CN116219430A - High-temperature-resistant lead-bismuth alloy environment erosion and abrasion alloy coating and preparation method thereof - Google Patents
High-temperature-resistant lead-bismuth alloy environment erosion and abrasion alloy coating and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
- C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
- C23C24/103—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
- C23C24/106—Coating with metal alloys or metal elements only
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E30/00—Energy generation of nuclear origin
- Y02E30/30—Nuclear fission reactors
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Abstract
The invention discloses a high temperature resistant lead bismuth alloy environment erosion and abrasion alloy coating and a preparation method, the invention applies a laser cladding technology to prepare, the coating comprises: the high-entropy alloy layer gradually forms an oxide layer in a liquid lead bismuth alloy environment, the oxide layer comprises one or more of titanium oxide, aluminum oxide, silicon oxide and chromium oxide, and the elements of the high-entropy alloy layer consist of one or more of Al, ti and Si, one or more of Fe and Cr, and one or more of Y, mo and Nb. The technological parameters of the laser cladding are as follows: the working chamber is filled with 99.9% of inert gas, the laser power is 180W-230W, the laser scanning speed is 27mm/s-33mm/s, the focal point is-0.1 mm-0.5 mm, the spot diameter is 0.3mm-0.9mm, and the multi-pass lap joint rate is 50%. The invention combines the process raw materials and the process parameters to obtain the coating material with the functions of resisting the dynamic and static corrosion, the erosion and the abrasion of the lead-bismuth alloy, and the coating has better comprehensive performance compared with the prior art.
Description
Technical Field
The invention discloses a high-temperature-resistant lead-bismuth alloy environment erosion and abrasion alloy coating and a preparation method thereof, and relates to the technical field of preparation of high-temperature-resistant lead-bismuth alloy environment erosion and abrasion coatings.
Background
The liquid lead bismuth eutectic alloy has excellent thermal hydraulic and neutron properties, and is one of the most important cooling working media of the fourth-generation liquid metal cooling fast reactor. However, ferrite/martensite (F/M) steel, which is a main candidate material for a liquid lead-bismuth cooled fast reactor cladding tube, has serious problems of Liquid Metal Embrittlement (LME) and Liquid Metal Corrosion (LMC) in a high-temperature liquid lead-bismuth alloy environment, which hinders the engineering application process of the liquid lead-bismuth fast reactor to a certain extent. Studies have shown that the manner of preparing protective coatings on the surface of F/M steel is one of the effective means for inhibiting the occurrence of LME and LMC phenomena.
However, the liquid lead bismuth alloy flowing at high speed in the reactor can cause relative tiny movement between the cladding material and the support winding wire, and micro-abrasion damage is induced on the surface of the material. In order to improve the performance of the high-entropy alloy coating under dynamic corrosion and abrasion corrosion (i.e. abrasion) conditions, in the prior art (patent CN113106394 a) (patent CN108866471 a), sand blasting is mainly adopted to improve the surface smoothness, so as to improve the erosion resistance of the coating material (the erosion resistance is an index of the dynamic corrosion resistance of the coating material), but the comprehensive performance of the dynamic corrosion resistance of the coating material obtained in this way is still poor.
Summary of the invention
The invention aims to provide a high-temperature-resistant lead-bismuth alloy environmental erosion and abrasion alloy coating and a preparation method thereof, which solve the problem that the high-entropy alloy coating in the prior art does not have excellent dynamic corrosion resistance of liquid lead-bismuth alloy.
In order to achieve the technical purpose and the technical effect, the invention is realized by the following technical scheme:
a high temperature resistant lead bismuth alloy environmental erosion and abrasion alloy coating and a preparation method thereof comprise the following steps: the high-entropy alloy layer gradually forms an oxide layer in a liquid lead bismuth alloy environment, the oxide layer comprises one or more of titanium oxide, aluminum oxide, silicon oxide and chromium oxide, and the elements of the high-entropy alloy layer consist of one or more of Al, ti and Si, one or more of Fe and Cr, and one or more of Y, mo and Nb.
Further, the elements of the high-entropy alloy layer include Fe, al, cr, ti, nb, and the oxide layer includes alumina, titania, and chromia oxidized from the high-entropy alloy layer.
The invention further aims at disclosing a preparation method of a high-temperature resistant lead bismuth alloy environmental erosion and abrasion alloy coating, which comprises the following specific steps of:
step 1, polishing the surface of a substrate, and polishing the surface of the substrate to have certain roughness by using a polishing tool;
step 2, mixing process raw materials, namely, selecting one or more of Al, ti and Si, one or more of Fe and Cr and one or more of Y, mo and Nb, and mixing the selected process raw materials to obtain mixed metal powder;
and step 3, performing laser cladding, and cladding the mixed metal powder on the surface of the matrix by using a laser cladding technology.
Further, al and Ti are selected from among Al, ti and Si.
Further, the step 2 further comprises mixing the mixed metal powder with polyvinyl alcohol glue (pva) according to a certain proportion to obtain the mixed metal powder.
Further, the technological parameters of the laser cladding are as follows:
the working chamber is filled with 99.9% of inert gas, the laser power is 180W-230W, the laser scanning speed is 27mm/s-33mm/s, the focal point is-0.1 mm-0.5 mm, the spot diameter is 0.3mm-0.9mm, and the multi-pass lap joint rate is 50%.
Further, the process raw materials comprise Fe, al, cr, ti, nb.
Specifically, the process raw materials comprise 20% of Fe, 20% of Al, 20% of Cr, 20% of Ti and 20% of Nb.
Alternatively, the process raw material ratio is 22.2% Fe, 22.2% Al, 22.2% Cr, 22.2% Ti, 11.1% Nb.
The beneficial effects are that:
the invention selects one or more of Al, ti and Si, one or more of Fe and Cr, and one or more of Y, mo and Nb, and a laser cladding technology is applied, and the coating material with the resistance to dynamic and static corrosion, erosion and abrasion of the lead-bismuth alloy is obtained by controlling parameters.
Specifically, al and Ti are selected as raw materials, and the high hardness and high temperature resistance obtained by combining laser cladding with high-entropy alloy can avoid the problem of coating falling off in dynamic corrosion; in addition, compared with the high-entropy alloy coating material in the prior art, the coating material prepared by the method has better dynamic corrosion resistance through experiments, and is probably caused by the compact and smooth oxide layer structure generated after the oxidation of the coating.
Of course, it is not necessary for any one product to practice the invention to achieve all of the advantages set forth above at the same time.
Drawings
FIG. 1 is a graph of the macro morphology of a coating after laser cladding and heat treatment in an embodiment of the present invention;
FIG. 2 is an Electron Back Scattering Diffraction (EBSD) diagram of the microstructure of the laser clad and heat treated coating according to an embodiment of the present invention;
FIG. 3 is an EBSD of the original structure of the T91 alloy in the embodiment of the invention;
FIG. 4 is a graph comparing the hardness of high entropy alloy samples prepared in examples of the present invention with that of a ferritic-martensitic steel matrix material;
FIG. 5 shows the morphology of a ferrite-martensitic steel matrix subjected to erosion by a liquid lead bismuth alloy with a flow rate of 2m/s for 5000 hours in an environment of 500 ℃ in an embodiment of the invention;
FIG. 6 shows the morphology of a high-entropy alloy coating subjected to laser cladding and heat treatment in an environment of 500 ℃ after being subjected to erosion by a liquid lead-bismuth alloy with a flow rate of 2m/s for 5000 hours in the embodiment of the invention;
FIG. 7 is a morphology of a ferrite-martensitic steel matrix sample of an embodiment of the present invention after being etched for 5000 hours in a liquid lead bismuth alloy having a flow rate of 5m/s at 500 ℃;
FIG. 8 shows the morphology of a high-entropy alloy coating subjected to laser cladding and heat treatment in the embodiment of the invention after being subjected to erosion for 5000 hours by a liquid lead-bismuth alloy with the flow rate of 5m/s in an environment of 500 ℃;
FIG. 9 shows the morphology of a FeCrAlNb coating without Ti addition prepared by laser cladding in the embodiment of the invention after being eroded for 5000 hours by a liquid lead bismuth alloy with the flow rate of 5m/s in an environment of 500 ℃;
FIG. 10 is an SEM image of the wear morphology of a FeCrAlNb high-entropy alloy coating, a FeCrAlNb coating without Ti addition, and a ferrite-martensite steel matrix after being subjected to laser cladding and heat treatment in a lead-bismuth alloy environment at 500 ℃ after 10000 cycles of abrasion;
FIG. 11 is a three-dimensional image of the abrasion of the FeCrAlNb high-entropy alloy coating, the FeCrAlNb coating without Ti addition and the ferrite-martensite steel matrix after abrasion 10000 cycles in a lead-bismuth alloy environment at 500 ℃ after laser cladding and heat treatment in the embodiment of the invention;
FIG. 12 is a comparison of thickness of oxidized layers of FeCrAlNb coating, feCrAlNb and base material prepared by laser cladding in a static lead-bismuth alloy at 500 ℃ after corrosion for 500 hours in an embodiment of the invention;
Detailed Description
In order to more clearly describe the technical scheme of the embodiment of the present invention, the embodiment of the present invention will be described in detail below with reference to the accompanying drawings.
Example 1
In combination with the high-entropy alloy coating technology in the prior art, and the prior art has shown that the coating structure with a smooth surface can effectively improve the surface integrity of the coating material in fretting abrasion and high-flow-rate erosion environments. The applicant divides the high-entropy alloy constituent elements into three categories, and in this embodiment, a high-temperature resistant lead-bismuth alloy environmental erosion and abrasion alloy coating comprises a high-entropy alloy layer.
The high-entropy alloy layer gradually forms an oxide layer in a liquid lead bismuth alloy environment, the oxide layer comprises one or more of titanium oxide, aluminum oxide, silicon oxide and chromium oxide, and the elements of the high-entropy alloy layer consist of one or more of Al, ti and Si, one or more of Fe and Cr, and one or more of Y, mo and Nb.
In combination with the foregoing, the applicant has identified that the high-entropy alloy coating materials are divided into three groups, wherein one or more of Al, ti and Si is the first group, and wherein Al, ti and Si, when in a lead bismuth alloy liquid environment, combine with free oxygen to form a more dense oxide such as Al2O3, siO2 or TiO2, and the formation process is slow, so that the surface structure is generally smoother. The dense oxide layer can effectively improve the corrosion resistance of the coating material, and the smooth dense structure of the oxide layer can improve the dynamic corrosion resistance of the lead-bismuth alloy liquid.
One or more of Fe and Cr is the second group, and one or more of Y, mo and Nb is the third group, and researches show that the atomic radius of the elements such as Y, mo and Nb is larger than that of the elements such as Fe and Cr, so that larger lattice distortion can be caused, and the corrosion resistance of the whole coating to the lead-bismuth alloy is improved. Therefore, the elements of the second group and the third group are combined to prepare the coating material with better corrosion resistance of the lead-bismuth alloy. In addition, the addition of difficult-to-hold elements such as Y, mo, nb and the like can improve the high-temperature mechanical property of the material, promote the precipitation of second phase particles at the interface, and improve the high-temperature resistance of the coating material on the basis of the above.
In summary, in this embodiment, the applicant combines one or more of the three groups of elements to prepare the high-entropy alloy coating, on the one hand, the first group of raw materials are separated out to improve the smoothness of the surface of the coating material, and compared with the prior art that the surface roughness is reduced by polishing or the like, the smoothness of the coating is improved from the microstructure perspective. On the other hand, the atomic radius of the first group of raw materials is similar to that of the second group of raw materials, and the first group of raw materials can promote the precipitation of second phase particles, so that the corrosion resistance of the high-temperature-resistant lead-bismuth alloy coating is improved.
In one embodiment, the applicant has specifically selected process raw materials comprising Fe, al, cr, ti, nb to synthesize a high-entropy alloy, in which case the oxide layer formed after the high-entropy alloy coating is contacted with oxygen or oxygen ions in the liquid lead bismuth alloy comprises aluminum oxide, titanium oxide, and chromium oxide.
The alloy structure shows good resistance to corrosion of lead-bismuth alloy liquid in static, dynamic and high-temperature environments under experimental verification, and compared with the prior art, the alloy structure has comprehensive performance which is not shown in the prior art.
Example 2
In practice, the materials involved in the embodiment 1 are obtained by selecting two parts including process raw materials and process parameters, in this embodiment, a class of preparation methods capable of obtaining the high-entropy alloy coating involved in the embodiment 1 is listed first, and in this embodiment, the applicant discloses a preparation method of a high-temperature resistant lead-bismuth alloy environmental erosion and abrasion alloy coating, and the specific steps for preparing the high-entropy alloy layer and the oxide layer include:
and 1, polishing the surface of the substrate, and polishing the surface of the substrate to have a certain roughness by using a polishing tool.
This step aims at improving the bonding properties of the substrate to the coating.
And 2, mixing process raw materials, namely selecting one or more of Al, ti and Si, one or more of Fe and Cr and one or more of Y, mo and Nb, and mixing the selected process raw materials to obtain mixed metal powder.
It should be noted that the choice of materials may be different in different embodiments, and although the disclosure of Fe, al, cr, ti, nb process raw materials is not related in the disclosure of all embodiments of the present invention, in practice, based on the description of the principles in embodiment 1, a certain effect may be achieved by selecting a combination of the foregoing raw materials, so that embodiments specifically including some specific detailed combinations of different process raw materials will not be repeated herein.
And step 3, performing laser cladding, and cladding the mixed metal powder on the surface of the matrix by using a laser cladding technology.
In some embodiments, the step 2 further comprises mixing the mixed metal powder with polyvinyl alcohol glue (pva) in a certain ratio under stirring to obtain the mixed metal powder.
The target coatings obtained from the various combined process materials corresponding to example 1 were prepared by combining laser cladding techniques with the raw materials that can produce the high entropy alloy and dense oxide coating.
Example 3
In this embodiment, the applicant has performed a specific implementation procedure based on the content of embodiment 2, and has described a corresponding scheme for obtaining the effect of this embodiment by dividing the content into two parts.
Based on the selection of the process raw materials, in this embodiment, al and Ti are selected from the Al, ti and Si. The material is selected to improve the dynamic lead bismuth alloy corrosion resistance of the material.
First dynamic corrosion, i.e. a relative movement of the two nominally stationary contact surfaces at microscopic angles with very small magnitudes of displacement (typically on the order of microns), which in this embodiment results between the coating material and the lead bismuth alloy liquid.
One of the solutions to this problem, as already mentioned in the previous examples, is to increase the smoothness of the coating material, which in turn reduces the dynamic corrosion at microscopic angles. In the prior art, the corresponding problem is most commonly solved by an alumina layer structure, but Al 2 O 3 The fact that the protective coating cannot stably exist under the action of coupling fretting friction and high-flow-rate liquid lead bismuth alloy strong erosion (fretting abrasion) is proved by the prior study, and one of the reasons for the occurrence of the phenomenon is that Al 2 O 3 The poor high temperature mechanical properties of the protective coating itself.
In combination with the foregoing, for Al 2 O 3 The applicant adds Ti into the material to protect the defects of the coating, and selects Al and Ti post-coating materialsThe composite oxide layer structure is formed after contacting oxygen atoms in the lead bismuth alloy solution or dissolved oxygen, and the structure is found to have better performance through experimental comparison, and the specific result is shown in fig. 9.
On the other hand, poor high-temperature mechanical properties of the Al2O3 protective coating can not lead to the stable existence of the Al2O3 protective coating under the actions of coupling fretting friction and high-flow-rate liquid lead bismuth alloy strong erosion (fretting abrasion). Then one or more of Fe and Cr and one or more of Y, mo and Nb are selected to form high-entropy alloy, so that the high-temperature resistance of the coating is improved.
In summary, the method adopts Al and Ti as the process raw materials, so that the problem of poor dynamic corrosion resistance of the lead-bismuth alloy of the single oxide layer of aluminum oxide is solved, and the problem of possibly poor high temperature resistance of the oxide layer is also solved by forming high-entropy alloy.
In the prior art, only patent (CN 202210017528) is available as a coating material for improving the dynamic corrosion resistance of the lead-bismuth alloy from the aspect of process raw material selection, but the dependent materials are Ai and Ti alloys, and the essence of the coating material is different from that of the alumina-titanium oxide combined compact protective film in the embodiment invention.
Example 4
In addition to the improved surface smoothness as referred to in the previous examples to improve the dynamic lead bismuth alloy corrosion resistance of the coating, improving the surface hardness of the material, improving the bonding force is also one of the shutdown factors that improve its fretting wear resistance. In the prior art, surface structure refinement induced by plastic deformation improves the hardness to a certain extent, thereby improving the fretting wear resistance. However, this would certainly reduce the corrosion resistance of the steel sheet, since severe plastic deformation pairs would lead to an increase in surface defects. That is, increasing hardness and decreasing surface smoothness are contradictory in the sense that the applicant solves this problem by setting specific process parameters in this example in order to provide the coating material with both of the aforementioned properties.
In this embodiment, the synthesis process is laser cladding, and the process parameters of the laser cladding are as follows:
the working chamber is filled with 99.9% of inert gas, the laser power is 180W-230W, the laser scanning speed is 27mm/s-33mm/s, the focal point is-0.1 mm-0.5 mm, the spot diameter is 0.3mm-0.9mm, and the multi-pass lap joint rate is 50%.
In the embodiment, the tissue structure of the coating is further optimized by adjusting laser process parameters such as power, spot diameter, scanning rate, overlap ratio and the like, so that the surface performance of the coating reaches the optimal state.
In one embodiment, by controlling the laser parameters, a surface with a significantly finer grain size is obtained, with an average grain size of about 5-8 μm. FeCrAlNb high-entropy alloy coating with the effective thickness of 200-300 mu m.
The corresponding test results in example 5 show that the hardness of the coating material obtained by combining the high-entropy alloy material with the laser cladding technology is also higher. In addition, compared with the coating material prepared by the laser cladding technology in the embodiment, the protective coating prepared by adopting the technologies of thermal spraying, magnetron sputtering and the like has weaker bonding force with the matrix material, so that the coating disclosed by the embodiment has better bonding force and is not easy to fall off.
In combination with the contents of examples 3-4, compared with the prior art, the invention of the embodiment adopts the selection of the process raw materials of Ai, ti and high-entropy alloy and the selection of special process parameters, and theoretically, the coating material has the performances of high temperature resistance, smooth surface and high hardness, and has the three performances, so that the coating material has the dynamic corrosion and abrasion resistance of lead-bismuth alloy which are never available in the prior art.
Example 5
In order to demonstrate the excellent dynamic corrosion resistance of the lead bismuth alloy of the inventive materials referred to in example 4, the applicant tested the materials and parameter selections of two specific examples, both in the case of abrasion and in the case of erosion.
In an embodiment, the process raw material ratio is 20% fe, 20% al, 20% cr, 20% ti, nb20%, the substrate is selected from a T91 steel substrate, and the T91 steel substrate is processed by: the T91 steel plate is cut into samples with length, width and height of 30mm, 10mm and 3mm respectively by using linear cutting, wherein the surface with the length, width and the height is a laser working surface.
Step 1: the specific steps of polishing the surface of the substrate are that the sample cut by the wire cutting is polished by 120#SiC and 600#SiC black sand paper in sequence to obtain the surface with certain roughness, the oxide skin on the surface is removed, and finally the sample is cleaned by absolute ethyl alcohol and then dried by a blower at a cold air gear to be used as a laser sample to be processed.
Step 2: the specific steps of the raw materials of the mixing process are that Fe, al, cr, ti and Nb powder are mixed according to the equimolar ratio and added into a ceramic pot of a ball mill, and ceramic pellets are added according to the powder ratio of 1:10, wherein the ratio of the large pellets to the small pellets is 1:1. After mixing and adding, the mixture is plugged by a rubber plug, and is taken out for standby after mixing for 10 hours under the condition that the rotating speed of the ball mill is 120 r/min.
The step 2 further comprises the steps of presetting high-entropy alloy coating metal powder on the surface of the T91 steel: placing the cut T91 steel sample on a grinding tool prepared in advance, then stirring and mixing the mixed metal powder with polyvinyl alcohol glue (pva) according to a certain proportion, uniformly scraping and coating the mixed metal powder on the surface of a base material, and finally placing the sample with the preset metal powder into a drying furnace at 70 ℃ for drying for 3-4 hours, and taking out for later use.
Step 3: the specific step of performing laser cladding is to fix a sample of preset high-entropy alloy metal powder on a sample stage of a BLT-A160D laser, and then to introduce 99.9% argon into a working chamber to avoid oxidation of the sample in the laser process. Then, setting laser parameters and setting laser beam paths. Starting a laser, loading voltage, and carrying out laser cladding treatment on the surface of the T91 steel material. The technological parameters of the laser surface treatment are as follows: laser power 180W, laser scanning speed 27mm/s, focal point-0.1 mm and spot diameter 0.3mm. Finally, taking out the sample after the temperature of the sample is reduced to room temperature.
And (3) after the steps, sequentially polishing by using 120# black SiC abrasive paper, 600# black SiC abrasive paper and 2000# black SiC abrasive paper, and then placing the polished SiC abrasive paper into a heat treatment furnace for homogenization and stabilization treatment, wherein the heat treatment furnace is a conventional tube furnace, the heat treatment temperature is 380 ℃, the heat treatment is argon atmosphere, and the heat preservation time is 3.5h. And after the heat treatment is finished, air cooling to the room temperature.
In order to further improve the dynamic corrosion resistance of the lead-bismuth alloy of the coating material, the step of carrying out smooth treatment on the surface of the coating material is added on the basis of the previous step, namely, the coating material is sequentially polished by No. 120, no. 600 and No. 2000 black SiC sand paper, then polished by a 400r/min polishing machine, and a proper amount of 2.5 mu m diamond grinding spray is sprayed on the surface of polishing cloth, so that the surface which is free from obvious scratches and is bright is obtained, and finally, the high-entropy alloy coating is obtained by washing with absolute ethyl alcohol and drying with a blower in a cold air gear.
In another specific embodiment, the process raw material ratio is 22.2% Fe, 22.2% Al, 22.2% Cr, 22.2% Ti, 11.1% Nb. The technological parameters of the laser surface treatment are as follows: the laser power is 220W, the laser scanning speed is 32mm/s, the focal point is +0.4mm, and the spot diameter is 0.8mm. The rest of the steps are the same as in the previous embodiment.
As can be seen in connection with fig. 1-3, the specific preparation methods in both of the foregoing specific examples obtained the intended high entropy alloy coating, which showed a compact and smooth structure.
In order to demonstrate the effect required in the foregoing examples, the applicant carried out a dynamic corrosion environmental simulation of the lead bismuth alloy for the two coating materials prepared in this example.
In this embodiment, erosion environment simulation and abrasion environment simulation are performed on the coating material respectively, and the erosion conditions are: the temperature is 500 ℃, the relative flow rate is 2m/s, and the erosion time is 5000 hours;
the abrasion conditions are as follows: the temperature is 500 ℃, the normal load is 100N, the abrasion displacement amplitude is 100 mu m, and the abrasion is 10000 times.
The applicant has examined the various properties of the coating material and finally has obtained experimental results as shown in fig. 4-10, verifying the various property improvements involved in the foregoing examples:
1. the invention can obtain the surface with obvious fine warp organization by controlling the laser parameters, and the average grain size is about 5-8 mu m (see the description of figure 2). FeCrAlNb high-entropy alloy coating with the effective thickness of 200-300 mu m (see figure 4 for illustration); in addition, the interface between the remelted coating prepared by the method and the matrix material is typical metallurgical bonding, the bonding strength of the coating is obviously higher, and the coating has higher hardness (the microhardness of the matrix is about 220HV, and the hardness of the coating can reach 510HV, as shown in the description of figure 4). This shows that the method can obtain coating materials with good hardness and strong binding force.
2. Based on the two test results, the dynamic corrosion resistance of the lead-bismuth alloy to the material shows that the erosion pit formed on the surface of the coating after 5000 hours of erosion is only 1/5 of the erosion pit on the surface of the ferrite-martensite steel (see figures 5-8); the abrasion volume of the coating after 1000 times of cyclic abrasion is only 1/9 of that of the matrix ferrite-martensite steel in the same environment (see the description of figure 11); the composite material formed by improving the surface smoothness of the coating material, the hardness of the coating and the binding force achieves excellent dynamic corrosion resistance of the lead-bismuth alloy.
Finally, it should be noted that the laser cladding process provided by the invention is not only suitable for T91 cladding tube materials, but also suitable for other stainless steels, and the foregoing embodiment is only a preferred embodiment, such as 316L stainless steel; the laser parameters are adjusted within the scope of the present embodiment invention according to the type of substrate.
The foregoing has illustrated that the coating material of example 1 has good resistance to high temperatures and dynamic corrosion (and also has good hardness), and that the applicant has also studied the static corrosion properties of the material in view of the specific application of the coating material.
The invention of the embodiment has good corrosion resistance under the static corrosion condition of the lead-bismuth alloy from microscopic view. Particularly, compared with the prior art, the FeCrAlNb high-entropy alloy coating has better dynamic and static corrosion resistance of the lead-bismuth alloy in the high-temperature environment and better hardness compared with other high-entropy alloy coatings in the prior art, so that the FeCrAlNb high-entropy alloy coating has good application prospect.
The above is only an example portion of the application and is not intended to limit the application in any way. Any simple modification, equivalent variation and modification of any of the simple modification embodiments described above still fall within the scope of the claims.
Claims (9)
1. A high temperature resistant lead bismuth alloy environment erosion and abrasion alloy coating is characterized in that: the high-entropy alloy layer gradually forms an oxide layer in a liquid lead bismuth alloy environment, wherein the oxide layer comprises one or more of titanium oxide, aluminum oxide, silicon oxide and chromium oxide, and the elements of the high-entropy alloy layer consist of one or more of Al, ti and Si, one or more of Fe and Cr, and one or more of Y, mo and Nb.
2. The high temperature resistant lead bismuth alloy environmental erosion and abrasion alloy coating according to claim 1, wherein: the elements of the high-entropy alloy layer include Fe, al, cr, ti, nb, and the oxide layer includes alumina, titania, and chromia oxidized from the high-entropy alloy layer.
3. The method for preparing the high-temperature resistant lead-bismuth alloy environmental erosion and abrasion alloy coating according to any one of claims 1-2, wherein the specific steps for preparing the high-entropy alloy layer comprise:
step 1, polishing the surface of a substrate, and polishing the surface of the substrate to have certain roughness by using a polishing tool;
step 2, mixing process raw materials, namely, selecting one or more of Al, ti and Si, one or more of Fe and Cr and one or more of Y, mo and Nb, and mixing the selected process raw materials to obtain mixed metal powder;
and step 3, performing laser cladding, and cladding the mixed metal powder on the surface of the matrix by using a laser cladding technology.
4. The method for preparing the high-temperature resistant lead bismuth alloy environmental erosion and abrasion alloy coating according to claim 3, wherein Al and Ti are selected from the group consisting of Al, ti and Si.
5. The method for preparing the high-temperature resistant lead-bismuth alloy environmental erosion and abrasion alloy coating according to claim 4, wherein the step 2 further comprises the step of mixing the mixed metal powder with polyvinyl alcohol glue (pva) according to a certain proportion to obtain the mixed metal powder.
6. The method for preparing the high-temperature resistant lead bismuth alloy environmental erosion and abrasion alloy coating according to claim 4, wherein the technological parameters of laser cladding are as follows:
the working chamber is filled with 99.9% of inert gas, the laser power is 180W-230W, the laser scanning speed is 27mm/s-33mm/s, the focal point is-0.1 mm-0.5 mm, the spot diameter is 0.3mm-0.9mm, and the multi-pass lap joint rate is 50%.
7. The method of producing a high temperature resistant lead bismuth alloy environmental erosion and abrasion alloy coating according to any one of claims 5 to 6 wherein said process feedstock comprises Fe, al, cr, ti, nb.
8. The method for preparing the high-temperature resistant lead-bismuth alloy environmental erosion and abrasion alloy coating according to any one of claim 7, wherein the raw materials of the process comprise 20% of Fe, 20% of Al, 20% of Cr, 20% of Ti and 20% of Nb.
9. The method for preparing the high-temperature resistant lead-bismuth alloy environmental erosion and abrasion alloy coating according to claim 7, wherein the raw material ratio of the process is 22.2% of Fe, 22.2% of Al, 22.2% of Cr, 22.2% of Ti and 11.1% of Nb.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070107810A1 (en) * | 2005-11-14 | 2007-05-17 | The Regents Of The University Of California | Amorphous metal formulations and structured coatings for corrosion and wear resistance |
| KR20170124441A (en) * | 2016-05-02 | 2017-11-10 | 한국과학기술원 | High- strength and heat-resisting high entropy alloy matrix composites and method of manufacturing the same |
| CN109072398A (en) * | 2016-05-04 | 2018-12-21 | 布里卡拉反应堆斯德哥尔摩股份有限公司 | Pump for high temperature corrosion fluid |
| CN115142018A (en) * | 2022-07-01 | 2022-10-04 | 四川大学 | High-entropy alloy coating resistant to high-temperature liquid lead/lead bismuth alloy corrosion and preparation method thereof |
| CN115627405A (en) * | 2022-10-21 | 2023-01-20 | 中国科学院金属研究所 | High-entropy alloy resistant to liquid lead and bismuth corrosion and preparation method thereof |
-
2023
- 2023-03-06 CN CN202310203947.1A patent/CN116219430A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070107810A1 (en) * | 2005-11-14 | 2007-05-17 | The Regents Of The University Of California | Amorphous metal formulations and structured coatings for corrosion and wear resistance |
| KR20170124441A (en) * | 2016-05-02 | 2017-11-10 | 한국과학기술원 | High- strength and heat-resisting high entropy alloy matrix composites and method of manufacturing the same |
| CN109072398A (en) * | 2016-05-04 | 2018-12-21 | 布里卡拉反应堆斯德哥尔摩股份有限公司 | Pump for high temperature corrosion fluid |
| CN115142018A (en) * | 2022-07-01 | 2022-10-04 | 四川大学 | High-entropy alloy coating resistant to high-temperature liquid lead/lead bismuth alloy corrosion and preparation method thereof |
| CN115627405A (en) * | 2022-10-21 | 2023-01-20 | 中国科学院金属研究所 | High-entropy alloy resistant to liquid lead and bismuth corrosion and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| JIAN YANG等: "A novel AlCrFeMoTi high-entropy alloy coating with a high corrosion-resistance in lead-bismuth eutectic alloy", 《CORROSION SCIENCE》, vol. 187, 1 May 2021 (2021-05-01), pages 109524, XP086580410, DOI: 10.1016/j.corsci.2021.109524 * |
| 梁娜等: "铅冷快堆结构材料耐蚀涂层技术研究概述", 《材料导报》, vol. 36, no. 23, 31 December 2022 (2022-12-31), pages 1 - 7 * |
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