diffractions of Y₂O₃ became weak gradually whereas the (400) diffraction was strengthened. The color of the Y₂O₃ HIPB changed from brown to gray. The bonding strength decreased by 61% with increasing hydrogen treatment time, and finally remained unchanged. Meanwhile, the electrical resistivity of the Y₂O₃ HIPB decreased from 8.2 × 10⁹ Ω cm by over two orders of magnitude and then tended to be constant. The oxygen loss as well as hydrogen incorporation was proposed to be responsible for these modifications and indications of the present work for preparation of HIPB with high reliability were discussed.     

Influence of the nanoscale structural features on the properties and electronic structure of Al-doped ZnO thin films: An X-ray absorption study

Transparent Al-doped ZnO thin films were deposited by reactive magnetron sputtering with different oxygen flow rates. The electronic resistivity, measured by the 4 point-probe method, is very sensitive to the sample position relative to the magnetron axis: the closer the magnetron from the axis the higher the resistivity. This is more pronounced for the films deposited under higher oxygen flow rate. Neither Rutherford backscattering spectroscopy nor Zn-K edge X-ray absorption near-edge structure (XANES) analyses evidenced any change in chemical composition such as a measurable variation of the oxygen stoichiometry. XANES at the Al-K and O-K edges show that (i) a portion of the aluminum atoms get positioned in octahedral conformation with oxygen, consistent with the formation of an Al₂O₃(ZnO)_m nanolaminate structure, (ii) the films exhibit relaxed O-terminated (0 0 0 1) surfaces with a higher density of empty states in more resistive samples. These two findings are believed to play a significant role on the electrical measurements by dopant deactivation and by creating an insulating barrier at the film surface, respectively.     

Effects of surface oxide films on hydrogen permeation and susceptibility to embrittlement of X80 steel under hydrogen atmosphere

Hydrogen embrittlement (HE) induced by hydrogen permeation is a serious threat to the hydrogen transmission pipeline. In this study, oxide films were prepared on X80 steel by applying high-temperature oxidation, blackening treatment and passivation in concentrated H₂SO₄, and their effects on hydrogen permeation and HE susceptibility of X80 substrate were studied by conducting hydrogen permeation tests and slow strain rate tension (SSRT) tests. A numerical diffusion model was established to quantitatively determine the resistance of these oxide films to hydrogen permeation. Results showed that the oxide film prepared by high-temperature oxidation presented the highest resistance to hydrogen permeation with the ?_m/?_f value of 3828, and the corresponding HE index decreased from 38.07% for bare X80 steel to only 4.00% for that covered with oxide film. The characteristic of the corresponding fracture surfaces changed from brittle features such as quasi cleavage facets and secondary cracks to typical ductile dimple feature.     

Investigation on properties of BaZr0.6Hf0.2Y0.2O3-δ with sintering aids (ZnO,NiO, Li2O) and its application for hydrogen permeation

BaZr_0.8Y_0.2O_3-δ proton conductor has the characteristics of excellent chemical stability, but its impoverished sinterability and low conductivity hinder its applications in fuel cell and hydrogen separation. Hf doping in Zr site improves BaZr_0.6Hf_0.2Y_0.2O_3-δ sinterability and conductivity. To further enhance BaZr_0.6Hf_0.2Y_0.2O_3-δ properties, three kinds of sintering aids ZnO, NiO or Li₂O were introduced and their effect on the sinterability, microstructure and conductivity of BaZr_0.6Hf_0.2Y_0.2O_3-δ were studied. The experimental results display that 4 mol% ZnO can enhance the sinterability and conductivity of BaZr_0.6Hf_0.2Y_0.2O_3-δ sample sintered at 1400 °C. Compared with BaZr_0.6Hf_0.2Y_0.2O_3-δ sintered at 1600 °C, BaZr_0.6Hf_0.2Y_0.2O_3-δ with 4 mol% ZnO is of larger grain size, higher relative density (95.5%) and lower sintering temperature (reducing by 200 °C). Meanwhile, the conductivity of BaZr_0.6Hf_0.2Y_0.2O_3-δ with 4 mol% ZnO reaches 4.17 × 10^?3 S cm^?1 in wet 5% H₂/Ar at 700 °C, due to the reduction of the grain boundary resistance of sample. BaZr_0.6Hf_0.2Y_0.2O_3-δ with 4 mol% ZnO membrane for hydrogen separation via external short circuit was developed. The membrane with a thickness of 1.08 mm gives a hydrogen permeation flux of 0.098 mL min^?1cm^?2 at 800 °C with 50% H₂/He as feed gas. The presence of water vapor significantly promotes the hydrogen permeability of the membrane. In addition, introduction of 3% CO₂ or 100 ppm H₂S into feed gas does not decrease the hydrogen permeation flux of the membrane.     

Influence of gas ambient on the synthesis of co-doped ZnO:(Al,N) films for photoelectrochemical water splitting

Al and N co-doped ZnO thin films, ZnO:(Al,N), are synthesized by radio-frequency magnetron sputtering in mixed Ar and N₂ and mixed O₂ and N₂ gas ambient at 100 °C. The ZnO:(Al,N) films deposited in mixed Ar and N₂ gas ambient did not incorporate N, whereas ZnO:(Al,N) films grown in mixed O₂ and N₂ gas ambient showed enhanced N incorporation and crystallinity as compared to ZnO:N thin films grown in the same gas ambient. As a result, ZnO:(Al,N) films grown in mixed O₂ and N₂ gas ambient showed higher photocurrents than the ZnO:(Al,N) thin films deposited in mixed Ar and N₂ gas ambient. Our results indicate that the gas ambient plays an important role in N incorporation and crystallinity control in Al and N co-doped ZnO thin films.     

Hebb-Wagner polarization assessment of enhanced oxygen permeability for surface modified oxygen transport membranes

Tri-layered “porous | dense | porous” La_0.8Sr_0.2Cr_0.5Fe_0.5O_3?δ-Zr_0.84Y_0.16O_2?δ (LSCrF-YSZ) oxygen transport membranes (OTMs) were fabricated and permeation resistances from oxygen reduction and evolution reactions were determined by using Hebb-Wagner polarization method after introducing additional electron-blocking YSZ thin layers within the dense LSCrF-YSZ layers. Adding nano-scale catalysts, i.e. La_0.6Sr_0.4Co_0.2Fe_0.8O_3?δ (LSCoF) on air side and Ce_0.8Sm_0.2O_1.9?δ/Ni (SDC/Ni) on CH₄ side, into the porous LSCrF-YSZ layers yielded substantially reduced interfacial polarization resistances, and thereby allowed for high oxygen permeability at reduced temperatures under the air/CH₄ gradient, e.g., 1.1 and 4.3 ml cm^?2 min^?1 at 650 and 800 °C, respectively. Analysis of the impedance spectra suggest that the oxygen reduction kinetics on air side was probably limited by charge transfer reaction at T ≥ 750 °C and surface oxygen exchange at T ≤ 700 °C. Meanwhile, oxygen evolution reactions on CH₄ side dominated the total resistances to oxygen permeation through the tri-layered OTMs.     

Chemical stability and hydrogen permeation performance of Ni–BaZr0.1Ce0.7Y0.2O3−δ in an H2S-containing atmosphere

Composite membranes based on Ni and Zr-doped BaCeO₃ are promising for hydrogen separation. Such composites show high proton conductivity and adequate chemical stability in H₂O and CO₂, but may be unstable in H₂S. In this work, the hydrogen permeation performance of Ni–BaZr_0.1Ce_0.7Y_0.2O_3−δ was measured in an H₂S-containing atmosphere at 900 °C. The hydrogen permeation flux began to degrade in 60 ppm H₂S and decreased by about 45% in 300 ppm H₂S. After hydrogen permeation tests, X-ray diffraction analysis revealed the formation of BaS, doped CeO₂, Ni₃S₂ and Ce₂O₂S. Analysis of the microstructure and phase composition, and results of thermodynamic calculations suggest that reaction between H₂S and doped BaCeO₃ caused the performance loss of the Ni–BaZr_0.1Ce_0.7Y_0.2O_3−δ.     

Enhanced photoelectrochemical properties of WO3 thin films fabricated by reactive magnetron sputtering

Polycrystalline WO₃ thin films were fabricated by reactive magnetron sputtering at a substrate temperature of 350 °C under different Ar/O₂ gas pressures. In order to study the thickness dependence of photoelectrochemical (PEC) behavior of WO₃, the thickness-gradient films were fabricated and patterned using a micro-machined Si-shadow mask during the deposition process. The variation of the sputter pressure leads to the evolution of different microstructures of the thin films. The films fabricated at 2 mTorr sputter pressure are dense and show diminished PEC properties, while the films fabricated at 20 mTorr and 30 mTorr are less dense and exhibit enhanced water photooxidation efficiency. The enhanced photooxidation is attributed to the coexistence of porous microstructure and space charge region enabling improved charge carrier transfer to the electrolyte and back contact. A steady-state photocurrent as high as 2.5 mA cm⁻² at 1 V vs. an Ag/AgCl (3 M KCl) reference electrode was observed. For WO₃ films fabricated at 20 mTorr and 30 mTorr, the photocurrent increases continuously up to a thickness of 600 nm.     

Development and testing of anode-supported solid oxide fuel cells with slurry-coated electrolyte and cathode

A laboratory setup was designed and put into operation for the development of solid oxide fuel cells (SOFCs). The whole project consisted of the preparation of the component materials: anode, cathode and electrolyte, and the buildup of a hydrogen leaking-free sample chamber with platinum leads and current collectors for measuring the electrochemical properties of single SOFCs. Several anode-supported single SOFCs of the type (ZrO₂:Y₂O₃ + NiO) thick anode/(ZrO₂:Y₂O₃) thin electrolyte/(La_0.65Sr_0.35MnO₃ + ZrO₂:Y₂O₃) thin cathode have been prepared and tested at 700 and 800 °C after in situ H₂ anode reduction. The main results show that the slurry-coating method resulted in single-cells with good reproducibility and reasonable performance, suggesting that this method can be considered for fabrication of SOFCs.