CN113088835A - Co-Ta-B-Si bulk amorphous alloy material used as neutron shield and preparation method thereof - Google Patents
Co-Ta-B-Si bulk amorphous alloy material used as neutron shield and preparation method thereof Download PDFInfo
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- 229910000808 amorphous metal alloy Inorganic materials 0.000 title claims abstract description 160
- 239000000956 alloy Substances 0.000 title claims abstract description 91
- 238000002360 preparation method Methods 0.000 title abstract description 32
- 238000000576 coating method Methods 0.000 claims abstract description 37
- 238000002834 transmittance Methods 0.000 claims abstract description 17
- 229910052796 boron Inorganic materials 0.000 claims abstract description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 100
- 238000003723 Smelting Methods 0.000 claims description 88
- 229910045601 alloy Inorganic materials 0.000 claims description 80
- 229910052786 argon Inorganic materials 0.000 claims description 50
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 32
- 239000011248 coating agent Substances 0.000 claims description 32
- 229910052802 copper Inorganic materials 0.000 claims description 32
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/04—Amorphous alloys with nickel or cobalt as the major constituent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D23/00—Casting processes not provided for in groups B22D1/00 - B22D21/00
- B22D23/003—Moulding by spraying metal on a surface
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
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- B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
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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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- 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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- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F1/00—Shielding characterised by the composition of the materials
- G21F1/02—Selection of uniform shielding materials
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- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F1/00—Shielding characterised by the composition of the materials
- G21F1/02—Selection of uniform shielding materials
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- B22F9/00—Making metallic powder or suspensions thereof
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- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
- B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
- B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
- B22F2009/0824—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid with a specific atomising fluid
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
- B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
- B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
- B22F2009/0848—Melting process before atomisation
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Abstract
The invention discloses a Co-Ta-B-Si bulk amorphous alloy material used as neutron shielding and a preparation method thereof, wherein the Co-Ta-B-Si bulk amorphous alloy consists of 5-15 at% of Ta, 17-34 at% of B, 1-10 at% of Si and the balance of Co. The Co-Ta-B-Si bulk amorphous alloy has a high boron content. The neutron transmittance is less than 50% in a wide wavelength range of 0.15nm to 0.85 nm. Particularly, the transmittance of neutrons with a wavelength of 0.85nm is only 10.0-25.0%. The block amorphous alloy has the characteristics of high hardness, high strength and high forming capability, and simultaneously keeps certain plasticity, can be used for neutron shielding coatings in a wide range, and can be used for wear-resistant coatings of parts such as gears and the like.
Description
Technical Field
The invention relates to a material with neutron shielding property, in particular to a Co-Ta-B-Si bulk amorphous alloy material as a coating material for shielding neutrons, and specifically relates to a Co-based bulk amorphous alloy with high glass forming capability, high strength, high hardness and certain compression plasticity.
Background
Radioprotection stems from the discovery and application of X-rays, radioactivity. In view of the early historical conditions and the state of the art. There is a price paid in the practice of studying and applying nuclear and ionizing radiation techniques. Experience at home and abroad shows that the radiation safety and protection problems caused by the application of the nuclear energy technology and the research units or projects of ionizing radiation must be considered.
Generally, amorphous alloys having a three-dimensional dimension greater than 1mm are so-called Bulk amorphous alloys (Bulk glass alloys), also known as Bulk amorphous alloys.
Bulk amorphous alloys have characteristics of both liquids and solids, metals and glasses, and thus have unique physicochemical properties. Such as: compared with the traditional crystalline alloy material, the bulk amorphous alloy has more excellent mechanical property, magnetic property, corrosion resistance, casting forming property, thermoplastic forming property and the like, so that the material is expected to be used as a high-performance novel structure function integrated material. Has great application prospect in the fields of aerospace, electronic and electrotechnics, biological medical treatment and the like.
The neutrons have a mass approximately equal to that of the protons and are not charged as well as the gamma rays. Thus, there is no electrostatic interaction between neutrons and nuclei or electrons. When the neutron interacts with the substance, the neutron mainly interacts with nuclear force between atomic nuclei, but does not interact with shell electrons. The type of interaction of a neutron and a substance depends primarily on the neutron energy. In radiation protection, neutrons are divided into slow neutrons, intermediate neutrons and fast neutrons according to the energy level of the neutrons. The nuclear interaction process of neutrons with matter can be essentially divided into two categories: scattering and absorption. Scattering can in turn be divided into elastic and inelastic scattering. The main form of interaction of slow neutrons with nuclei is absorption. The result of the absorption process is a change in the nature of the nuclei being struck. The external irradiation protection to neutrons is mainly to shield fast neutrons. The decay process of neutrons in matter is substantially similar to gamma rays.
At present, the Co-based amorphous alloy which has good protection effect and the raw materials with high specific strength, high hardness and certain plastic deformation capability has not been reported.
Disclosure of Invention
In order to develop Co-based amorphous alloy with high specific strength, high hardness and certain plastic deformation capacity, the invention designs Co-Ta-B-Si bulk amorphous alloy with Si element partially replacing B element.
The Co-Ta-B-Si bulk amorphous alloy used as neutron shielding consists of 5-15 at% of Ta, 17-34 at% of B, 1-10 at% of Si and the balance of Co, and the sum of the atomic percentages of all elements is 100. The preparation technology adopts a method combining vacuum high-temperature melting and rapid solidification.
The specific process for preparing the Co-Ta-B-Si bulk amorphous alloy material used as neutron shielding comprises the following steps:
the method comprises the following steps: batching according to the nominal components;
weighing each element according to the nominal components of the Co-Ta-B-Si bulk amorphous alloy, wherein the purity of each element is not lower than 99.0 percent, the atomic percentage content is 100 percent, and uniformly mixing the simple substance elements weighed according to the proportion to obtain a smelting raw material;
step two: performing vacuum induction melting on a prefabricated Co-Ta-B-Si alloy ingot;
mixing all the materialsPutting the uniform smelting raw material into a quartz tube, then putting the quartz tube into a vacuum smelting induction furnace, and vacuumizing the furnace to the vacuum degree of 5.0 multiplied by 10 by adopting a method of firstly low vacuum and then high vacuum－3～3.0×10－2Pa, then opening an air inlet valve and filling argon with the purity of 99.9 percent under 0.05 Mpa; under the protection of a high-purity argon atmosphere and at a high-frequency smelting temperature of 1000-2000 ℃, smelting for 3-5 min, repeatedly smelting for 2-5 times, cooling along with the furnace, and taking out to obtain a prefabricated alloy ingot;
step three: smelting by vacuum arc to prepare Co-Ta-B-Si master alloy;
scrubbing a copper mould in the vacuum arc furnace, putting the copper mould into the prefabricated Co-Ta-B-Si alloy ingot smelted in the step two, and then vacuumizing the furnace to the vacuum degree of 3.0 multiplied by 10－3～2.0×10－2Pa, introducing high-purity argon of 0.05 MPa; under the protection of argon atmosphere, arc melting is carried out for 2-5 min at 1000-3000 ℃, the alloy is turned over and repeatedly melted for 3-5 times after being cooled, and the alloy is cooled for 30min along with the furnace after being uniformly melted and taken out, so that a Co-Ta-B-Si master alloy is obtained;
step four: rapidly solidifying to prepare Co-Ta-B-Si bulk amorphous alloy;
placing the Co-Ta-B-Si master alloy crucible prepared in the third step into an induction furnace of a rapid solidification device, and vacuumizing the furnace to 5.0 multiplied by 10－3～5.0×10－2Pa, then introducing high-purity argon of 0.05 MPa;
adjusting the position between the copper mold and the crucible, wherein the injection pressure is 0.03-0.1 MPa, starting high-frequency induction heating, the heating current is 10-40A, heating to melt the master alloy for 10-60 s, then, performing injection casting in a fixed copper mold, and cooling to obtain the bulk Co-Ta-B-Si amorphous alloy.
The cooling rate is 10-103K/s。
Step five: preparing Co-Ta-B-Si amorphous alloy powder by gas atomization;
firstly, putting the Co-Ta-B-Si bulk amorphous alloy into a smelting furnace, vacuumizing the smelting furnace to ensure that the vacuum degree is less than 10Pa, heating to raise the temperature until the raw materials begin to melt, filling argon to ensure that the argon pressure reaches about 0.05MPa, and then continuing to heat for 10 min; opening a nozzle high-pressure argon gas valve, pouring the obtained Co-Ta-B-Si amorphous alloy liquid into a tundish of a vacuum induction melting gas atomization powder making device after the gas pressure is stabilized at about 3.5MPa, preheating the tundish to 1300 ℃ before pouring the alloy liquid into the tundish, enabling the alloy liquid to flow out to an atomization chamber along a guide pipe at the bottom of the tundish, and carrying out atomization cooling to obtain Co-Ta-B-Si amorphous alloy powder; then sieving is carried out to obtain Co-Ta-B-Si amorphous alloy powder with the average grain diameter of 30 microns.
Step six: laser cladding is carried out to prepare a Co-Ta-B-Si amorphous alloy coating;
performing laser cladding on Co-Ta-B-Si amorphous powder with the average grain diameter of 30 microns by adopting AHL-W180III laser equipment and a 180W Nd-YAG solid-state laser; the parameters for preparing the Co-Ta-B-Si amorphous alloy coating are that the loading voltage is 150V, the scanning speed is 250mm/min, the pulse width is 0.5ms, and the pulse frequency is 15 Hz. 1045 steel plates with the thickness of 3mm are used as a substrate of the laser cladding process. The surface of the substrate was polished with 800-grit SiC paper to remove the oxide film, and then cleaned with absolute ethanol under ultrasonic waves. The thickness of the Co-Ta-B-Si powder layer is 80 mu m per layer, and 4 layers are cladded to reduce the dilution of the coating by the matrix.
The Co-Ta-B-Si bulk amorphous alloy has the advantages that:
(1) the Co-Ta-B series amorphous alloys have been widely regarded as having ultra-high strength and specific strength, but their zero plasticity and low glass forming ability limit their possible applications. Therefore, it is important to improve the plasticity and forming ability of the ultra-high strength Co-based amorphous. On the basis of the original Co-Ta-B, Si element is added through the replacement of similar elements, so that the plasticity of the amorphous alloy is greatly increased, high strength and high hardness are kept, and the application range of the amorphous alloy as a structural material is enlarged.
(2) The Si element and the B element are replaced similarly, and the atomic ratio of the system is further changed, so that the glass forming capability of the Co-Ta-B-Si bulk amorphous alloy is greatly improved, the critical diameter can reach 5mm at most, and the high thermal stability of the Co-Ta-B-Si bulk amorphous alloy is maintained.
(3) The material cost in the amorphous alloy can influence the application of the amorphous alloy, and the prepared Co-Ta-B-Si bulk amorphous alloy has low cost on the basis of retaining the excellent performance of the amorphous alloy by replacing similar elements and replacing part of B elements with Si elements with lower price.
(4) The B element has a large neutron scattering cross section, is easy to capture neutrons, has high hardness and certain plasticity, and can be used for wide-range neutron shielding coatings, such as nuclear power stations and the like. The neutron transmittance of the prepared amorphous alloy is 50-60% in a wide wavelength range of 0.15-0.85 nm, particularly the neutron with the wavelength of 0.85nm, and the transmittance is only 10.0-25%.
(5) The element B is easy to splash in the smelting process to cause inconsistency of actual components and nominal components, the method firstly adopts a vacuum high-frequency induction heating mode in the process of smelting master alloy to form prealloy and then adopts vacuum arc smelting, so that the splashing loss of raw materials in the smelting process can be prevented in the maximum range.
Drawings
FIG. 1 shows Co in example 1 of the present invention55Ta10B34Si1X-ray diffraction (XRD) pattern of bulk amorphous alloy.
FIG. 2 shows Co in example 1 of the present invention55Ta10B34Si1Differential Scanning Calorimeter (DSC) profile of bulk amorphous alloy.
FIG. 3 shows the Co obtained by the method of the present invention55Ta10B34Si1、Co55Ta10B33Si2、Co63Ta10B25Si2、Co55Ta10B28Si7、Co55Ta13B22Si10Compressive stress strain profile of bulk amorphous alloy.
FIG. 4 shows Co in example 1 of the present invention55Ta10B34Si1Neutron transmittance map of bulk amorphous alloy.
FIG. 5 shows Co in example 2 of the present invention55Ta10B33Si2X-ray diffraction (XRD) pattern of bulk amorphous alloy.
FIG. 6 shows Co in example 2 of the present invention55Ta10B33Si2Differential Scanning Calorimeter (DSC) profile of bulk amorphous alloy.
FIG. 7 shows Co in example 3 of the present invention63Ta10B25Si2X-ray diffraction (XRD) pattern of bulk amorphous alloy.
FIG. 8 shows Co in example 3 of the present invention63Ta10B25Si2Differential Scanning Calorimeter (DSC) profile of bulk amorphous alloy.
FIG. 9 is the Co prepared by the rapid solidification of the invention of example 363Ta10B25Si2And (5) a picture of the shape of the block amorphous alloy bar.
FIG. 10 is the Co prepared by the rapid solidification of the invention of example 363Ta10B25Si2And another picture of the shape of the bulk amorphous alloy bar.
FIG. 11 shows Co in example 4 of the present invention55Ta10B28Si7X-ray diffraction (XRD) pattern of bulk amorphous alloy.
FIG. 12 shows Co in example 4 of the present invention55Ta10B28Si7Differential Scanning Calorimeter (DSC) profile of bulk amorphous alloy.
FIG. 13 shows Co in example 5 of the present invention55Ta13B22Si10X-ray diffraction (XRD) pattern of bulk amorphous alloy.
FIG. 14 shows Co in example 5 of the present invention55Ta13B22Si10Differential Scanning Calorimeter (DSC) profile of bulk amorphous alloy.
FIG. 15 is a flow chart of the present invention for preparing Co-Ta-B-Si bulk amorphous alloy material for neutron shielding.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
The invention designs the Co-Ta-B-Si amorphous alloy with the Si element partially replacing the B element, so that the novel quaternary amorphous alloy has high specific strength, high hardness and certain plastic deformation capacity.
The Co-Ta-B-Si bulk amorphous alloy used as neutron shielding consists of 5-15 at% of Ta, 17-34 at% of B, 1-10 at% of Si and the balance of Co, and the sum of the atomic percentages of all elements is 100. The preparation technology adopts a method combining vacuum high-temperature melting and rapid solidification.
Referring to FIG. 15, the preparation of the Co-Ta-B-Si amorphous alloy material for neutron shielding according to the present invention comprises the following steps:
the method comprises the following steps: batching according to the nominal components;
weighing each element according to the nominal components of the Co-Ta-B-Si bulk amorphous alloy, wherein the purity of each element is not lower than 99.0 percent, the atomic percentage content is 100 percent, and uniformly mixing the simple substance elements weighed according to the proportion to obtain a smelting raw material;
step two: performing vacuum induction melting on a prefabricated Co-Ta-B-Si alloy ingot;
putting the uniformly mixed smelting raw materials into a quartz tube, then putting the quartz tube into a vacuum smelting induction furnace, and vacuumizing the furnace to the vacuum degree of 5.0 multiplied by 10 by adopting a method of firstly low vacuum and then high vacuum－3～3.0×10－2Pa, then opening an air inlet valve and filling argon with the purity of 99.9 percent under 0.05 Mpa; under the protection of a high-purity argon atmosphere and at a high-frequency smelting temperature of 1000-2000 ℃, smelting for 3-5 min, repeatedly smelting for 2-5 times, cooling along with the furnace, and taking out to obtain a prefabricated alloy ingot;
step three: smelting by vacuum arc to prepare Co-Ta-B-Si master alloy;
scrubbing a copper mould in the vacuum arc furnace, putting the copper mould into the prefabricated Co-Ta-B-Si alloy ingot smelted in the step two, and then vacuumizing the furnace to the vacuum degree of 3.0 multiplied by 10－3～2.0×10－2Pa, introducing high-purity argon of 0.05 MPa; under the protection of argon atmosphere, arc melting is carried out for 2-5 min at 1000-3000 ℃, the alloy is turned over and repeatedly melted for 3-5 times after being cooled, and the alloy is cooled for 30min along with the furnace after being uniformly melted and taken out, so that a Co-Ta-B-Si master alloy is obtained;
step four: rapidly solidifying to prepare Co-Ta-B-Si bulk amorphous alloy;
placing the Co-Ta-B-Si master alloy crucible prepared in the third step into an induction furnace of a rapid solidification device, and vacuumizing the furnace to 5.0 multiplied by 10－3～5.0×10－2Pa, then introducing high-purity argon of 0.05 MPa;
adjusting the position between the copper mold and the crucible, wherein the injection pressure is 0.03-0.1 MPa, starting high-frequency induction heating, the heating current is 10-40A, heating to melt the master alloy for 10-60 s, then, performing injection casting in a fixed copper mold, and cooling to obtain the bulk Co-Ta-B-Si amorphous alloy.
The cooling rate is 10-103K/s。
The sample prepared by the method is characterized and tested for performance.
The sample of the invention is subjected to phase analysis by using a Japanese science D/max2500 PC type X-ray diffractometer, and the sample has continuous diffuse scattering peaks and no obvious crystallization peaks, thereby indicating that the sample is completely composed of an amorphous phase.
The Vickers microhardness of the sample measured by adopting an H450-SVDH type Vickers microhardness meter is 14.5-16.5 GPa.
The sample prepared by the invention is subjected to compression mechanical property test by adopting an SANS-CMT5504 type universal tester, the breaking strength is up to 6.5GPa, and the maximum plastic deformation can be up to 7.0%.
In the invention, the Co-Ta-B-Si amorphous alloy has good thermal stability and the glass transition temperature of 850K-970K measured by a relaxation-resistant STA-449F3 type high-temperature synchronous thermal analyzer.
Example 1 preparation of Co55Ta10B34Si1Bulk amorphous alloy
The method comprises the following steps: batching according to the nominal components;
according to Co55Ta10B34Si1(atomic percent, namely at.%) nominal composition of bulk amorphous alloy, weighing the required elementary raw materials: 5.951g of Co, 3.322g of Ta, 0.675g of B and 0.052g of Si, wherein each raw material is accurate to 0.001g, 10g of raw materials are weighed in total, the purity of each simple substance is more than 99.0 percent, and the raw materials are uniformly mixed to obtain the catalystAnd (4) smelting raw materials.
Step two: vacuum induction smelting prefabricated Co55Ta10B34Si1An alloy ingot;
putting the uniformly mixed smelting raw materials into a quartz tube, then putting the quartz tube into a vacuum smelting induction furnace, and vacuumizing the furnace to the vacuum degree of 2.0 multiplied by 10－2Pa, then opening an air inlet valve and filling argon with the purity of 99.9 percent under 0.05 Mpa; under the protection of argon atmosphere and at a high-frequency smelting temperature of 1600 ℃, smelting for 4min, repeatedly smelting for 4 times, cooling along with the furnace, and taking out to obtain a prefabricated alloy ingot.
Step three: vacuum arc melting for Co55Ta10B34A Si master alloy;
scrubbing the copper mold in the vacuum arc furnace, and putting the copper mold into the prefabricated Co smelted in the step two55Ta10B34Si alloy ingot, and then vacuumizing the furnace to the vacuum degree of 1.0 multiplied by 10－2Pa, introducing high-purity argon of 0.05 MPa; then under the protection of argon, smelting for 3min by using high-temperature electric arc, cooling, turning over and repeatedly smelting for 4 times, cooling for 30min along with the furnace after smelting is finished, and taking out to obtain Co55Ta10B34Si1A master alloy.
Step four: preparation of Co by rapid solidification55Ta10B34Si1Bulk amorphous alloy;
the Co prepared in the third step is filled in55Ta10B34Si1Putting the mother alloy crucible into an induction furnace of a rapid solidification device, and vacuumizing the furnace to 4.0 multiplied by 10－2Pa, then introducing high-purity argon of 0.05 MPa;
adjusting the position between the copper mold and the crucible, adjusting the injection pressure to 0.03MPa, starting high-frequency induction heating with the heating current of 30A, heating to melt the master alloy for 20s, then performing injection casting in a fixed copper mold, and cooling to obtain block Co55Ta10B34Si1Bulk amorphous alloys.
Step five: preparation of Co by gas atomization55Ta10B34Si1Amorphous alloy powder;
firstly, the methodMixing Co55Ta10B34Si1Putting the bulk amorphous alloy into a smelting furnace, vacuumizing the smelting furnace to ensure that the vacuum degree is less than 10Pa, heating to raise the temperature until the raw materials begin to melt, filling argon to ensure that the argon pressure reaches about 0.05MPa, and then continuing heating for 10 min; opening a nozzle high-pressure argon gas valve, and obtaining Co after the gas pressure is stabilized at about 3.5MPa55Ta10B34Si1Pouring the amorphous alloy liquid into a tundish of a vacuum induction melting gas atomization powder making device, preheating the tundish to 1300 ℃ before pouring the alloy liquid into the tundish, enabling the alloy liquid to flow out to an atomization chamber along a guide pipe at the bottom of the tundish, and carrying out atomization cooling to obtain Co55Ta10B34Si1Amorphous alloy powder; then sieving is carried out to obtain Co with the average grain diameter of 30 microns55Ta10B34Si1Amorphous alloy powder.
Step six: laser cladding Co preparation55Ta10B34Si1An amorphous alloy coating;
co with an average particle size of 30 μm was aligned using an AHL-W180III laser apparatus and a 180W Nd-YAG solid-state laser55Ta10B34Si1Carrying out laser cladding on the amorphous powder; preparation of Co55Ta10B34Si1The parameters of the amorphous alloy coating comprise loading voltage of 150V, scanning speed of 250mm/min, pulse width of 0.5ms and pulse frequency of 15 Hz. 1045 steel plates with the thickness of 3mm are used as a substrate of the laser cladding process. The surface of the substrate was polished with 800-grit SiC paper to remove the oxide film, and then cleaned with absolute ethanol under ultrasonic waves. Co55Ta10B34Si1The thickness of the powder layer is 80 μm/layer, and 4 layers are clad to reduce the dilution of the coating by the substrate.
Performance testing
Co prepared in example 155Ta10B34Si1The phase analysis of the bulk amorphous alloy bar is carried out by an X-ray diffractometer (XRD), the scanning speed is 4 degrees/min, and the result is shown in figure 1, which is a single steamed bread peak without obvious crystallization peak, and indicates that the sample is a complete amorphous phase composition.
The Differential Scanning Calorimeter (DSC) curve of the amorphous sample prepared in example 1 is shown in FIG. 2, the heating rate is 0.33K/s, and the glass transition temperature and crystallization exothermic peak are obvious, and is 955K.
Example 1 results of the compression mechanics experiment for preparing an amorphous sample are shown in fig. 3, with a strain rate of 4 × 10-4s-1The results show that Co55Ta10B34Si1The bulk amorphous fracture strength was 5.932GPa, and the plastic deformation was 1.6%.
Co prepared in example 155Ta10B34Si1The protective effect of the amorphous alloy coating is as follows: having Co of 200 μm thickness due to high neutron absorption cross section of B element55Ta10B34Si1The amorphous alloy coating shows a good shielding effect, as shown in fig. 4, i.e., the neutron transmittance is less than 50% in a wide wavelength range of 0.15nm to 0.85 nm. In particular, neutrons having a wavelength of 0.85nm have a transmittance of only 11.0%.
Example 2 preparation of Co55Ta10B33Si2Bulk amorphous alloy
The method comprises the following steps: batching according to the nominal components;
according to Co55Ta10B33Si2(atomic percent, namely at.%) nominal composition of bulk amorphous alloy, weighing the required elementary raw materials: 5.932g of Co, 3.312g of Ta, 0.653g of B and 0.103g of Si, wherein each raw material is accurate to 0.001g, 10g of raw materials are weighed in total, the purity of each simple substance is more than 99.0 percent, and the raw materials are uniformly mixed to obtain the smelting raw material.
Step two: vacuum induction smelting prefabricated Co55Ta10B33Si2An alloy ingot;
putting the uniformly mixed smelting raw materials into a quartz tube, then putting the quartz tube into a vacuum smelting induction furnace, and vacuumizing the furnace to the vacuum degree of 8.0 multiplied by 10－3Pa, then opening an air inlet valve and filling argon with the purity of 99.9 percent under 0.05 Mpa; smelting for 4min at 1500 deg.C under the protection of argon atmosphere, repeatedly smelting for 4 times, cooling with the furnace, and taking out to obtain the prefabricated productAnd (3) alloy ingots.
Step three: vacuum arc melting for Co55Ta10B33Si2A master alloy;
scrubbing the copper mold in the vacuum arc furnace, and putting the copper mold into the prefabricated Co smelted in the step two55Ta10B33Si2Alloy ingot, and then vacuumizing the furnace to 6.0 × 10－3Pa, introducing high-purity argon of 0.05 MPa; then under the protection of argon, smelting for 3min by using high-temperature electric arc, cooling, turning over and repeatedly smelting for 5 times, cooling for 30min along with the furnace after smelting is finished, and taking out to obtain Co55Ta10B33Si2A master alloy.
Step four: preparation of Co by rapid solidification55Ta10B33Si2Bulk amorphous alloy
The Co prepared in the third step is filled in55Ta10B33Si2Putting the mother alloy crucible into an induction furnace of a rapid solidification device, and vacuumizing the furnace to 2.0 multiplied by 10－2Pa, then introducing high-purity argon of 0.05 MPa;
adjusting the position between the copper mold and the crucible, adjusting the injection pressure to 0.03MPa, starting high-frequency induction heating with the heating current of 25A, heating to melt the master alloy for 25s, then performing injection casting in a fixed copper mold, and cooling to obtain block Co55Ta10B33Si2Bulk amorphous alloys.
Step five: preparation of Co by gas atomization55Ta10B33Si2Amorphous alloy powder;
firstly, Co is added55Ta10B33Si2Putting the bulk amorphous alloy into a smelting furnace, vacuumizing the smelting furnace to ensure that the vacuum degree is less than 10Pa, heating to raise the temperature until the raw materials begin to melt, filling argon to ensure that the argon pressure reaches about 0.05MPa, and then continuing heating for 10 min; opening a nozzle high-pressure argon gas valve, and obtaining Co after the gas pressure is stabilized at about 3.5MPa55Ta10B33Si2Amorphous alloy liquid is poured into a tundish of a vacuum induction melting gas atomization powder making device, and the tundish is preheated before the alloy liquid is poured into the tundishAt 1300 ℃, making the mixture flow out to an atomizing chamber along a flow guide pipe at the bottom of the tundish, and atomizing and cooling to obtain Co55Ta10B33Si2Amorphous alloy powder; then sieving is carried out to obtain Co with the average grain diameter of 30 microns55Ta10B33Si2Amorphous alloy powder.
Step six: laser cladding Co preparation55Ta10B33Si2An amorphous alloy coating;
co with an average particle size of 30 μm was aligned using an AHL-W180III laser apparatus and a 180W Nd-YAG solid-state laser55Ta10B33Si2Carrying out laser cladding on the amorphous powder; preparation of Co55Ta10B33Si2The parameters of the amorphous alloy coating comprise loading voltage of 150V, scanning speed of 250mm/min, pulse width of 0.5ms and pulse frequency of 15 Hz. 1045 steel plates with the thickness of 3mm are used as a substrate of the laser cladding process. The surface of the substrate was polished with 800-grit SiC paper to remove the oxide film, and then cleaned with absolute ethanol under ultrasonic waves. Co55Ta10B33Si2The thickness of the powder layer is 60 mu m/layer, and 6 layers are cladded to reduce the dilution of the coating by the substrate.
Performance testing
Co prepared in example 255Ta10B33Si2The X-ray diffraction pattern (XRD) of the bulk amorphous alloy bar is shown in figure 2, and is a single steamed bun peak, no obvious crystallization peak appears, and the sample is a complete amorphous phase composition.
The Differential Scanning Calorimeter (DSC) curve of the amorphous sample prepared in example 2 is shown in FIG. 5, and has distinct glass transition and crystallization exothermic peaks, and the glass transition temperature is 945K.
Example 2 the results of the compression mechanics experiment for preparing an amorphous sample are shown in fig. 6, indicating that Co55Ta10B33Si2The bulk amorphous fracture strength was 5.817GPa, and the plastic deformation was 3.3%.
Co prepared in example 255Ta10B33Si2The protective effect of the amorphous alloy coating is as follows: due to B elementHigh neutron absorption cross section of element with 200 μm thick Co55Ta10B33Si2The amorphous alloy coating shows good shielding effect, namely the neutron transmittance is less than 50% in a wide wavelength range of 0.15 nm-0.85 nm. In particular, neutrons having a wavelength of 0.85nm have a transmittance of only 15.0%.
Example 3 preparation of Co63Ta10B25Si2Bulk amorphous alloy
The method comprises the following steps: batching according to the nominal components;
according to Co63Ta10B25Si2(atomic percent, namely at.%) nominal composition of bulk amorphous alloy, weighing the required elementary raw materials: 6.348g of Co, 3.094g of Ta, 0.462g of B and 0.096g of Si, wherein each raw material is accurate to 0.001g, 10g of raw materials are weighed in total, the purity of each simple substance is more than 99.0%, and the raw materials are uniformly mixed to obtain the smelting raw material.
Step two: vacuum induction smelting prefabricated Co63Ta10B25Si2An alloy ingot;
putting the uniformly mixed smelting raw materials into a quartz tube, then putting the quartz tube into a vacuum smelting induction furnace, and vacuumizing the furnace to the vacuum degree of 1.0 multiplied by 10－2Pa, then opening an air inlet valve and filling argon with the purity of 99.9 percent under 0.05 Mpa; under the protection of argon atmosphere and at a high-frequency smelting temperature of 1800 ℃, smelting for 3min, repeatedly smelting for 4 times, cooling along with the furnace, and taking out to obtain a prefabricated alloy ingot.
Step three: vacuum arc melting for Co63Ta10B25Si2Master alloy
Scrubbing the copper mold in the vacuum arc furnace, and putting the copper mold into the prefabricated Co smelted in the step two63Ta10B25Si2Alloy ingot, and then vacuumizing the furnace to 6.0 × 10－3Pa, introducing high-purity argon of 0.05 MPa; then under the protection of argon, smelting for 3min by using high-temperature electric arc, cooling, turning over and repeatedly smelting for 5 times, cooling for 30min along with the furnace after smelting is finished, and taking out to obtain Co63Ta10B25Si2A master alloy.
Step four: preparation of Co by rapid solidification63Ta10B25Si2Bulk amorphous alloy
The Co prepared in the third step is filled in63Ta10B25Si2Putting the mother alloy crucible into an induction furnace of a rapid solidification device, and vacuumizing the furnace to 2.0 multiplied by 10－2Pa, then introducing high-purity argon of 0.05 MPa;
adjusting the position between the copper mold and the crucible, adjusting the injection pressure to 0.03MPa, starting high-frequency induction heating with the heating current of 30A, heating to melt the master alloy for 20s, then performing injection casting in a fixed copper mold, and cooling to obtain block Co63Ta10B25Si2Bulk amorphous alloys. Co obtained by the step63Ta10B25Si2The photographs of the morphology of the bulk amorphous alloy rods are shown in FIGS. 9 and 10, in which Co is present63Ta10B25Si2The diameter of the bulk amorphous alloy is 5mm and the length is 50 mm.
Step five: preparation of Co by gas atomization63Ta10B25Si2Amorphous alloy powder;
firstly, Co is added63Ta10B25Si2Putting the bulk amorphous alloy into a smelting furnace, vacuumizing the smelting furnace to ensure that the vacuum degree is less than 10Pa, heating to raise the temperature until the raw materials begin to melt, filling argon to ensure that the argon pressure reaches about 0.05MPa, and then continuing heating for 10 min; opening a nozzle high-pressure argon gas valve, and obtaining Co after the gas pressure is stabilized at about 3.5MPa63Ta10B25Si2Pouring the amorphous alloy liquid into a tundish of a vacuum induction melting gas atomization powder making device, preheating the tundish to 1300 ℃ before pouring the alloy liquid into the tundish, enabling the alloy liquid to flow out to an atomization chamber along a guide pipe at the bottom of the tundish, and carrying out atomization cooling to obtain Co63Ta10B25Si2Amorphous alloy powder; then sieving is carried out to obtain Co with the average grain diameter of 30 microns63Ta10B25Si2Amorphous alloy powder.
Step six: laser cladding Co preparation63Ta10B25Si2An amorphous alloy coating;
co with an average particle size of 30 μm was aligned using an AHL-W180III laser apparatus and a 180W Nd-YAG solid-state laser63Ta10B25Si2Carrying out laser cladding on the amorphous powder; preparation of Co63Ta10B25Si2The parameters of the amorphous alloy coating comprise loading voltage of 150V, scanning speed of 250mm/min, pulse width of 0.5ms and pulse frequency of 15 Hz. 1045 steel plates with the thickness of 3mm are used as a substrate of the laser cladding process. The surface of the substrate was polished with 800-grit SiC paper to remove the oxide film, and then cleaned with absolute ethanol under ultrasonic waves. Co63Ta10B25Si2The thickness of the powder layer is 70 μm/layer, and 4 layers are clad to reduce the dilution of the coating by the substrate.
Performance testing
Co prepared in example 363Ta10B25Si2The X-ray diffraction pattern (XRD) of the bulk amorphous alloy bar is shown in figure 3, and is a single steamed bun peak, no obvious crystallization peak appears, and the sample is a complete amorphous phase composition.
The Differential Scanning Calorimeter (DSC) curve of the amorphous sample prepared in example 3 is shown in FIG. 7, and has distinct glass transition and crystallization exothermic peaks, and the glass transition temperature is 874K.
Example 3 the results of the compression mechanics experiment for preparing the amorphous sample are shown in fig. 8, indicating that Co63Ta10B25Si2The bulk amorphous fracture strength was 5.519GPa, and the plastic deformation was 6.4%.
Co prepared in example 363Ta10B25Si2The protective effect of the amorphous alloy coating is as follows: having Co of 200 μm thickness due to high neutron absorption cross section of B element63Ta10B25Si2The amorphous alloy coating shows good shielding effect, namely the neutron transmittance is less than 58% in a wide wavelength range of 0.15 nm-0.85 nm. In particular, neutrons having a wavelength of 0.85nm have a transmittance of only 20.0%.
Example 4 preparation of Co55Ta10B28Si7Bulk amorphous alloy
The method comprises the following steps: mixing according to nominal composition
According to Co55Ta10B28Si7(atomic percent, namely at.%) nominal composition of bulk amorphous alloy, weighing the required elementary raw materials: 5.840g of Co, 3.260g of Ta, 0.545g of B and 0.354g of Si, wherein each raw material is accurate to 0.001g, 10g of raw materials are weighed in total, the purity of each simple substance is more than 99.0 percent, and the raw materials are uniformly mixed to obtain the smelting raw material.
Step two: vacuum induction smelting prefabricated Co55Ta10B28Si7An alloy ingot;
putting the uniformly mixed smelting raw materials into a quartz tube, then putting the quartz tube into a vacuum smelting induction furnace, and vacuumizing the furnace to the vacuum degree of 2.0 multiplied by 10－2Pa, then opening an air inlet valve and filling argon with the purity of 99.9 percent under 0.05 Mpa; under the protection of argon atmosphere and at a high-frequency smelting temperature of 1200 ℃, smelting for 5min, repeatedly smelting for 4 times, cooling along with the furnace, and taking out to obtain a prefabricated alloy ingot.
Step three: vacuum arc melting for Co55Ta10B28Si7A master alloy;
scrubbing the copper mold in the vacuum arc furnace, and putting the copper mold into the prefabricated Co smelted in the step two55Ta10B28Si7Alloy ingot, then vacuum pumping the furnace to the vacuum degree of 1.0X 10－2Pa, introducing high-purity argon of 0.05 MPa; then under the protection of argon, smelting for 3min by using high-temperature electric arc, cooling, turning over and repeatedly smelting for 4 times, cooling for 30min along with the furnace after smelting is finished, and taking out to obtain Co55Ta10B28Si7A master alloy.
Step four: preparation of Co by rapid solidification55Ta10B28Si7Bulk amorphous alloy;
the Co prepared in the third step is filled in55Ta10B28Si7Putting the mother alloy crucible into an induction furnace of a rapid solidification device, and vacuumizing the furnace to 5.0 multiplied by 10－2Pa, then introducing high-purity argon of 0.05 MPa;
adjusting the position between the copper mold and the crucible, adjusting the injection pressure to 0.04MPa, starting high-frequency induction heating with the heating current of 20A, heating to melt the master alloy for 30s, then performing injection casting in a fixed copper mold, and cooling to obtain a block Co55Ta10B28Si7Bulk amorphous alloys.
Step five: preparation of Co by gas atomization55Ta10B28Si7Amorphous alloy powder;
firstly, Co is added55Ta10B28Si7Putting the bulk amorphous alloy into a smelting furnace, vacuumizing the smelting furnace to ensure that the vacuum degree is less than 10Pa, heating to raise the temperature until the raw materials begin to melt, filling argon to ensure that the argon pressure reaches about 0.05MPa, and then continuing heating for 10 min; opening a nozzle high-pressure argon gas valve, and obtaining Co after the gas pressure is stabilized at about 3.5MPa55Ta10B28Si7Pouring the amorphous alloy liquid into a tundish of a vacuum induction melting gas atomization powder making device, preheating the tundish to 1300 ℃ before pouring the alloy liquid into the tundish, enabling the alloy liquid to flow out to an atomization chamber along a guide pipe at the bottom of the tundish, and carrying out atomization cooling to obtain Co55Ta10B28Si7Amorphous alloy powder; then sieving is carried out to obtain Co with the average grain diameter of 30 microns55Ta10B28Si7Amorphous alloy powder.
Step six: laser cladding Co preparation55Ta10B28Si7An amorphous alloy coating;
co with an average particle size of 30 μm was aligned using an AHL-W180III laser apparatus and a 180W Nd-YAG solid-state laser55Ta10B28Si7Carrying out laser cladding on the amorphous powder; preparation of Co55Ta10B28Si7The parameters of the amorphous alloy coating comprise loading voltage of 150V, scanning speed of 250mm/min, pulse width of 0.5ms and pulse frequency of 15 Hz. 1045 steel plates with the thickness of 3mm are used as a substrate of the laser cladding process. The surface of the substrate was polished with 800-grit SiC paper to remove the oxide film, and then cleaned with absolute ethanol under ultrasonic waves. Co55Ta10B28Si7Powder layerThe thickness is 80 μm/layer, and 4 layers are clad to reduce the dilution of the coating by the substrate.
Performance testing
Co prepared in example 455Ta10B28Si7The X-ray diffraction pattern (XRD) of the bulk amorphous alloy bar is shown in figure 4, and is a single steamed bun peak, no obvious crystallization peak appears, and the sample is completely composed of an amorphous phase.
The Differential Scanning Calorimeter (DSC) curve of the amorphous sample prepared in example 4 is shown in FIG. 11, and has distinct glass transition and crystallization exothermic peaks, and the glass transition temperature is 916K.
Example 4 the results of the compression mechanics experiment for preparing an amorphous sample are shown in fig. 12, indicating that Co55Ta10B28Si7The bulk amorphous fracture strength was 5.651GPa, and the plastic deformation was 0.3%.
Co prepared in example 455Ta10B28Si7The protective effect of the amorphous alloy coating is as follows: having Co of 200 μm thickness due to high neutron absorption cross section of B element55Ta10B28Si7The amorphous alloy coating shows good shielding effect, namely the neutron transmittance is less than 55% in a wide wavelength range of 0.15 nm-0.85 nm. In particular, neutrons having a wavelength of 0.85nm have a transmittance of only 18.0%.
Example 5 preparation of Co55Ta13B22Si10Bulk amorphous alloy
The method comprises the following steps: mixing according to nominal composition
According to Co55Ta13B22Si10(atomic percent, namely at.%) nominal composition of bulk amorphous alloy, weighing the required elementary raw materials: 5.786g of Co, 3.230g of Ta, 0.482g of B and 0.501g of Si, wherein each raw material is accurate to 0.001g, 10g of raw materials are weighed in total, the purity of each simple substance is more than 99.0 percent, and the raw materials are uniformly mixed to obtain the smelting raw material.
Step two: vacuum induction smelting prefabricated Co55Ta13B22Si10An alloy ingot;
mixing the raw materialsPutting the uniform smelting raw materials into a quartz tube, then putting the quartz tube into a vacuum smelting induction furnace, and vacuumizing the furnace to the vacuum degree of 1.0 multiplied by 10－2Pa, then opening an air inlet valve and filling argon with the purity of 99.9 percent under 0.05 Mpa; under the protection of argon atmosphere and at a high-frequency smelting temperature of 1800 ℃, smelting for 3min, repeatedly smelting for 4 times, cooling along with the furnace, and taking out to obtain a prefabricated alloy ingot.
Step three: vacuum arc melting for Co55Ta13B22Si10A master alloy;
scrubbing the copper mold in the vacuum arc furnace, and putting the copper mold into the prefabricated Co smelted in the step two55Ta13B22Si10Alloy ingot, and then vacuumizing the furnace to the vacuum degree of 8.0 multiplied by 10－3Pa, introducing high-purity argon of 0.05 MPa; then under the protection of argon, smelting for 3min by using high-temperature electric arc, cooling, turning over and repeatedly smelting for 5 times, cooling for 30min along with the furnace after smelting is finished, and taking out to obtain Co55Ta13B22Si10A master alloy.
Step four: preparation of Co by rapid solidification55Ta13B22Si10Bulk amorphous alloy;
the Co prepared in the third step is filled in55Ta13B22Si10Putting the mother alloy crucible into an induction furnace of a rapid solidification device, and vacuumizing the furnace to 3.0 multiplied by 10－2Pa, then introducing high-purity argon of 0.05 MPa;
adjusting the position between the copper mold and the crucible, adjusting the injection pressure to 0.03MPa, starting high-frequency induction heating with the heating current of 35A, heating to melt the master alloy for 18s, then performing injection casting in a fixed copper mold, and cooling to obtain a block Co55Ta13B22Si10Bulk amorphous alloys.
Step five: preparation of Co by gas atomization55Ta13B22Si10Amorphous alloy powder;
firstly, Co is added55Ta13B22Si10Putting the bulk amorphous alloy into a smelting furnace, vacuumizing the smelting furnace to ensure that the vacuum degree is less than 10Pa, heating to raise the temperature until the raw material is boiledWhen melting begins, argon is filled to ensure that the argon pressure reaches about 0.05MPa, and then heating is continued for 10 min; opening a nozzle high-pressure argon gas valve, and obtaining Co after the gas pressure is stabilized at about 3.5MPa55Ta13B22Si10Pouring the amorphous alloy liquid into a tundish of a vacuum induction melting gas atomization powder making device, preheating the tundish to 1300 ℃ before pouring the alloy liquid into the tundish, enabling the alloy liquid to flow out to an atomization chamber along a guide pipe at the bottom of the tundish, and carrying out atomization cooling to obtain Co55Ta13B22Si10Amorphous alloy powder; then sieving is carried out to obtain Co with the average grain diameter of 30 microns55Ta13B22Si10Amorphous alloy powder.
Step six: laser cladding Co preparation55Ta13B22Si10An amorphous alloy coating;
co with an average particle size of 30 μm was aligned using an AHL-W180III laser apparatus and a 180W Nd-YAG solid-state laser55Ta13B22Si10Carrying out laser cladding on the amorphous powder; preparation of Co55Ta13B22Si10The parameters of the amorphous alloy coating comprise loading voltage of 150V, scanning speed of 250mm/min, pulse width of 0.5ms and pulse frequency of 15 Hz. 1045 steel plates with the thickness of 3mm are used as a substrate of the laser cladding process. The surface of the substrate was polished with 800-grit SiC paper to remove the oxide film, and then cleaned with absolute ethanol under ultrasonic waves. Co55Ta13B22Si10The thickness of the powder layer is 100 mu m per layer, 5 layers are cladded to reduce the dilution of the coating by the substrate.
Performance testing
Co prepared in example 555Ta13B22Si10The X-ray diffraction pattern (XRD) of the bulk amorphous alloy bar is shown in figure 5, and is a single steamed bun peak, no obvious crystallization peak appears, and the sample is completely composed of an amorphous phase.
The Differential Scanning Calorimeter (DSC) curve of the amorphous sample prepared in example 5 is shown in FIG. 13, and has distinct glass transition and crystallization exothermic peaks, and the glass transition temperature is 905K.
Co prepared in example 555Ta13B22Si10The protective effect of the amorphous alloy coating is as follows: having Co of 200 μm thickness due to high neutron absorption cross section of B element55Ta13B22Si10The amorphous alloy coating shows good shielding effect, namely the neutron transmittance is less than 60% in a wide wavelength range of 0.15 nm-0.85 nm. In particular, neutrons having a wavelength of 0.85nm have a transmittance of only 23.5%.
The above illustration is only a partial example of the present invention and is not intended to limit the present invention. Various substitutions and equivalent changes in the design and preparation of the components according to the invention are intended to be included within the scope of the invention, without departing from the spirit and scope of the invention and the appended claims.
Claims (10)
1. A Co-Ta-B-Si bulk amorphous alloy material used as neutron shielding is characterized in that: the Co-Ta-B-Si bulk amorphous alloy consists of 5-15 at% of Ta, 17-34 at% of B, 1-10 at% of Si and the balance of Co.
2. The bulk amorphous alloy Co-Ta-B-Si material for neutron shielding according to claim 1, wherein: the Co-Ta-B-Si bulk amorphous alloy material has high glass forming capability, the critical diameter is 2-5 mm, and certain plastic deformation capability is increased.
3. The method for preparing Co-Ta-B-Si bulk amorphous alloy for neutron shielding according to claim 1, characterized by comprising the following steps:
the method comprises the following steps: batching according to the nominal components;
weighing each element according to the nominal components of the Co-Ta-B-Si bulk amorphous alloy, wherein the purity of each element is not lower than 99.0 percent, the atomic percentage content is 100 percent, and uniformly mixing the simple substance elements weighed according to the proportion to obtain a smelting raw material;
step two: performing vacuum induction melting on a prefabricated Co-Ta-B-Si alloy ingot;
putting the uniformly mixed smelting raw materials into a quartz tube, then putting the quartz tube into a vacuum smelting induction furnace, and vacuumizing the furnace to the vacuum degree of 5.0 multiplied by 10 by adopting a method of firstly low vacuum and then high vacuum－3～3.0×10－2Pa, then opening an air inlet valve and filling argon with the purity of 99.9 percent under 0.05 Mpa; under the protection of a high-purity argon atmosphere and at a high-frequency smelting temperature of 1000-2000 ℃, smelting for 3-5 min, repeatedly smelting for 2-5 times, cooling along with the furnace, and taking out to obtain a prefabricated alloy ingot;
step three: smelting by vacuum arc to prepare Co-Ta-B-Si master alloy;
scrubbing a copper mould in the vacuum arc furnace, putting the copper mould into the prefabricated Co-Ta-B-Si alloy ingot smelted in the step two, and then vacuumizing the furnace to the vacuum degree of 3.0 multiplied by 10－3～2.0×10－2Pa, introducing high-purity argon of 0.05 MPa; under the protection of argon atmosphere, arc melting is carried out for 2-5 min at 1000-3000 ℃, the alloy is turned over and repeatedly melted for 3-5 times after being cooled, and the alloy is cooled for 30min along with the furnace after being uniformly melted and taken out, so that a Co-Ta-B-Si master alloy is obtained;
step four: rapidly solidifying to prepare Co-Ta-B-Si bulk amorphous alloy;
placing the Co-Ta-B-Si master alloy crucible prepared in the third step into an induction furnace of a rapid solidification device, and vacuumizing the furnace to 5.0 multiplied by 10－3～5.0×10－2Pa, then introducing high-purity argon of 0.05 MPa;
adjusting the position between a copper mold and a crucible, wherein the injection pressure is 0.03-0.1 MPa, starting high-frequency induction heating, the heating current is 10-40A, heating to melt the master alloy for 10-60 s, then, performing injection casting into a fixed copper mold, and cooling to obtain a bulk Co-Ta-B-Si amorphous alloy;
step five: preparing Co-Ta-B-Si amorphous alloy powder by gas atomization;
firstly, putting the Co-Ta-B-Si bulk amorphous alloy into a smelting furnace, vacuumizing the smelting furnace to ensure that the vacuum degree is less than 10Pa, heating to raise the temperature until the raw materials begin to melt, filling argon to ensure that the argon pressure reaches about 0.05MPa, and then continuing to heat for 10 min; opening a nozzle high-pressure argon gas valve, pouring the obtained Co-Ta-B-Si amorphous alloy liquid into a tundish of a vacuum induction melting gas atomization powder making device after the gas pressure is stabilized at about 3.5MPa, preheating the tundish to 1300 ℃ before pouring the alloy liquid into the tundish, enabling the alloy liquid to flow out to an atomization chamber along a guide pipe at the bottom of the tundish, and carrying out atomization cooling to obtain Co-Ta-B-Si amorphous alloy powder; then sieving is carried out to obtain Co-Ta-B-Si amorphous alloy powder with the average grain diameter of 30 microns.
Step six: laser cladding is carried out to prepare a Co-Ta-B-Si amorphous alloy coating;
performing laser cladding on Co-Ta-B-Si amorphous powder with the average grain diameter of 30 microns by adopting AHL-W180III laser equipment and a 180W Nd-YAG solid-state laser; the parameters for preparing the Co-Ta-B-Si amorphous alloy coating are that the loading voltage is 150V, the scanning speed is 250mm/min, the pulse width is 0.5ms, and the pulse frequency is 15 Hz. 1045 steel plates with the thickness of 3mm are used as a substrate of the laser cladding process. The surface of the substrate was polished with 800-grit SiC paper to remove the oxide film, and then cleaned with absolute ethanol under ultrasonic waves. The thickness of the Co-Ta-B-Si powder layer is 80 mu m per layer, and 4 layers are cladded to reduce the dilution of the coating by the matrix.
4. The method for preparing Co-Ta-B-Si bulk amorphous alloy material according to claim 3, characterized in that: the X-ray diffraction analysis of the prepared bulk amorphous alloy shows that no obvious crystallization peak appears, and the crystallization peak is a continuous diffuse scattering peak, which indicates that the sample completely consists of an amorphous phase under the condition.
5. The method of claim 3, wherein the bulk amorphous alloy is Co-Ta-B-Si, comprising: the prepared bulk amorphous alloy comprises the following components: co55Ta10B34Si amorphous alloy, Co55Ta10B33Si2Amorphous alloy, Co59Ta10B29Si2Amorphous alloy, Co67Ta10B21Si2Amorphous formAlloy, Co55Ta10B30Si5Amorphous alloy, Co55Ta10B28Si7Amorphous alloy, Co55Ta10B25Si10Amorphous alloy, Co63Ta10B25Si2And (3) amorphous alloy.
6. The method of claim 3, wherein the bulk amorphous alloy is Co-Ta-B-Si, comprising: the Vickers microhardness of the prepared Co-Ta-B-Si bulk amorphous alloy is 14.5-16.5 GPa.
7. The method of claim 3, wherein the bulk amorphous alloy is Co-Ta-B-Si, comprising: the prepared Co-Ta-B-Si bulk amorphous alloy has the fracture strength as high as 6.5GPa and the maximum plastic deformation as high as 7.0 percent through the analysis of a compression mechanics experiment.
8. The method of claim 3, wherein the bulk amorphous alloy is Co-Ta-B-Si, comprising: the prepared Co-Ta-B-Si bulk amorphous alloy has good thermal stability and glass transition temperature of 850K-970K.
9. The method of claim 3, wherein the bulk amorphous alloy is Co-Ta-B-Si, comprising: the prepared amorphous alloy has high boron content, high hardness and certain plasticity, and can be used for neutron shielding coatings in a wide range and wear-resistant coatings of parts such as gears and the like.
10. The method of claim 3, wherein the bulk amorphous alloy is Co-Ta-B-Si, comprising: the neutron transmittance of the prepared amorphous alloy is 50-60% in a wide wavelength range of 0.15-0.85 nm, particularly the neutron with the wavelength of 0.85nm, and the transmittance is only 10.0-25%.
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