CN111139422A - Preparation method of amorphous alloy coating for radiation protection of nuclear waste container - Google Patents
Preparation method of amorphous alloy coating for radiation protection of nuclear waste container 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
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- 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
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- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
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Abstract
The invention discloses a preparation method of an amorphous alloy coating for radiation protection of a nuclear waste container, which comprises the following steps: mixing Al2O3Mixing the powder and Fe-Cr-C-Si-Gd-B iron-based amorphous alloy powder by a high-speed mixer; carrying out ultrasonic screening on the mixed powder by using high-power ultrasonic waves; mixing Al2O3Drying the powder and the iron-based amorphous alloy composite powder; and directly spraying the composite powder on the surface of the nuclear waste container by adopting a supersonic flame spraying method. The preparation method of the amorphous alloy coating for radiation protection of the nuclear waste container improves the binding force, the density, the amorphous content and the wear resistance of the Fe-Cr-C-Si-Gd-B iron-based amorphous alloy composite coating and the nuclear reactor waste container, reduces the porosity of the amorphous alloy composite coating, and simultaneously coats the amorphous alloy composite coatingThe layer has excellent neutron absorption capability.
Description
Technical Field
The invention particularly relates to a preparation method of an amorphous alloy coating for radiation protection of a nuclear waste container.
Background
Generally, each million kilowatt nuclear power unit can discharge 25t of spent fuel every year, and the current spent fuel accumulated in China reaches more than 1000t. At present, most of the storage modes of the spent fuel at home and abroad adopt 'wet' storage (namely, the spent fuel is stored on a grid frame of a pool) and 'dry' storage, and a dry storage container has the functions of storing and transporting the spent fuel. The spent fuel discharged from the nuclear reactor has extremely strong radioactivity, has certain neutron emissivity, and needs to be stored in a spent fuel pool for a period of time so as to enable most of radioactive nuclides with short half-life period to decay away and take away decay heat. The materials for processing the spent fuel are required to have high thermal neutron absorption capacity, and also have the characteristics of high strength, high temperature corrosion resistance, irradiation resistance, low thermal expansion coefficient and the like. At present, the spent fuel storage and transportation equipment and the grid work material used abroad are mainly boron-containing steel, boron-aluminum alloy and B4C/Al composite material, cadmium-gadolinium-containing neutron absorbing material, organic polymer and the like.
Organic polymer such as boron-containing polyethylene belongs to nonmetal-based neutron absorption materials, the matrix of the material is nonmetal, so the material has no good mechanical structure performance, and can only be used as a single functional material, the radiation resistance and the corrosion resistance of the material are not good, and the polyethylene is easy to age and become brittle under a strong dose of radiation field to limit the use of the material.
The existing commonly used nuclear waste storage and transportation container is mainly composed of boron-containing steel, but the boron-containing steel has low boron content, low absorption capacity for thermal neutrons and epithermal neutrons, poor neutron absorption capacity, and is difficult to meet the storage and transportation of the nuclear waste, and the boron content of the boron-containing steel and boron-aluminum alloy is low, and the strength is reduced along with the increase of the boron content; in addition, cadmium-gadolinium materials are prone to produce neutron poisons.
B4The C/Al composite material combines the advantages of toughness, ductility, formability and the like of aluminum metal with the advantages of hardness, ablation resistance, low density and the like of boron carbide ceramic, and B4The C/Al composite material has low density, high thermal conductivity, good mechanical property and high neutron absorption capacity, is already applied abroad, but the material has high price and cannot be popularized and applied in a large scale. And B4The combination of the C/Al composite coating and the stainless steel substrate provides a more economical solution for the treatment of the spent fuel, but the requirements of the container are metThe aim of radioactive shielding is achieved while the structural strength is required, and the process for arranging the composite material coating on the stainless steel substrate has higher requirements. The Chinese academy utilized the cold spraying process to prepare B on a steel matrix4C/Al composite coating. The cold spray process is a coating formed by plastic deformation of high velocity powder particles as they impact a substrate at low temperatures. B obtained by the method4In the C/Al composite coating, the porosity is below 5%, the binding force is higher than 30MPa, the thickness is above 500 mu m, B4The C particles are substantially uniformly distributed in the Al matrix. However, due to the limitation of the process principle, the prepared coating has low binding force with a substrate and high porosity, when the coating is used for a long time in a complex environment containing radioactivity and high corrosivity, tiny primary batteries are easily generated on the surface of a container to cause pore corrosion, and the coating falls off when the coating is serious.
The amorphous alloy (also called metallic glass) is a new type metal structure material with long-range disordered atomic arrangement, common alloy and B4Compared with the C ceramic, the amorphous alloy has no defects of crystal grains, crystal boundaries, dislocation and the like, so that the amorphous alloy shows a plurality of excellent physical and chemical properties, has a series of excellent mechanical properties such as high elasticity and high strength, and has wide application prospects in the fields of spaceflight, national defense, energy sources and the like. The iron-based amorphous alloy has the characteristics of low raw material cost, excellent wear resistance and corrosion resistance, superior thermal stability and the like, so that the iron-based amorphous alloy can be applied to corrosive medium environments such as various acids, seawater, sewage and the like. The amorphous alloy contains a high content of B element and has excellent neutron absorption capacity, and according to the records of foreign literature documents, the neutron absorption capacity of the amorphous alloy is 7 times that of stainless steel and Ni-based high-temperature alloy (C22) and is more than 3 times that of boron steel, so that the amorphous alloy can be used as a neutron absorption material in the field of nuclear radiation protection. However, amorphous alloys are not suitable as structural materials because of their poor plastic deformation ability and low fracture toughness.
High Velocity Oxygen (HVOF) is a high temperature, high velocity combustion flame stream generated by combustion of a hydrocarbon fuel gas such as propane or propylene, or hydrogen and high pressure oxygen in a combustion chamber or in a special nozzle. The supersonic flame spraying has moderate heat input, high spraying speed, difficult crystallization of the coating and compact structure, and is the preferred technology for preparing the iron-based amorphous coating. At present, the application of the supersonic spraying amorphous alloy coating in the radiation protection field of the nuclear waste container is not reported at home, and the amorphous alloy coating prepared by domestic scientific research and enterprises in other application fields still has the defects of low coating hardness (the Vickers hardness is generally between 530 and 950 HV), low amorphous content (below 80 percent), low bonding force between the coating and a substrate (between 25 and 45 MPa), low boron content (below 15 percent of atomic content), high friction coefficient (above 0.4) and the like. Therefore, the invention provides a novel preparation method of the amorphous alloy coating for radiation protection of the nuclear waste container.
Disclosure of Invention
The invention aims to solve the problems and provides a method for preparing an amorphous alloy coating for radiation protection of a nuclear waste container.
The purpose of the invention is realized as follows:
the preparation method of the amorphous alloy coating for radiation protection of the nuclear waste container comprises the following steps:
s1: 15-25% and 75-85% of Al in percentage by mass2O3Mixing the powder and Fe-Cr-C-Si-Gd-B iron-based amorphous alloy powder by a high-speed mixer, wherein the mixing power is 15-30 kW, the rotating speed is 4000-5000 r/min, and the mixing time is 60-240 min to obtain mixed powder, wherein the Fe-Cr-C-Si-Gd-B iron-based amorphous alloy comprises 42.4-51.4 wt% of iron, 40.0-45.0 wt% of chromium, less than or equal to 0.2 wt% of carbon, 1.5-2.5 wt% of silicon, 2.0-3.5 wt% of gadolinium and 5.0-6.5 wt% of boron;
s2: using high-power ultrasonic waves to perform ultrasonic screening on the mixed powder obtained in the step S1 to obtain Al2O3Powder and iron-based amorphous alloy composite powder, wherein the working frequency is 30-40 KHz, and the time is 15-30 min;
s3: mixing Al2O3Putting the powder and the iron-based amorphous alloy composite powder into an oven for drying at the drying temperature of 100 +/-3 ℃ for 60 +/-10 min, and then naturally cooling to room temperature; and
s4: directly spraying the composite powder in the S3 to the surface of the nuclear waste container by a spray gun by adopting a supersonic flame spraying method to obtain a layer of Fe-Cr-C-Si-Gd-B iron-based amorphous alloy composite coating, and repeatedly spraying the iron-based amorphous alloy composite coating above the surface of the nuclear waste container back and forth by the spray gun to stack the iron-based amorphous alloy composite coating layer by layer, wherein the thickness of each layer of the composite coating is 10-20 mu m; the flame flow speed of supersonic flame spraying is more than 2000m/s, the sprayed particle speed is 400-500 m/s, the temperature of the outer surface of the container is less than 100 ℃ during spraying, the oxygen flow is 200-250L/min, the powder feeding rate is 25-35 g/min, and the distance between a spray gun and the surface of the nuclear waste container is 200-275 mm during spraying.
Al in the preparation method of the amorphous alloy coating for radiation protection of the nuclear waste container2O3The particle size range of the powder is 15-50 μm, and the particle size range of the amorphous alloy is 15-50 μm.
The Fe-Cr-C-Si-Gd-B iron-based amorphous alloy comprises the following components: 42.4 to 51.4 weight percent of iron, 40.0 to 45.0 weight percent of chromium, less than or equal to 0.2 weight percent of carbon, 1.5 to 2.5 weight percent of silicon, 2.0 to 3.5 weight percent of gadolinium and 5.0 to 6.5 weight percent of boron.
In the preparation method of the amorphous alloy coating for radiation protection of the nuclear waste container, the porosity of the accumulated Fe-Cr-C-Si-Gd-B iron-based amorphous alloy composite coating is less than 0.8 percent, the amorphous content of the coating is more than 80 percent, the Vickers hardness of the coating is more than 1100HV, the bonding force between the coating and a matrix is more than 50MPa, and the thickness is 50-2000 mu m.
The thermal neutron absorption capacity of the Fe-Cr-C-Si-Gd-B iron-based amorphous alloy composite coating accumulated in the preparation method of the amorphous alloy coating for radiation protection of the nuclear waste container is more than or equal to 95 percent.
The preparation method of the amorphous alloy coating for radiation protection of the nuclear waste container improves the binding force, the density, the amorphous content and the wear resistance of the Fe-Cr-C-Si-Gd-B iron-based amorphous alloy composite coating and the nuclear reactor waste container, reduces the porosity of the amorphous alloy composite coating, and simultaneously the coating has excellent neutron absorption capacity.
Detailed Description
The present invention will be further described with reference to examples 1 to 3 and comparative examples 1 to 3.
Example 1
The preparation method of the amorphous alloy coating for radiation protection of the nuclear waste container comprises the following steps:
s1: 20 percent to 80 percent of Al2O3Mixing the powder and Fe-Cr-C-Si-Gd-B iron-based amorphous alloy powder by a high-speed mixer, wherein the mixing power is 20kW, the rotating speed is 4000 revolutions per minute, and the mixing time is 120min to obtain mixed powder;
s2: using high-power ultrasonic waves to perform ultrasonic screening on the mixed powder obtained in the step S1 to obtain Al2O3The powder and the iron-based amorphous alloy composite powder achieve the effects of breaking agglomeration and uniformly dispersing, the working frequency is 30-40 KHz, and the time is 20 min;
s3: al to be prepared2O3And (3) putting the powder and the iron-based amorphous alloy composite powder into an oven for drying, removing water in the powder, and preventing the powder from generating air holes in the heating and spraying process to cause the reduction of the quality of a coating. Drying at 100 deg.C for 60min, and naturally cooling to room temperature; and
s4: directly spraying the composite powder in the S3 to the surface of the nuclear waste container by a spray gun by adopting a supersonic flame spraying method to obtain a layer of Fe-Cr-C-Si-Gd-B iron-based amorphous alloy composite coating, and repeatedly spraying the iron-based amorphous alloy composite coating above the surface of the nuclear waste container back and forth by the spray gun to stack the iron-based amorphous alloy composite coating layer by layer, wherein the thickness of each layer of the composite coating is 10-20 mu m; when the supersonic flame spraying is carried out, the flame flow speed of the supersonic flame spraying is more than 2000m/s, the speed of sprayed particles is 400-500 m/s, the temperature of the outer surface of the container is less than 100 ℃ when the spraying is carried out, the oxygen flow is 250L/min, the powder feeding rate is 30g/min, and the distance between a spray gun and the surface of the nuclear waste container is 250mm when the spraying is carried out.
Wherein, Al in S12O3The granularity of the mixed powder of the Fe-based amorphous alloy and the Al alloy in S1 is 30 mu m;
the porosity of the deposited iron-based amorphous alloy composite coating in S4 is 0.56% according to GB/T13298-2015 standard, the bonding force of the coating is 52MPa according to GB/T8642-2002 standard, and the thickness of the coating is 300 microns; vickers hardness detection of coating surfaceThe result was 1170HV, and the test was carried out by a ball-and-disk type rotary friction tester (using Si with a diameter of 4 mm)3N4The ball is used as a friction pair, the load is 10N), the friction coefficient of the coating is 0.19, and the content of amorphous components in the coating is detected to be 82 percent by a differential scanning calorimeter;
the thermal neutron absorption performance of the iron-based amorphous alloy composite coating deposited in S4 is more than 95%, and the thermal neutron absorption performance is carried out in a reactor by 4.0 x 1013～2.5×1014cm～2After the neutron irradiation of the fluence, the material has no obvious irradiation damage and adverse phase change; the corrosion current of the coating obtained by the Tafel polarization curve test of the electrochemical workstation is about 1.6 multiplied by 10～5A/cm2。
When the surface of the mixed powder obtained in the step S1 is subjected to ultrasonic screening by using high-power ultrasonic waves in the step S2, the mixed powder is sent into an ultrasonic crusher for ultrasonic vibration screening, the ultrasonic frequency is 30000-40000 Hz, large particles of the mixed powder are reduced from agglomerating and adhering into blocks, the screening amount is increased, the number of the large particles is reduced, and Al is added2O3The iron-based amorphous alloy mixed powder is more dispersed, and the gradation is more uniform;
wherein the nuclear waste container is a 316L stainless steel substrate.
Comparative example 1:
the preparation method of the amorphous alloy coating for radiation protection of the nuclear waste container of the comparative example comprises the following steps:
s1: carrying out ultrasonic screening on 100% Fe-Cr-C-Si-Gd-B iron-based amorphous alloy powder by using high-power ultrasonic waves to obtain pure iron-based amorphous alloy powder, so that the effects of breaking agglomeration and uniformly dispersing are achieved, the working frequency is 30-40 KHz, and the time is 20 min;
s3: and the prepared pure iron-based amorphous alloy powder is put into an oven to be dried, so that the moisture in the powder is removed, and the powder is prevented from generating air holes in the heating and spraying process to cause the reduction of the coating quality. Drying at 100 deg.C for 60min, and naturally cooling to room temperature; and
s4: directly spraying the powder in the S3 on the surface of a nuclear waste container by a spray gun by adopting a supersonic flame spraying method to obtain a layer of Fe-Cr-C-Si-Gd-B iron-based amorphous alloy coating, and repeatedly spraying the iron-based amorphous alloy coating by the spray gun back and forth above the surface of the nuclear reactor waste container to stack the iron-based amorphous alloy coating layer by layer, wherein the thickness of each layer of coating is 10 to 20 mu m; when the supersonic flame spraying is carried out, the flame flow speed of the supersonic flame spraying is more than 2000m/s, the speed of sprayed particles is 400-500 m/s, the temperature of the outer surface of the container is less than 100 ℃ when the spraying is carried out, the oxygen flow is 250L/min, the powder feeding rate is 30g/min, and the distance between a spray gun and the surface of the nuclear waste container is 250mm when the spraying is carried out.
The granularity of the pure iron-based amorphous alloy powder in the S1 is 30 mu m;
the porosity of the deposited iron-based amorphous alloy composite coating in S4 is 1.26% according to GB/T13298-2015 standard, the bonding force of the coating is 43MPa according to GB/T8642-2002 standard, and the thickness of the coating is 300 microns; the Vickers hardness detection result of the coating surface is 1085HV, and the coating surface is tested by a ball-disk type rotating friction tester (Si with the diameter of 4mm is selected)3N4The ball is used as a friction pair, the load is 10N), the friction coefficient of the coating is 0.43, and the content of amorphous components in the coating is detected by a differential scanning calorimeter to be 84%;
the thermal neutron absorption performance of the iron-based amorphous alloy composite coating deposited in S4 is more than 95%, and the thermal neutron absorption performance is carried out in a reactor by 4.0 x 1013～2.5×1014cm～2After the neutron irradiation of the fluence, the material has no obvious irradiation damage and adverse phase change; the corrosion current of the coating obtained by the Tafel polarization curve test of the electrochemical workstation is about 3.1 multiplied by 10～5A/cm2。
When the iron-based amorphous alloy powder obtained in the S1 is subjected to ultrasonic screening by using high-power ultrasonic waves in the S2, the powder is sent into an ultrasonic crusher for ultrasonic vibration screening, the ultrasonic frequency is 30000-40000 Hz, so that the aggregation and adhesion of large particles of the iron-based amorphous alloy powder into blocks are reduced, the screening amount is increased, the number of the large particles is reduced, the iron-based amorphous alloy powder is more dispersed, and the grading is more uniform;
the nuclear waste container is a 316L stainless steel substrate.
Example 2
The preparation method of the amorphous alloy coating for radiation protection of the nuclear waste container comprises the following steps:
s1: 20 percent to 80 percent of Al2O3Mixing the powder and Fe-Cr-C-Si-Gd-B iron-based amorphous alloy powder by a high-speed mixer, wherein the mixing power is 20kW, the rotating speed is 4000 revolutions per minute, and the mixing time is 120min to obtain mixed powder;
s2: using high-power ultrasonic waves to perform ultrasonic screening on the mixed powder obtained in the step S1 to obtain Al2O3The powder and the iron-based amorphous alloy composite powder achieve the effects of breaking agglomeration and uniformly dispersing, the working frequency is 30-40 KHz, and the time is 20 min;
s3: al to be prepared2O3And (3) putting the powder and the iron-based amorphous alloy composite powder into an oven for drying, removing water in the powder, and preventing the powder from generating air holes in the heating and spraying process to cause the reduction of the quality of a coating. Drying at 100 deg.C for 60min, and naturally cooling to room temperature; and
s4: directly spraying the composite powder in the S3 to the surface of the nuclear waste container by a spray gun by adopting a supersonic flame spraying method to obtain a layer of Fe-Cr-C-Si-Gd-B iron-based amorphous alloy composite coating, and repeatedly spraying the iron-based amorphous alloy composite coating above the surface of the nuclear waste container back and forth by the spray gun to stack the iron-based amorphous alloy composite coating layer by layer, wherein the thickness of each layer of the composite coating is 10-20 mu m; when the supersonic flame spraying is carried out, the flame flow speed of the supersonic flame spraying is more than 2000m/s, the speed of sprayed particles is 400-500 m/s, the temperature of the outer surface of the container is less than 100 ℃ when the spraying is carried out, the oxygen flow is 270L/min, the powder feeding rate is 25g/min, and the distance between a spray gun and the surface of the nuclear waste container is 225mm when the spraying is carried out.
Al in S12O3The granularity of the mixed powder of the Fe-based amorphous alloy and the Al alloy in S1 is 30 mu m;
the porosity of the deposited iron-based amorphous alloy composite coating in S4 is 0.64% according to GB/T13298-2015 standard, the bonding force of the coating is 54MPa according to GB/T8642-2002 standard, and the thickness of the coating is 300 microns; vickers hardness of coating surfaceThe detection result is 1210HV, and the test result is tested by a ball-disk type rotating friction tester (Si with the diameter of 4mm is selected)3N4The ball is used as a friction pair, the load is 10N), the friction coefficient of the coating is 0.18, and the content of amorphous components in the coating is detected to be 80 percent by a differential scanning calorimeter;
the thermal neutron absorption performance of the iron-based amorphous alloy composite coating deposited in S4 is more than 95%, and the thermal neutron absorption performance is carried out in a reactor by 4.0 x 1013～2.5×1014cm～2After the neutron irradiation of the fluence, the material has no obvious irradiation damage and adverse phase change; the corrosion current of the coating obtained by the Tafel polarization curve test of the electrochemical workstation is about 1.5 multiplied by 10～5A/cm2。
When the surface of the mixed powder obtained in the step S1 is subjected to ultrasonic screening by using high-power ultrasonic waves in the step S2, the mixed powder is sent into an ultrasonic crusher for ultrasonic vibration screening, the ultrasonic frequency is 30000-40000 Hz, large particles of the mixed powder are reduced from agglomerating and adhering into blocks, the screening amount is increased, the number of the large particles is reduced, and Al is added2O3The iron-based amorphous alloy mixed powder is more dispersed, and the gradation is more uniform;
the nuclear waste container is a No. 45 steel matrix.
Comparative example 2
The preparation method of the amorphous alloy coating for radiation protection of the nuclear waste container of the comparative example comprises the following steps:
s1: 20 percent to 80 percent of Al2O3Mixing the powder and Fe-Cr-C-Si-Gd-B iron-based amorphous alloy powder by a high-speed mixer, wherein the mixing power is 20kW, the rotating speed is 4000 revolutions per minute, and the mixing time is 120min to obtain mixed powder;
s2: using high-power ultrasonic waves to perform ultrasonic screening on the mixed powder obtained in the step S1 to obtain Al2O3The powder and the iron-based amorphous alloy composite powder achieve the effects of breaking agglomeration and uniformly dispersing, the working frequency is 30-40 KHz, and the time is 20 min;
s3: al to be prepared2O3Putting the powder and the iron-based amorphous alloy composite powder into an oven for bakingAnd drying to remove water in the powder and prevent the powder from generating air holes in the heating spraying process, so that the quality of the coating is reduced. Drying at 100 deg.C for 60min, and naturally cooling to room temperature; and
s4: directly spraying the composite powder in the S2 to the surface of the nuclear waste container by a spray gun by adopting a supersonic flame spraying method to obtain a layer of Fe-Cr-C-Si-Gd-B iron-based amorphous alloy composite coating, and repeatedly spraying the iron-based amorphous alloy composite coating above the surface of the nuclear waste container back and forth by the spray gun to stack the iron-based amorphous alloy composite coating layer by layer, wherein the thickness of each layer of the composite coating is 10-20 mu m; when the supersonic flame spraying is carried out, the flame flow speed of the supersonic flame spraying is more than 2000m/s, the speed of sprayed particles is 400-500 m/s, the temperature of the outer surface of the container is less than 100 ℃ when the spraying is carried out, the oxygen flow is 150L/min, the powder feeding rate is 20g/min, and the distance between a spray gun and the surface of the nuclear waste container is 150mm when the spraying is carried out.
Al in S12O3The granularity of the mixed powder of the Fe-based amorphous alloy and the Al alloy in S1 is 30 mu m;
the porosity of the deposited iron-based amorphous alloy composite coating in S4 is 1.28% according to GB/T13298-2015 standard, the bonding force of the coating is 39MPa according to GB/T8642-2002 standard, and the thickness of the coating is 300 microns; the Vickers hardness detection result of the surface of the coating is 1100HV, and the coating is detected by a ball-disk type rotating friction tester (Si with the diameter of 4mm is selected)3N4The ball is used as a friction pair, the load is 10N), the friction coefficient of the coating is 0.19, and the content of amorphous components in the coating is detected to be 62 percent by a differential scanning calorimeter;
the thermal neutron absorption performance of the iron-based amorphous alloy composite coating deposited in S4 is about 86%, and the thermal neutron absorption performance is carried out in a reactor at 4.0 x 1013～2.5×1014cm～2After the neutron irradiation of the fluence, the material has no obvious irradiation damage and adverse phase change; the corrosion current of the coating obtained by the Tafel polarization curve test of the electrochemical workstation is about 5.3 multiplied by 10～5A/cm2。
When the surface of the mixed powder obtained in S1 was ultrasonically sieved using high-power ultrasonic waves in S2, the mixed powder was sent to an ultrasonic crusher to be subjected to ultrasonic crushingUltrasonic vibration screening is carried out, the ultrasonic frequency is 30000-40000 Hz, so that the agglomeration and conglomeration of large particles of mixed powder are reduced, the screening amount is increased, the number of large particles is reduced, and Al is contained2O3The iron-based amorphous alloy mixed powder is more dispersed, and the gradation is more uniform;
the nuclear waste container is a No. 45 steel matrix.
Example 3
The preparation method of the amorphous alloy coating for radiation protection of the nuclear waste container comprises the following steps:
s1: 20 percent to 80 percent of Al2O3Mixing the powder and Fe-Cr-C-Si-Gd-B iron-based amorphous alloy powder by a high-speed mixer, wherein the mixing power is 20kW, the rotating speed is 4000 revolutions per minute, and the mixing time is 120min to obtain mixed powder;
s2: using high-power ultrasonic waves to perform ultrasonic screening on the mixed powder obtained in the step S1 to obtain Al2O3The powder and the iron-based amorphous alloy composite powder achieve the effects of breaking agglomeration and uniformly dispersing, the working frequency is 30-40 KHz, and the time is 20 min;
s3: al to be prepared2O3And (3) putting the powder and the iron-based amorphous alloy composite powder into an oven for drying, removing water in the powder, and preventing the powder from generating air holes in the heating and spraying process to cause the reduction of the quality of a coating. Drying at 100 deg.C for 60min, and naturally cooling to room temperature; and
s4: directly spraying the composite powder in the S3 to the surface of the nuclear waste container by a spray gun by adopting a supersonic flame spraying method to obtain a layer of Fe-Cr-C-Si-Gd-B iron-based amorphous alloy composite coating, and repeatedly spraying the iron-based amorphous alloy composite coating above the surface of the nuclear waste container back and forth by the spray gun to stack the iron-based amorphous alloy composite coating layer by layer, wherein the thickness of each layer of the composite coating is 10-20 mu m; when the supersonic flame spraying is carried out, the flame flow speed of the supersonic flame spraying is more than 2000m/s, the speed of sprayed particles is 400-500 m/s, the temperature of the outer surface of the container is less than 100 ℃ when the spraying is carried out, the oxygen flow is 200L/min, the powder feeding rate is 35g/min, and the distance between a spray gun and the surface of the nuclear waste container is 200mm when the spraying is carried out.
Al in S12O3The granularity of the mixed powder of the Fe-based amorphous alloy and the Al alloy in S1 is 30 mu m;
the porosity of the deposited iron-based amorphous alloy composite coating in S4 is 0.73% according to GB/T13298-2015 standard, the bonding force of the coating is 53MPa according to GB/T8642-2002 standard, and the thickness of the coating is 300 microns; the Vickers hardness test result of the surface of the coating is 1250HV, and the test result is tested by a ball-disk type rotating friction tester (Si with the diameter of 4mm is selected)3N4The ball is used as a friction pair, the load is 10N), the friction coefficient of the coating is 0.18, and the content of amorphous components in the coating is 81 percent detected by a differential scanning calorimeter;
the thermal neutron absorption performance of the iron-based amorphous alloy composite coating deposited in S4 is more than 95%, and the thermal neutron absorption performance is carried out in a reactor by 4.0 x 1013～2.5×1014cm～2After the neutron irradiation of the fluence, the material has no obvious irradiation damage and adverse phase change; the corrosion current of the coating obtained by the Tafel polarization curve test of the electrochemical workstation is about 2.1 multiplied by 10～5A/cm2。
When the surface of the mixed powder obtained in the step S1 is subjected to ultrasonic screening by using high-power ultrasonic waves in the step S2, the mixed powder is sent into an ultrasonic crusher for ultrasonic vibration screening, the ultrasonic frequency is 30000-40000 Hz, large particles of the mixed powder are reduced from agglomerating and adhering into blocks, the screening amount is increased, the number of the large particles is reduced, and Al is added2O3The iron-based amorphous alloy mixed powder is more dispersed, and the gradation is more uniform;
the nuclear waste container is a No. 45 steel matrix.
Comparative example 3
The preparation method of the amorphous alloy coating for radiation protection of the nuclear waste container of the comparative example comprises the following steps:
s1: 20 percent to 80 percent of Al2O3Mixing the powder and Fe-Cr-C-Si-Gd-B iron-based amorphous alloy powder by a high-speed mixer, wherein the mixing power is 20kW, the rotating speed is 4000 revolutions per minute, and the mixing time is 120min to obtain mixed powder;
s2: using high-power ultrasonic waves to perform ultrasonic screening on the mixed powder obtained in the step S1 to obtain Al2O3The powder and the iron-based amorphous alloy composite powder achieve the effects of breaking agglomeration and uniformly dispersing, the working frequency is 30-40 KHz, and the time is 20 min;
s3: directly spraying the composite powder in the S2 to the surface of the nuclear waste container by a spray gun by adopting a supersonic flame spraying method to obtain a layer of Fe-Cr-C-Si-Gd-B iron-based amorphous alloy composite coating, and repeatedly spraying the iron-based amorphous alloy composite coating above the surface of the nuclear waste container back and forth by the spray gun to stack the iron-based amorphous alloy composite coating layer by layer, wherein the thickness of each layer of the composite coating is 10-20 mu m; when the supersonic flame spraying is carried out, the flame flow speed of the supersonic flame spraying is more than 2000m/s, the speed of sprayed particles is 400-500 m/s, the temperature of the outer surface of the container is less than 100 ℃ when the spraying is carried out, the oxygen flow is 150L/min, the powder feeding rate is 20g/min, and the distance between a spray gun and the surface of the nuclear waste container is 150mm when the spraying is carried out.
Al in S12O3The granularity of the mixed powder of the Fe-based amorphous alloy and the Al alloy in S1 is 30 mu m;
the porosity of the deposited iron-based amorphous alloy composite coating in S4 is 1.95% according to GB/T13298-2015 standard, the bonding force of the coating is 45MPa according to GB/T8642-2002 standard, and the thickness of the coating is 300 microns; the Vickers hardness test result of the coating surface is 1130HV, and the coating surface is tested by a ball-disk type rotating friction tester (Si with the diameter of 4mm is selected)3N4The ball is used as a friction pair, the load is 10N), the friction coefficient of the coating is 0.25, and the content of amorphous components in the coating is detected to be 68 percent by a differential scanning calorimeter;
the thermal neutron absorption performance of the iron-based amorphous alloy composite coating deposited in S4 is about 84%, and the thermal neutron absorption performance is carried out in a reactor at 4.0 x 1013～2.5×1014cm～2After the neutron irradiation of the fluence, the material has no obvious irradiation damage and adverse phase change; the corrosion current of the coating obtained by the Tafel polarization curve test of the electrochemical workstation is about 6.2 multiplied by 10～5A/cm2。
In S2, the surface of the mixed powder obtained in S1 is treated with high-power ultrasonic wavesWhen ultrasonic screening is carried out, the mixed powder is sent into an ultrasonic crusher for ultrasonic vibration screening, the ultrasonic frequency is 30000-40000 Hz, so that large particles of the mixed powder are reduced from agglomerating and adhering into blocks, the screening amount is increased, the number of the large particles is reduced, and Al is added2O3The iron-based amorphous alloy mixed powder is more dispersed, and the gradation is more uniform;
the nuclear waste container is a No. 45 steel matrix.
As can be seen from examples 1 to 3 and comparative examples 1 to 3, Al obtained by the surface treatment method of the present invention2O3And iron-based amorphous alloy composite coating Al2O3The speed of the iron-based amorphous alloy powder impacting the surface of the nuclear reactor waste container is greatly improved, the compactness, the bonding strength and the amorphous content are further ensured, the porosity of the composite coating is less than 0.8%, the amorphous content is more than 80%, the Vickers hardness is more than 1100HV, and the bonding force between the coating and the matrix is more than 50 MPa; the Fe-Cr-C-Si-Gd-B iron-based amorphous alloy composite coating has high boron content, and the B atom content is more than or equal to 45 percent; the iron-based amorphous alloy composite coating has strong thermal neutron absorption capacity, wherein the neutron absorption cross section is far superior to that of common boron-containing stainless steel, and the thermal neutron absorption capacity is more than or equal to 95 percent; al (Al)2O3The doping of the aluminum alloy greatly improves the friction resistance of the coating, the friction coefficient is less than 0.25, and Al2O3The dispersion distribution within the coating prevents stress concentration and microcracking from occurring, thereby improving the corrosion resistance of the coating. The invention greatly improves the density and bonding strength by a high-speed mixer mixing, ultrasonic screening, oven drying and supersonic flame spraying method.
The above embodiments are provided only for illustrating the present invention and not for limiting the present invention, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention, and therefore all equivalent technical solutions should also fall within the scope of the present invention, and should be defined by the claims.
Claims (5)
1. A preparation method of an amorphous alloy coating for radiation protection of a nuclear waste container is characterized by comprising the following steps:
s1: mixing 15-25% and 75-85% of Al2O3 powder and Fe-Cr-C-Si-Gd-B iron-based amorphous alloy powder in percentage by mass by using a high-speed mixer, wherein the mixing power is 15-30 kW, the rotating speed is 4000-5000 rpm, and the mixing time is 60-240 min, so as to obtain mixed powder;
s2: using high-power ultrasonic waves to perform ultrasonic screening on the mixed powder obtained in the step S1 to obtain Al2O3Powder and iron-based amorphous alloy composite powder, wherein the working frequency is 30-40 KHz, and the time is 15-30 min;
s3: adding the Al2O3Putting the powder and the iron-based amorphous alloy composite powder into an oven for drying at the drying temperature of 100 +/-3 ℃ for 60 +/-10 min, and then naturally cooling to room temperature; and
s4: directly spraying the composite powder in the S3 to the surface of the nuclear waste container by a spray gun by adopting a supersonic flame spraying method to obtain a layer of Fe-Cr-C-Si-Gd-B iron-based amorphous alloy composite coating, and repeatedly spraying the iron-based amorphous alloy composite coating above the surface of the nuclear waste container back and forth by the spray gun to stack the iron-based amorphous alloy composite coating layer by layer, wherein the thickness of each layer of the composite coating is 10-20 mu m; the flame flow speed of the supersonic flame spraying is more than 2000m/s, the spraying particle speed is 400-500 m/s, the temperature of the outer surface of the container is less than 100 ℃ during spraying, the oxygen flow is 200-250L/min, the powder feeding rate is 25-35 g/min, and the distance between a spray gun and the surface of the nuclear waste container is 200-275 mm during spraying.
2. The method for preparing an amorphous alloy coating for radiation protection of a nuclear waste container as claimed in claim 1, wherein the Fe-Cr-C-Si-Gd-B Fe-based amorphous alloy includes 42.4-51.4 wt% of Fe, 40.0-45.0 wt% of Cr, 0.2 wt% or less of C, 1.5-2.5 wt% of Si, 2.0-3.5 wt% of Gd, and 5.0-6.5 wt% of B.
3. The method of preparing an amorphous alloy coating for radiation protection of nuclear waste containers as claimed in claim 1, wherein said Al is2O3The particle size range of the powder is 15-50 mu m, and the particle size range of the amorphous alloy is15-50μm。
4. The method for preparing the amorphous alloy coating for the radiation protection of the nuclear waste container as claimed in claim 1, wherein the porosity of the Fe-Cr-C-Si-Gd-B iron-based amorphous alloy composite coating after stacking is less than 0.8%, the amorphous content of the coating is more than 80%, the Vickers hardness of the coating is more than 1100HV, the bonding force between the coating and the substrate is more than 50MPa, and the thickness is 50-2000 μm.
5. The method for preparing an amorphous alloy coating for radiation protection of a nuclear waste container as claimed in claim 1, wherein the thermal neutron absorption capacity of the Fe-Cr-C-Si-Gd-B iron-based amorphous alloy composite coating after stacking is not less than 95%.
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