CN114990475A - Low-temperature high-activity aluminizing method - Google Patents
Low-temperature high-activity aluminizing method Download PDFInfo
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Images
Classifications
-
- 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
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
- C23C10/34—Embedding in a powder mixture, i.e. pack cementation
- C23C10/36—Embedding in a powder mixture, i.e. pack cementation only one element being diffused
- C23C10/48—Aluminising
- C23C10/50—Aluminising of ferrous surfaces
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention belongs to the technical field of an iron-chromium-aluminum surface aluminizing process, and particularly relates to a low-temperature high-activity aluminizing method. The method adopts specific components and proportion of the aluminizing agent, improves the concentration of active aluminum atoms by improving the content of aluminum in the aluminizing agent, selects aluminum chloride as a new activating agent, and can successfully prepare the aluminized layer with the thickness of dozens of mu m by only preserving heat for 1h-6h (especially preserving heat for 2h at 700 ℃) at 550 ℃ and 700 ℃ under the simple experimental condition of no atmosphere protection. The invention can realize embedding aluminizing treatment at low temperature in a short time, thereby greatly reducing the possibility of damaging a matrix material, and the prepared aluminized layer is compact and uniform, has good continuous transition, no obvious holes and no through cracks on the cross section. The process can treat workpieces in any shapes, does not need complex equipment, has simple flow and short time consumption, and is suitable for preparing the tritium-resistant coating on the engineering scale.
Description
Technical Field
The invention belongs to the technical field of an iron-chromium-aluminum surface aluminizing process, and particularly relates to a low-temperature high-activity aluminizing method.
Background
The nuclear energy is a clean, safe and efficient energy source, and is a preferred scheme for dealing with future energy crisis. However, the fusion reactor has a wide application prospect in the nuclear energy field, and is expected by people, but because of strong activity of tritium, the tritium is easy to permeate outwards through a structural material, so that not only is the tritium lost, but also radioactive pollution is caused to the environment. Especially in the common liquid cladding, the structural material also faces the problems of flowing lead-lithium corrosion, magnetohydrodynamic effect and the like. Therefore, for the safety and economy of fusion reactors, it is necessary to produce a multifunctional coating that is both corrosion resistant and tritium resistant.
The Fe-Cr-Al has a thermal expansion coefficient similar to that of the structural material of the fusion reactor, so researchers try to treat the Fe-Cr-Al to enable the Fe-Cr-Al to have tritium resistance, and then attach the Fe-Cr-Al to the surface of the structural material of the fusion reactor to be used as a tritium resistance coating. In addition, the iron-chromium-aluminum is regarded as an accident fault-tolerant fuel with great prospect due to good thermal property, mechanical property, corrosion resistance, irradiation resistance and the like, is used for replacing the traditional zirconium alloy cladding of the fuel pellet of the fission reactor, but is easy to cause radioactive pollution of a loop coolant due to strong tritium permeability, so that the wastewater treatment is extremely expensive. Therefore, whether the reactor is a fission reactor or a fusion reactor, the tritium-resistant coating is necessarily prepared on the surface of the iron, chromium and aluminum.
Fe-Al/Al 2 O 3 The composite oxide coating has good lead-lithium compatibility, good thermal matching effect with a substrate, and excellent tritium resistance and self-repairing performance, so that the composite oxide coating becomes the first choice for tritium resistance coatings in most countries. Wherein, how to prepare the Fe-Al layer (namely the aluminized layer) with good performance and uniform transition is the basis for preparing the composite coating. The powder pack aluminizing method has been widely used in many fields as a well-established surface modification technique, but in the conventional art, commonly used aluminizing agents include 10-30 wt% Fe 2 Al 5 Or ferro-aluminium alloy powder such as FeAl, 1-10 wt% ammonium chloride and the rest of aluminium oxide powder. However, when the above-mentioned alumetizing agent is used for alumetizing, it is necessary to carry out alumetizing in a protective atmosphere H 2 Or heating to over 900-1100 ℃ under Ar, and then preserving heat for 4-16 h, so that the process is completed for a long time, and atmosphere protection is required, which limits the application of the method under certain conditions. Therefore, it is necessary to develop a low-temperature high-activity aluminizing method requiring less preparation conditions.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a low-temperature high-activity aluminizing method so as to solve the problems that the existing aluminizing process needs overhigh temperature, special equipment and longer process time and the like.
In order to realize the purpose, the invention is realized by the following technical scheme:
the invention provides a low-temperature high-activity aluminizing method, which comprises the following steps:
s1, placing the powdery aluminizing agent and the matrix in a crucible, enabling the matrix to be wrapped in the aluminizing agent and be positioned in the center of the crucible, meanwhile, filling the upper part of the crucible with graphite powder, compacting graphite powder, and exhausting air in the crucible as far as possible, wherein the aluminizing agent comprises aluminum powder, aluminum chloride powder, cerium oxide and aluminum oxide powder;
s2, sealing the crucible, standing and drying for 24-36h at room temperature, and then transferring to 75-85 ℃ for heat preservation for 1-2h to completely dry the refractory mortar and ensure good sealing performance;
s3, heating the sealed crucible to 550-700 ℃, preserving heat, heating for 1-6 h for embedding and aluminizing, and cooling to room temperature after heating.
Preferably, step S3 is 700 ℃ incubation for 2 h.
The invention discloses a method for preparing a Fe-Al layer on the surface of FeCrAl, which is innovatively provided, the prepared Fe-Al layer has excellent performance, no through cracks and holes, a matrix is tightly combined with the Fe-Al layer, the thickness can be accurately controlled, the tritium resistance is excellent, and the penetration rate of the matrix tritium can be reduced by 2-3 orders of magnitude. For the subsequent preparation of Fe-Al/Al with better performance 2 O 3 The composite tritium-resistant coating lays a solid foundation and has wide application prospect;
the traditional embedding aluminizing needs to be heated to more than 900 ℃ in protective atmosphere, and then the heat preservation is carried out for 4-16 h, so that the damage to the matrix material is easily caused.
Preferably, the temperature rise rate of step S3 is 7-15 deg.C/min. Further, the temperature rise rate was 10 ℃/min.
Preferably, the aluminizing agent comprises 20-50 wt% of aluminum powder, 3-10 wt% of aluminum chloride, 0-5 wt% of cerium oxide, and the balance of aluminum oxide powder. The formula of the aluminizing agent belongs to the optimal formula of the invention, and under the formula system, the dosage of each raw material can be properly floated up and down as long as the low-temperature high-activity aluminizing effect of the invention can be achieved.
Preferably, the matrix comprises a ferrochromium aluminum matrix. Tests prove that the low-temperature high-activity aluminizing method is suitable for the iron-chromium-aluminum matrix, but does not exclude the possibility that the method is also suitable for other matrixes.
Preferably, step S2 is to seal the crucible with a mixture of refractory mortar and water glass. Of course, other sealing methods are also suitable for the present invention, as long as the crucible is protected from oxygen and is resistant to 550 ℃ and 700 ℃.
Preferably, after cooling to room temperature in step S3, the method further includes the step of rinsing with alcohol to remove the residual aluminizing agent on the surface. Of course, other solvents that can dissolve the aluminizing agent of the present invention may be used to clean and remove the aluminizing agent remaining on the surface.
Compared with the prior art, the invention has the beneficial effects that:
the invention discloses a low-temperature high-activity aluminizing method, which adopts specific aluminizing agent components and proportion, improves the concentration of active aluminum atoms by improving the content of aluminum in the aluminizing agent, selects aluminum chloride as a new activating agent, and can successfully prepare an aluminized layer with the thickness of dozens of microns by only preserving heat for 1h-6h (especially preserving heat for 2h at 700 ℃) at 550 ℃ and 700 ℃ under the simple experimental condition of no atmosphere protection. The traditional process needs to be carried out in special equipment, protective atmosphere or vacuum condition needs to be provided, and the traditional process needs to be heated to 900-1100 ℃ and kept for 4-16 hours to complete the aluminizing. Therefore, the invention can realize the embedding aluminizing treatment in a short time at a low temperature, thereby greatly reducing the possibility of damaging the matrix material, and the prepared aluminized layer is compact and uniform, mainly consists of an outermost aluminum-rich layer and an inner diffusion layer close to the matrix, has good continuous transition and is not obviousThe holes are shown, the cross section has no through cracks, and the main phase on the surface of the aluminized sample is Fe 2 Al 5 And FeAl 3 . The process can treat workpieces in any shapes, does not need complex equipment, has simple flow and short time consumption, and is suitable for preparing the tritium-resistant coating on the engineering scale.
Drawings
FIG. 1 is an illustration of the embedding of an aluminizing agent and a matrix in a crucible;
FIG. 2 is a surface topography under an electron microscope of the aluminized specimen of example 1;
FIG. 3 is a sectional view of the sample of aluminized steel according to example 1 under an electron microscope;
FIG. 4 is a elemental line scan of a cross-section of the aluminized sample of example 1 under an electron microscope;
FIG. 5 is a cross-sectional element line scanning view of CLAM steel low-activity aluminized steel under an electron microscope;
FIG. 6 is an XRD pattern of the aluminized sample of example 1;
FIG. 7 is a surface topography under an electron microscope of the aluminized sample of example 2;
FIG. 8 is a sectional view of the aluminized sample of example 2 under an electron microscope;
FIG. 9 is a elemental line scan of a cross-section of the aluminized sample of example 2 under an electron microscope;
FIG. 10 is the XRD pattern of the aluminized specimen of example 2;
FIG. 11 is a surface topography under an electron microscope of the aluminized sample of example 3;
FIG. 12 is a sectional view of the aluminized sample of example 3 under an electron microscope;
FIG. 13 is a elemental line scan of the cross-section of the aluminized specimen of example 3 under an electron microscope;
FIG. 14 is the XRD pattern of the aluminized specimen of example 3;
FIG. 15 is a schematic diagram of a gas driven permeation experimental apparatus;
FIG. 16 is a schematic diagram of a gas driven permeation experimental apparatus;
FIG. 17 is a topography map of an aluminized sample after 50 thermal shocks;
FIG. 18 is a graph showing the results of deuterium inhibition performance tests on the aluminized specimens.
Detailed Description
The following further describes the embodiments of the present invention. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the respective embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The experimental procedures in the following examples were carried out by conventional methods unless otherwise specified, and the test materials used in the following examples were commercially available by conventional methods unless otherwise specified.
Example 1A Low temperature high activity aluminizing method
The method comprises the steps of taking iron-chromium-aluminum as a base material, processing a cylindrical base material into a square sample with the thickness of 10mm multiplied by 10mm by a linear cutting process, grinding with 120#, 240#, 600#, 1000#, 1500# and 2000# abrasive paper to remove oxide skin on the surface, and then ultrasonically cleaning the surface with absolute ethyl alcohol. The aluminising agent used included 40 wt% aluminium powder, 55 wt% aluminium oxide powder, 1 wt% cerium oxide and 4 wt% aluminium chloride powder. The specific aluminizing process comprises the following steps:
(1) respectively placing aluminum powder, aluminum oxide powder and aluminum chloride powder in a drying beaker, placing the drying beaker in a constant-temperature air-blast drying oven at 80 ℃ for drying for 2 hours to remove water and other low-melting-point impurities, then weighing 40 wt% of aluminum powder, 56 wt% of aluminum oxide powder and 4 wt% of aluminum chloride powder, filling the weighed materials into a plastic bottle according to the proportion, and placing the plastic bottle in an oscillating oven for oscillating for 0.5 hour to uniformly mix the powder;
(2) placing the mixed aluminizing agent and a base material into a crucible together, ensuring that a matrix is wrapped in the aluminizing agent and is positioned at the most central position of the crucible, filling the uppermost part of the crucible with graphite powder to cover (as shown in figure 1), slightly compacting by hands, further exhausting air to improve the sealing degree (the graphite powder can react with residual oxygen in the crucible in the heating process to reduce the possibility of oxidizing the surface of a sample as much as possible), mixing and sealing the crucible with refractory mortar and water glass (the refractory mortar and the water glass are uniformly mixed and then sealed), and standing for 24 hours;
(3) keeping the crucible still, keeping the temperature of the crucible at 80 ℃ for 1h to completely dry the refractory mortar, then putting the refractory mortar into a muffle furnace, keeping the temperature of the crucible and heating the refractory mortar at 700 ℃ for 2h, taking out the crucible and keeping the crucible still, cooling the crucible to room temperature, taking out a sample, rinsing the sample with alcohol to remove the residual aluminizing agent on the surface, drying the sample by a blower, and bagging the sample to obtain an aluminized iron-chromium-aluminum sample.
As can be seen from the surface topography of FIG. 2, the calorized layer of the calorized sample has no obvious hole crack and is relatively flat; the thickness of the infiltrated layer is about 40 μm as can be seen from the cross-sectional topography of FIG. 3; from the cross-sectional element line scan of fig. 4, it can be seen that there are continuous transition elements at the interface between the substrate and the infiltrated layer, which can solve the problem of thermal mismatch between the substrate and the infiltrated layer well. In addition, compared with CLAM steel with BCC structure, the invention has high activity (if the surface phase of the aluminized layer is Fe with higher Al content) 2 Al 5 Or FeAl 3 Or the mixture of the two is high-activity aluminizing; if the surface phase of the aluminized layer is FeAl with lower Al content, the aluminized layer is low-activity aluminizing, so the surface phase of the aluminized layer is low-activity aluminizing with CLAM steel (the surface phase of the aluminized layer is FeAl, the Al content is 32.53 percent, and the surface phase of the aluminized layer of the embodiment is Fe 2 Al 5 With FeAl 3 The Al content of the mixture of the two is between 54.66 and 59.12 percent), in the low-activity aluminizing, the elements are in continuous transition in the whole Fe-Al layer (figure 5), while the high-activity aluminizing is in continuous transition only in the interface of the substrate and the aluminizing layer, and other parts of the Fe-Al layer are iron-aluminum compounds with high Al content, so that the Fe-Al layer can provide enough high-activity Al atoms and the coating has the self-repairing function of microcracks. From the XRD pattern of FIG. 6, it is understood that the surface of the case of the sample was composed mainly of Fe 2 Al 5 And FeAl 3 Two phases are formed.
Example 2A Low temperature high activity aluminizing method
The preparation method is the same as example 1, except that: after being put into a muffle furnace, the mixture is heated for 2 hours at 550 ℃.
As can be seen from the surface topography of FIG. 7, the surface of the infiltrated layer is rough and not smooth enough; as can be seen from the cross-sectional profile of FIG. 8, the infiltrated layer has a thickness of about 27.5 μm, is thinner than 700 deg.C, and is not includedThe presence of through-cracks, as well as a continuous transition layer of elements at 700 ℃ (FIG. 9), and the XRD test of the surface (FIG. 10) showed that the phase composition was also Fe 2 Al 5 And FeAl 3 。
Example 3A Low temperature high activity aluminizing method
The preparation method is the same as example 1, except that: after being put into a muffle furnace, the mixture is heated for 6 hours at 700 ℃.
As can be seen from the surface topography of fig. 11, fine cracks appeared on the surface of the infiltrated layer, but as can be seen from the cross-sectional topography of fig. 12, the cracks did not penetrate through the entire infiltrated layer, and the infiltrated layer thickness was about 124 μm, much larger than that of example 1, and example 2. Similar to examples 1 and 2, the cross-sectional element also changed in a continuous transition (FIG. 13), and the surface phase was Fe 2 Al 5 And FeAl 3 (FIG. 14).
Experimental example 1 thermal shock resistance and deuterium resistance test
The aluminized sample prepared in example 1 was subjected to thermal shock resistance and deuterium resistance tests (since hydrogen isotopes are similar, hydrogen environment background is large, and tritium has radioactivity, deuterium gas is generally used internationally for the tests, but the tritium resistance can be characterized to be good and bad).
The thermal shock resistance test method comprises the following steps: putting the aluminized sample into a muffle furnace at 730 ℃ for heat preservation for 5 minutes, taking out the aluminized sample, putting the aluminized sample into room-temperature water, and rapidly cooling the aluminized sample, wherein 1 circulation impact of 730-room-temperature water is completed.
The deuterium inhibition performance test is as follows: the method is carried out on a gas-driven permeation experimental device, the coating side faces to the high-pressure upstream end, an aluminized sample is sealed by a metal O ring and is loaded into a clamp, then the sample is heated to a set temperature in a heating furnace, the temperature rise and fall rate is selected to be 2 ℃/min, after the sample is heated to a specified temperature, the sample is subjected to heat preservation and degassing for 3h, so that gas absorbed in the sample is exhausted, then the background is measured under the condition of no deuterium gas, deuterium gas is introduced until steady state permeation is achieved, the ion current intensity of the sample at the steady state under the temperature can be obtained, then a mass spectrum signal is calibrated, the steady state permeation flux can be obtained, and then the permeability can be obtained through formula calculation.
The ion current intensity I and the permeability phi detected by the quadrupole mass spectrometer have the following conversion relation:
wherein P is driving pressure, d is sample thickness, Q is standard leak rate, and the leak rate of helium standard leak hole used in the experimental device is 4.92 multiplied by 10 -7 Pa·m 3 /s，I 1 The standard leakage rate is converted into deuterium ion current intensity, and the value is 6.45669 multiplied by 10 -11 (ii) a R is a gas constant with a value of 8.314J/(mol.K); s is the sample surface area and T is the thermodynamic temperature.
The gas driven permeation experimental apparatus used for the test is self-assembled (the physical diagram and the schematic diagram are respectively shown in fig. 15 and fig. 16), and all the components are obtained by purchasing. The gas-driven permeation experimental device mainly comprises a deuterium gas tank, a pressure stabilizing tank, a heating furnace, an electromagnetic valve (V1-V11), a quadrupole mass spectrometer, a molecular pump, a mechanical pump, a vacuum gauge and the like. The apparatus main body portion is divided into an upstream side, a heating zone, and a downstream side. The upstream side comprises a pressure stabilizing tank, an electromagnetic valve, a molecular pump, a mechanical pump, a stress film vacuum gauge (APR265) and various pipeline valves. The deuterium gas tank is connected with the pressure stabilizing tank through valves V2 and V3, and the change of the pressure of the deuterium gas in the pressure stabilizing tank is observed by the APR265 in real time. The solenoid valve is the check valve, is the closed condition under the conventional condition, if need change experimental gas, opens the solenoid valve and can empty the interior gas of surge tank. The molecular pump and the mechanical pump on the upstream side are responsible for continuously pumping the upstream part of the sample area through V9, and the internal vacuum degree is ensured to meet the experimental requirements. The downstream side comprises the test chamber, molecular pump, mechanical pump, hot cathode ion vacuum gauge (PBR260), and various plumbing valves. The sample heating zone is connected to the test chamber via V6, the molecular pump and mechanical pump are connected to the sample heating zone via V10, and the test chamber via V11, the sample and test chamber can be evacuated prior to the experiment.
The test result of FIG. 17 shows that the Fe-Al layer of the aluminized sample can resist the cyclic impact of 730-room temperature water for at least 50 times, and no surface shedding is found under an electron microscope, which indicates that the thermal shock resistance is good.
Meanwhile, the test result in FIG. 18 shows that after the Fe-Al layer is prepared on the surface of the FeCrAl substrate, the deuterium permeability of the FeCrAl substrate is reduced by about 2-3 magnitude levels when the deuterium permeability is 573-823K, which indicates that the Fe-Al layer has stronger tritium resistance.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, and the scope of protection is still within the scope of the invention.
Claims (7)
1. A low-temperature high-activity aluminizing method is characterized by comprising the following steps:
s1, placing the powdery aluminizing agent and the matrix in a crucible, enabling the matrix to be wrapped in the aluminizing agent and be positioned in the center of the crucible, meanwhile, filling the upper part of the crucible with graphite powder, compacting graphite powder, and exhausting air in the crucible as far as possible, wherein the aluminizing agent comprises aluminum powder, aluminum chloride powder, cerium oxide and aluminum oxide powder;
s2, sealing the crucible, standing and drying for 24-36h at room temperature, and then transferring to 75-85 ℃ for heat preservation for 1-2h to completely dry the refractory mortar and ensure good sealing performance;
s3, heating the sealed crucible to 550-700 ℃, preserving heat and heating for 1-6 h for embedding aluminizing, and cooling to room temperature after heating.
2. The method of claim 1, wherein step S3 is performed at 700 ℃ for 2 h.
3. The method of claim 1, wherein the temperature raising rate of step S3 is 7-15 ℃/min.
4. The low-temperature high-activity aluminizing method according to claim 1, wherein the aluminizing agent comprises 20-50 wt% of aluminum powder, 3-10 wt% of aluminum chloride powder, 0-5 wt% of cerium oxide, and the balance of aluminum oxide powder.
5. The method of claim 1, wherein the substrate comprises a ferrochromium substrate.
6. The method of claim 1, wherein step S2 is sealing the crucible with a mixture of refractory mortar and water glass.
7. The method of claim 1, further comprising the step of rinsing with alcohol to remove residual alumetizing agent on the surface after cooling to room temperature in step S3.
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