The present invention relates generally to materials used in high-temperature non-aqueous environments, such as in industrial processes and energy conversion technologies.

Background of the invention

In modern and future energy conversion technologies and industrial processes, high- temperature non-aqueous environments are becoming of great interest for increasing energy conversion efficiency and enabling new manufacturing processes.

The first and most important example are fourth-generation nuclear reactor technologies, which promise wide availability of safe and CCh-free energy. Several concepts involve the use of liquid metals (LM), heavy liquid metals (HLM), molten salt (MS) or He as a heat carrier to extract the heat generated in the reactor core from fast fission and fusion reactions. Lead-Cooled Fast Reactors (LFRs), accelerator-driven systems (ADSs) and fusion reactor designs involve cooling by LM such as lithium or sodium, HLM such as lead, lead-bismuth eutectic (LBE) and lead-lithium eutectic (LLE). Despite the attractive properties of LM coolants, liquid metal corrosion (LMC) drastically alters the microstructure and chemical composition of metal alloy-based structural components, resulting in deterioration of mechanical properties and ultimately increasing the risk of failure.

The requirements for application in the aforesaid nuclear systems are met by austenitic and ferritic/martensitic steels. However, these alloys are unable to resist selective dissolution by LM and HLM and are subject to liquid metal embrittlement (LME). In addition to nuclear applications, LM, HLM and molten salts are being studied as working fluids in many heat management applications and high-temperature energy conversion devices such as concentrating solar power plants. In these applications, mitigation strategies designed to protect steel from corrosion include the formation of surface alloys and protective coatings. Metal or metal alloy coatings should be pre-oxidized or should form a protective layer of oxide in situ. However, poor reliability and poor control of the oxidation process pose additional risks to the implementation of these technologies. Among the proposed ceramic coatings, only amorphous aluminum oxide coatings, a-AhCh, deposited on stainless steel substrates by pulsed laser deposition (PLD) have been shown to provide protection of the underlying metal from corrosion by LM and HLM and by permeation of hydrogen isotopes, while also exhibiting radiation tolerance and minimal discrepancy with the substrate in terms of mechanical properties. In particular, although many oxide compounds are stable to reduction by liquid lead, only a-AhCh has thermomechanical properties compatible with those of stainless steel.

As described in US 2014241485 Al, the outstanding properties of a-AhCh coatings are closely related to their integrity. Said integrity is in turn related to the stability of the microstructure of the coating. All the examples reported in US 2014241485 Al of a-AhCh- coated steels in HLM were executed at temperatures at or below 600°C. Above this temperature, a strong crystallization may induce cracking in the film due to the increase in density from the amorphous phase (p~3.5 g/cm ³ ) to the crystalline phase (3.5 g/cm ³ <p<4 g/cm ³ ), thus exposing the underlying support to corrosive environments. Stabilization and control of amorphous-crystalline phase transitions under the combined effects of radiation fields and high temperature are of primary importance for the final application. A nuclear reactor or other similar thermal system may in fact have transients that exceed the nominal operating temperature by as much as a few hundred degrees for limited periods of time.

Further, the effect of the radiation field should be considered. In particular, radiation- enhanced crystallization and radiation-induced crystallization are destabilization mechanisms that influence the crystallization temperature, or promote the nucleation of specific crystalline phases, in a material under irradiation with respect to that which might be observed in a purely thermal regime. As a result, the temperature thresholds for amorphous-crystalline and phase-to-phase transitions could shift rigidly toward lower values.

In conclusion, the microstructure of the coating affects the mechanical properties of the film, while phase transitions may lead to densification processes, crack formation and loss of adhesion and coating integrity. Therefore, fine-tuning and controlling the properties of the coating by stabilizing its microstructure would enable the advancement and development of advanced nuclear systems and other high-temperature technologies that make use of non-aqueous working fluids.

Summary of the invention

For the objects indicated above, the subject of the invention is a metallic component for high-temperature non-aqueous environments, comprising a body of metallic material and a protective coating applied to an outer surface of the body of metallic material, intended in use to contact a non-aqueous working fluid, wherein said protective coating includes at least one layer of amorphous aluminum oxide, said at least one layer of amorphous aluminum oxide comprising at least one doping element uniformly dispersed in the layer of amorphous aluminum oxide, said at least one doping element being selected from the group consisting of C, Na, K, Cs, Mg, Ca, Sr, P, Si, Fe, Y, Zr, Mo, W, La, Ce, Er, Yb.

For the purposes of this invention, “high temperature” means a temperature above 600°C.

In the event in which the metal component is steel, particularly austenitic steel or ferritic- martensitic steel, it is possible to obtain an aluminum oxide-based coating, composed of an amorphous material, with thermomechanical properties (i.e., Poisson’s coefficient, elastic modulus, and coefficient of thermal expansion) compatible with those of austenitic and ferritic-martensitic stainless steels. Further, the coating has greater hardness than stainless steel. As a result, it may withstand the substrate deformation expected for normal operation of stainless steel components and prevents wear damage to said metal components.

The coating of the present invention is resistant to crystallization and crack formation at high temperatures, at least up to 900°C.

By virtue of a matrix composed of aluminum oxide, the coating presented here is resistant to corrosive attack by liquid metal (LM), heavy liquid metal (HLM) or molten salt (MS). Therefore it is an efficient barrier to prevent corrosion of the stainless steel to which the coating is applied.

Further, the homogeneous and amorphous coating is thus an effective barrier against the permeation of hydrogen isotopes by preventing hydrogen isotope infiltration within the coated stainless steel and subsequent embrittlement.

In conclusion, the coating disclosed here is resistant to radiation and may withstand high doses without losing its protective properties.

The stabilization of the amorphous phase of aluminum oxide at high temperatures is desirable for application in many technological fields where resistance to wear, corrosion and irradiation is required. In particular, in the field of liquid-metal-cooled fast fission reactors, the increased resistance to crystallization allows for the application of aluminum oxide coatings on structural steel coatings. The qualified performance of aluminum oxide coatings in this field is thus extended to temperatures above the operating condition (600°C). The first consequence is increased radiation tolerance at currently established operating temperatures. Further, a delay in the amorphous-crystalline transition allows for the operating temperature setpoint to be increased according to the design and to ensure higher power generation efficiency.

Detailed description of the invention

Further features and advantages of the invention will become clearer from the following detailed description of an embodiment of the invention, made with reference to the accompanying drawings, provided purely for illustrative and non-limiting purposes, in which

Fig. 1 represents the phase diagram of the pseudo-binary system AI2O3-Y2O3, adapted from Fabrichnayan et al, Assessment of thermodynamic parameters in the system ZrO2-Y2O3-A12O3, Zeitschrift fur Metallkunde, 95, 2004;

Fig. 2 is a graph showing X-ray diffraction patterns of a pure AI2O3 film and doped AI2O3 films of the Example, after the deposition process; Fig. 3 is a graph showing X-ray diffraction (XRD) patterns of the pure A12O3 film and the doped A12O3 films of the Example, after annealing at 700°C for 72h;

Fig. 4 is a graph showing X-ray diffraction patterns of the pure AI2O3 film and the doped AI2O3 films of the Example, after annealing at 800°C for 72h;

Fig. 5 is a graph showing X-ray diffraction patterns of the pure AI2O3 film and the doped AI2O3 films of the Example, after annealing at 900°C for 72h;

Fig. 6 shows scanning electron microscope (SEM) images at lower magnification (left) and higher magnification (right) of the pure AI2O3 film after annealing at 700°C for 72h;

Fig. 7 shows scanning electron microscope (SEM) images at lower magnification (first row) and higher magnification (second row) of the pure AI2O3 film and the doped AI2O3 films of the Example, after annealing at 800°C for 72h;

Fig. 8 shows scanning electron microscope (SEM) images at lower magnification (first row) and higher magnification (second row) of the pure AI2O3 film and the doped AI2O3 films of the Example, after annealing at 900°C for 72h.

An AhCE-based coating is now described. The coating consists of an amorphous, homogeneous layer with thicknesses from 10 nm to 100 pm, preferably 0.1 to 10 pm, with a crystalline domain fraction of less than 1% by volume and in any case undetectable by XRD.

The composition of the coating disclosed here is characterized by an atomic dispersion of one or more dopants, uniformly distributed in an AI2O3 matrix. This dispersion of dopants has the effect of delaying the onset of the crystallization of the coating material. Further, once the crystallization threshold is reached, the dopants that are distributed in the coating material have the secondary effect of delaying the grain growth of the first metastable crystalline phase of AI2O3, namely Y-AI2O3, to higher temperatures than a pure AI2O3 coating. The advantage in this case is that Y-AI2O3 has a similar density to a-AECE, and therefore mechanical stresses are minimized upon its formation.

The dopants considered for stabilization of the amorphous matrix are selected from the group comprising C, Na, K, Cs, Mg, Ca, Sr, P, Si, Fe, Y, Zr, Mo, W, La, Ce, Er, Yb. The dopants may be added in the form of pure elements or in the form of the relevant most stable oxide compound. Further, the dopants could be added as a single-element dopant or multi-element dopant.

In the first case, the single-element dopant is introduced into the AI2O3 matrix in the form of the pure element or in the form of the relevant stable oxide, in a concentration that is specified as follows, with reference to Fig. 1. Given the pseudo-binary phase diagram of the AhCh-oxide doping system, the first ternary compound existing in the phase diagram and containing the highest molar concentration of AI2O3, CT, is identified. For the composition of the aforesaid ternary compound, the number NT is defined as the atomic ratio of doping atoms to Al atoms. The coating material described here has a doping oxide concentration Cd for which the condition 0<Nd<Nr is met, thus disclosing an atomic ratio of doping atoms to Al atoms that is less than the atomic ratio NT of the aforesaid ternary compound characterized by the molar concentration CT. In an embodiment of the same invention, the condition is limited to 0.001 * r<Nd<0.90 *NT. In a preferred embodiment, the condition is further limited to 0.01N r<Nd<0.70*NT.

In an embodiment of the invention (shown in Fig. 1), the single-element dopant would be yttrium (CT=37.5% mol, corresponding to a weight concentration of 57.1% wt) and the concentration Cd of Y2O3 selected in the range of 0.1-25% mol, corresponding to weight concentrations in the range of 0.3-43.0% wt, more precisely in the range of 11-22% mol, corresponding to weight concentrations in the range of 22-38% wt, still more precisely in the range of 15-20% mol, corresponding to weight concentrations in the range of 28- 35% wt. Hereinafter, for simplicity, reference will be made to concentrations expressed in % mol.

The phase diagram in Fig. 1 for the pseudo-binary AI2O3-Y2O3 system clarifies the correspondence between the mole fraction of the doping oxide and the doping atomic ratio on Al. In particular, NT is the atomic ratio Y/Al that characterizes yttrium-aluminum garnet (YAG), while Nd is calculated from the selected molar concentration of Y2O3 and is within the range specified above. The inventors thus found that the addition of the doping element in amorphous aluminum oxide allows the coating to be stabilized at temperatures above 600°C. The molar concentration range within which stable amorphous aluminum oxide occurs tends to narrow as the temperatures to which the coating is subjected increase. For example, in the case in which yttrium is used as a dopant for a coating applied on steel, the inventors have found that at temperatures below 800°C the amorphous aluminum oxide coating is stable for any value of the doping oxide concentration that is less than or equal to CT=37.5% mol. At temperatures between 800°C and 900°C, coatings having a doping oxide concentration between 11% mol and 22% mol are stable.

Preliminary experiments have shown that it is possible to increase the temperature of stability above 900°C by adding one or more additional dopants (always chosen from the elements listed above). In such a situation, there would be a first doping element, the concentration of which is defined in the same way as the case relating to the single dopant discussed above. Additional dopants would be added in such quantities as to have a molar concentration, for each dopant, less than or equal to that of the oxide of the first doping element.

For the specific case of oxides forming a solid solution with AI2O3, such as ZrCh, the doping oxide concentration is selected in the range 0.1%mol<Cd<50% mol.

The coating structure described above is composed of at least one layer of the AhCh-based material described above, however, it may also comprise a plurality of layers, each characterized by the same or a different chemical composition and microstructure. The thickness of each layer is between 10 nm and 100 pm, preferably in the range of 500 nm to 5 pm. For example, in one embodiment of the disclosed invention, the coating would comprise a single layer with a thickness of 3 pm.

The combination of amorphous structure and chemical composition based on an AI2O3 matrix gives several properties to the above-described coating material, namely wear resistance, mechanical compatibility with stainless steel, barrier to the permeation of the hydrogen isotopes, protection from LM, HLM and MS corrosion, radiation and crystallization resistance. The coating may be applied to multiple support materials, characterized by different geometries. Preferably, the coating applies to stainless steels of austenitic type (e.g., AISI 316/316L, 15-15 Ti) and ferritic/martensitic type (for example, reduced activation ferritic martensitic EUROFER). For example, the substrate could be a tube, in particular the cladding tube of the fuel for LM- or HLM- or MS-cooled nuclear reactors.

The growth of the coating may be obtained by vapor-phase techniques for thin-film deposition. For example, the coating is applied to the substrate material by pulsed laser deposition (PLD). Another example of a deposition technique is atomic layer deposition (ALD). In one embodiment of the present invention, the coating is applied with a deposition technique that does not make use of support heating, but rather limits the temperature of the components to be coated to the range going from room temperature to a few hundred degrees Celsius.

The crystallization temperature of the AECh-based coatings described above is at least 100°C higher than that of pure AI2O3 coatings. Further, as shown by preliminary investigations, when the temperature exceeds the threshold temperature for crystallization, the composition of AhCE-based coatings would allow the nucleation of nanometer-sized crystalline domains of y-A12O3, thus demonstrating the coating’s ability to induce a delaying effect on the amorphous-crystalline transition and control the nucleated crystalline phase within the coating material.

Further, the chemical composition of the coating is such that it prevents the nucleation of ternary compounds and second phases at high temperatures. As designers of new LFR and solar thermal systems are striving to achieve higher system efficiency, it is necessary to raise the coolant temperature above 650°C. Considering the safety margins for the operation and the effect of irradiation that could induce or accelerate crystallization, it is reasonable to assume that the coating should withstand temperatures up to 800°C.

The coating material described above is able to withstand even more extreme conditions, by virtue of its composition and microstructure, and resist crystallization and mechanical failure at least up to 900°C. The integrity of the coating, in particular, is of paramount importance for the protection of stainless steel from LM and HLM corrosion in nuclear reactors, as the generation of defects (loss of adhesion, bubble formation, crack formation) would expose the substrate and increase corrosion damage to the structural components of the reactor.

Example

An example of an application of the invention to LFR stainless steel cladding is now presented. AISI 316/316L tubes (outer diameter 10 mm, length 200 mm) were first polished and then coated with 3-pm-thick layers of AI2O3, pure and doped with an atomic dispersion of Y, obtained by ablation of a mixed target with Y2O3 doping concentration of 5, 10 16 and 23% mol in AI2O3, respectively. Segments 20 mm long were cut from each tube. These samples were subjected to heat treatment in a vacuum furnace for 72 hours at temperatures of 700, 800 and 900°C. The measured value for total pressure during the dwell time at the setpoint temperature was 10' ³ Pa: under these conditions, a small amount of oxygen is still present in the furnace and reacts rapidly with the steel substrates to form iron and chromium oxides on the uncoated surfaces of the tube segments (edges and uncoated inner surface) and on the outer surface where defects in the coating expose the substrate to the environment of the furnace.

The XRD patterns shown in Fig. 2-5 describe the evolution of the coatings from the amorphous phase to the crystalline phase and eventual nucleation of ternary compounds (i.e., yttrium garnet and aluminum garnet-YAG). The onset of crystallization for pure AI2O3 is detected for temperatures around 700°C, so XRD data for annealed samples are reported for temperatures of 800 and 900°C. Pure AI2O3 is well crystallized as early as 800°C, while the most significant delaying effect is confirmed for a doping concentration of 23% mol, for which only the presence of y-A12O3 is detected by XRD. Most of the reflections from the cubic y-A12O3 phase are missing, and the large peaks detected suggest that the material is in the early stages of crystallization. It is worth noting that with 23% mol of doping oxide, the film crystallizes rapidly in the YAG phase for the sample annealed at 900°C.

The top SEM views shown in Fig. 6 through 8 demonstrate the inability of the pure AI2O3 film to provide a compact protective barrier to the steel support, as evidenced by the formation of cracks and the growth of iron oxides therethrough. The crack formation is also detected for AI2O3 coatings doped at 5, 10 and 23% mol at 900°C. The densification process caused by the nucleation and growth of Y-AI2O3 crystalline and YAG phases induces the rupture of the coating and allows for the oxidation of the substrate. Only the sample with 16% mol dopant was found intact and adhered to the underlying steel.