CN113913719B - Martensitic steel-based composite material and preparation method thereof - Google Patents

Martensitic steel-based composite material and preparation method thereof Download PDF

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CN113913719B
CN113913719B CN202111071340.XA CN202111071340A CN113913719B CN 113913719 B CN113913719 B CN 113913719B CN 202111071340 A CN202111071340 A CN 202111071340A CN 113913719 B CN113913719 B CN 113913719B
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alb
martensitic steel
coating
composite material
alloy
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CN113913719A (en
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周生刚
段纪豪
曹勇
张毅
岳桉豫
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Kunming University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/08—Tin or alloys based thereon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K20/00—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating
    • B23K20/02—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating by means of a press ; Diffusion bonding
    • B23K20/023—Thermo-compression bonding
    • B23K20/026—Thermo-compression bonding with diffusion of soldering material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B32B15/013—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C13/00—Alloys based on tin
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C13/00—Alloys based on tin
    • C22C13/02—Alloys based on tin with antimony or bismuth as the next major constituent
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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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
    • C23C2/36—Elongated material
    • C23C2/40—Plates; Strips
    • C23C2/405—Plates of specific length
    • 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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
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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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/129—Flame spraying
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract

The invention discloses a martensitic steel matrix composite material and a preparation method thereof, wherein the martensitic steel matrix composite material comprises a martensitic steel matrix, a Sn metal layer, a Sn-Bi-Cu alloy layer and AlB 12 The surface of the martensitic steel matrix is coated with a Sn metal layer, the Sn-Bi-Cu alloy layer is arranged on the Sn metal layer, and the AlB is arranged on the Sn-Bi-Cu alloy layer 12 A coating; the composite material has the excellent characteristics of high shielding efficiency, high strength, no toxicity and long service life, and the metallurgical combined layered composite material is manufactured by the functional gradient layered composite technology, has the functional structure integrated characteristic of gamma rays and thermal neutrons, has the advantages of small weight and high strength, has wide application range, and is particularly suitable for mobile reactors and nuclear fuel transportation facility devices.

Description

Martensitic steel-based composite material and preparation method thereof
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a martensitic steel-based composite material and a preparation method thereof.
Background
With further development of national defense scientific research, radioscience and nuclear energy technology application, the traditional single shielding material cannot meet the use requirements of modern protective equipment, and particularly the shielding material used in a nuclear fusion reactor is more severe, and has the performances of high temperature resistance, radiation resistance, corrosion resistance and the like, and meanwhile, the shielding material also needs to be high in mechanical strength and good in processing cooperativity.
At present, whether the polymer material is used as the base to be doped with Pb and B compound or the metal base/B prepared by an infiltration method, a thermal spraying coating method or a powder metallurgy method 4 The composite material of C still has the problems of poor interfacial compatibility, low material uniformity, difficult compromise of shielding efficiency, mechanics and processability, etc.
Disclosure of Invention
In order to make up the defects of the prior art, the invention provides the martensitic steel-based composite material with a sandwich structure and a preparation method thereof, so as to realize the advantage complementation of various materials, thereby further improving the performances of the materials.
The invention is realized by the following technical scheme.
A martensitic steel-base composite material comprises a martensitic steel matrix, a Sn metal layer, a Sn-Bi-Cu alloy layer, and AlB 12 The surface of the martensitic steel matrix is coated with a Sn metal layer, the Sn-Bi-Cu alloy layer is arranged on the Sn metal layer, and the AlB is arranged on the Sn-Bi-Cu alloy layer 12 And (3) coating.
The thickness of the martensitic steel matrix is 6-8 mm, the thickness of the Sn metal layer is 200-250 mu m, the thickness of the Sn-Bi-Cu alloy layer is 2-6 mm, alB 12 The thickness of the coating is 80-150 mu m.
The Sn-Bi-Cu alloy layer comprises the following components in percentage by weight: the mass percentage content of Bi is 5-15%, the mass percentage content of Cu is 1-10%, and the balance is Sn; the AlB is 12 The coating is AlB 12 And Al 2 O 3 A mixture comprising the following components in mole percent60 to 70 percent of aluminum element.
The invention also provides a preparation method of the martensitic steel-based composite material, which specifically comprises the following steps:
(1) Weighing Sn, bi and Cu according to the ratio, adding the Sn, bi and Cu into an alloy smelting furnace for smelting to obtain an Sn-Bi-Cu intermediate alloy, and rolling the Sn-Bi-Cu intermediate alloy into an Sn-Bi-Cu thin plate;
(2) Sequentially carrying out sand blasting, oil removing and cosolvent treatment on the martensitic steel plate, and then plating Sn metal on the surface of the martensitic steel plate by a hot dip plating method;
(3) Al powder and B 2 O 3 Mixing the powder uniformly, adding into a ball mill, and performing high-energy mechanical ball milling to prepare AlB 12 -Al 2 O 3 Alloy mixed powder;
(4) AlB produced 12 -Al 2 O 3 Coating the alloy mixed powder on the surface of the Sn-Bi-Cu thin plate to obtain AlB 12 A coating;
(5) Coating an Sn-plated layer of an Sn-plated martensitic steel matrix with AlB 12 Coated Sn-Bi-Cu sheet material is not coated with AlB 12 One side of the coating is compounded by a hot-press diffusion welding method to obtain martensitic steel/Sn/Sn-Bi-Cu/AlB 12 -Al 2 O 3 Layered composite materials.
The smelting temperature of the step (1) is 1100-1400 ℃ and the time is 2-4 h, and the smelting is carried out under the protection of argon atmosphere.
The step (2) of degreasing adopts 10% sodium hydroxide by mass percent for cleaning; the cosolvent treatment is cleaning with sodium benzoate.
The temperature of the hot dip plating method in the step (2) is 250-280 ℃ and the time is 1-5 min.
The ball milling parameters of the step (3) are as follows: the rotating speed is 400-600 r/min, the time is 6-12 h, and the ball-material ratio is 10:1.
Step (4) AlB 12 -Al 2 O 3 The specific operation of coating the alloy mixed powder on the surface of the Sn-Bi-Cu thin plate is as follows: alB is prepared by extracting with alcohol or acetone 12 -Al 2 O 3 The alloy mixed powder is diluted and then directly coated on the surface of the Sn-Bi-Cu thin plate; or by thermal sprayingThe oxygen-acetylene flame spraying is adopted for coating, and the main parameters of thermal spraying are as follows: the spraying distance is 150-180mm, the oxygen pressure is 0.5-0.6MPa, and the acetylene pressure is 0.10-0.12MPa.
The technological parameters of the hot-pressing diffusion welding in the step (5) are as follows: the hot pressing temperature is 200-220 ℃, the heat preservation time is 2-4 h, and the pressure is 5-15 MPa.
The composite material of the invention has a layered structure, wherein martensitic steel is used as a matrix material and AlB 12 The Sn metal layer and the Sn-Bi-Cu alloy layer are designed for realizing the combination of the reinforcement and the matrix, and the martensitic steel has high strength and AlB just according to the requirements of actual performance (strength, shielding efficiency of the medium and the like) 12 The high B content in the coating ensures that the coating has excellent neutron absorption efficiency; the matrix martensitic steel material has the characteristics of high strength, high temperature resistance, gamma ray shielding and fast neutron moderation, sn-Bi-Cu is a welding agent of the overall material, and is a carrier material for absorbing radiation, the heavy metal elements such as W, pb, bi, fe, cu and the like are recognized gamma ray absorbing materials, and the characteristic of W is more outstanding, but the matrix martensitic steel material is expensive and difficult to process, cu can be used for replacing, bi has the gamma ray absorbing efficiency same as Pb, and is nontoxic, and Bi replaces Pb, so that the matrix martensitic steel material brings more convenience and environmental protection to the processing and the use of protective equipment; alB (AlB) 12 Having a structure with B 4 C is of similar structure, all are composed of B 12 The compound with icosahedron as unit has the features of high smelting point, low specific gravity, high hardness, acid and alkali corrosion resistance, and the composite material has high content of B, high lattice content, no secondary escape of gamma ray, easy protection and AlB 12 The proportion of B (82.8%) is higher than B 4 B proportion in C (78.28%), alB 12 The boron-containing material is a preferred material for absorbing neutrons, and has a very large thermal neutron absorption cross section (3840 target), a wider absorption spectrum, strong neutron capturing power, easy acquisition of various compounds and low price. At the same time, shielding against neutrons is focused on the density, density differences and uniformity of the material, where steelThe density of the board is 7.8g/cm 3 ，AlB 12 2.39g/cm 3 The density difference between the two is larger, which is more beneficial to the moderation and absorption of neutrons.
The composite material has the excellent characteristics of high shielding efficiency, high strength, no toxicity and long service life, and the metallurgical combined layered composite material is manufactured by the functional gradient layered composite technology, has the functional structure integrated characteristic of gamma rays and thermal neutrons, has the advantages of small weight and high strength, has wide application range, and is particularly suitable for mobile reactors and nuclear fuel transportation facility devices.
Drawings
FIG. 1 is a martensitic steel/Sn/Sn-Bi-Cu/AlB 12 Schematic structural diagram of layered composite material;
FIG. 2 shows a Sn-Bi-Cu master alloy matrix and AlB 12 Coating hardness comparison chart;
FIG. 3 is a graph showing the yield strength of Sn-Bi-Cu master alloys prepared in examples 2, 4, and 5.
Detailed Description
The present invention will be described in further detail with reference to the drawings and the specific embodiments, but the scope of the present invention is not limited to the above description, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the present invention.
Example 1
A martensitic steel-based composite nuclear shielding material, as shown in figure 1, comprises a martensitic steel matrix, a Sn metal layer, a Sn-Bi-Cu alloy layer, and AlB 12 The surface of the martensitic steel matrix is hot dip plated with a Sn metal layer, a Sn-Bi-Cu alloy layer is welded on the Sn metal layer, and the Sn-Bi-Cu alloy layer is coated with AlB 12 The thickness of the martensitic steel matrix is 6mm, the thickness of the Sn metal layer is 200 mu m, the thickness of the Sn-Bi-Cu alloy layer is 4mm, and AlB 12 The thickness of the coating is 80-100 mu m.
The specific preparation process comprises the following steps:
(1) Weighing Sn, bi and Cu according to the mass ratio of 90:5:5, adding the Sn, bi and Cu into an alloy smelting furnace for smelting at 1200 ℃, preserving heat for 2 hours to obtain an Sn-Bi-Cu intermediate alloy, and rolling the Sn-Bi-Cu intermediate alloy into a thin plate with the thickness of 4mm after cooling;
(2) Sequentially carrying out sand blasting, oil removal and cosolvent treatment on the martensitic steel plate with the thickness of 6mm, wherein the oil removal adopts 10% sodium hydroxide as an oil removal agent for cleaning, the cosolvent treatment adopts sodium benzoate as an cosolvent for cleaning, and then carrying out hot dip Sn metal plating on the martensitic steel plate at 260 ℃ for 3min; the thickness of the Sn metal layer is 200 mu m;
(3) Mixing Al powder with B 2 O 3 Uniformly mixing the powder in a molar ratio of 13:6, adding the mixture into a ball mill, and performing high-energy mechanical ball milling for 6 hours to prepare AlB 12 -Al 2 O 3 Alloy mixed powder; the ball milling parameters are as follows: the rotating speed is 600r/min, and the ball-material ratio is 10:1;
(4) AlB is treated with alcohol 12 -Al 2 O 3 The alloy mixed powder is diluted and then directly coated on the surface of the Sn-Bi-Cu thin plate, and the AlB is formed after drying 12 A coating layer with the thickness of 80-100 mu m;
(5) Coating an Sn-plated layer of an Sn-plated martensitic steel matrix with AlB 12 Coated Sn-Bi-Cu sheet material is not coated with AlB 12 Compounding one side of the coating by a hot-press diffusion welding method, wherein the sintering temperature is 220 ℃, the time is 2 hours, and the applied pressure is 10MPa, so as to obtain martensitic steel/Sn/Sn-Bi-Cu/AlB 12 -Al 2 O 3 Layered composite nuclear shielding materials.
Example 2
A martensitic steel-based composite nuclear shielding material comprises a martensitic steel matrix, a Sn metal layer, a Sn-Bi-Cu alloy layer and AlB 12 A layer, wherein the surface of the martensitic steel matrix is hot dip plated with a Sn metal layer, a Sn-Bi-Cu alloy layer is welded on the Sn metal layer, and the Sn-Bi-Cu alloy layer is coated with AlB 12 The thickness of the coating layer, the martensitic steel matrix is 7mm, the thickness of the Sn metal layer is 250 mu m, the thickness of the Sn-Bi-Cu alloy layer is 6mm, and the AlB 12 The thickness of the coating is 130-150 mu m.
The specific preparation process comprises the following steps:
(1) Weighing Sn, bi and Cu according to the mass ratio of 94:5:1, adding the Sn, bi and Cu into an alloy smelting furnace for smelting at 1100 ℃, preserving heat for 4 hours to obtain an Sn-Bi-Cu intermediate alloy, and rolling the Sn-Bi-Cu intermediate alloy into a sheet shape after cooling, wherein the thickness of the sheet is 6mm;
(2) Sequentially carrying out sand blasting, oil removal and cosolvent treatment on the martensitic steel plate with the thickness of 7mm, wherein 10% sodium hydroxide by mass fraction is adopted as an oil removal agent for cleaning; the cosolvent treatment is to clean the martensitic steel plate by using sodium benzoate as cosolvent, and then hot dip plating Sn metal is carried out on the martensitic steel plate at 250 ℃ for 5min; the thickness of the Sn metal layer is 250 μm;
(3) Mixing Al powder with B 2 O 3 Uniformly mixing the powder in a molar ratio of 12:8, adding the mixture into a ball mill, and performing high-energy mechanical ball milling for 10 hours to prepare AlB 12 -Al 2 O 3 Alloy mixed powder; the ball milling parameters are as follows: the rotating speed is 500r/min, and the ball-material ratio is 10:1;
(4) AlB prepared in step (3) 12 -Al 2 O 3 Coating the alloy mixed powder on the surface of a Sn-Bi-Cu thin plate, and preparing AlB by adopting a thermal spraying method 12 The coating is thermally sprayed by oxygen-acetylene flame spraying, and the main parameters of the thermal spraying are as follows: the spraying distance is 180mm, the oxygen pressure is 0.5MPa, and the acetylene pressure is 0.12MPa; alB (AlB) 12 The thickness of the coating is 130-150 mu m;
(5) Coating an Sn-plated layer of an Sn-plated martensitic steel matrix with AlB 12 Coated Sn-Bi-Cu sheet material is not coated with AlB 12 Compounding one side of the coating by a hot-press diffusion welding method, wherein the sintering temperature is 210 ℃, the time is 4 hours, and the applied pressure is 5MPa, so as to obtain martensitic steel/Sn/Sn-Bi-Cu/AlB 12 -Al 2 O 3 Layered composite nuclear shielding materials.
The Sn-Bi-Cu master alloy prepared in this example was martensitic steel/Sn/Sn-Bi-Cu/AlB 12 -Al 2 O 3 Layered composite nuclear shielding material AlB 12 The hardness of the coating versus, for example, that shown in fig. 2, it is seen from the figure that the resulting composite has a higher hardness.
Example 3
A martensitic steel-based composite nuclear shielding material comprises a martensitic steel matrix, a Sn metal layer and Sn-Bi-Cu alloyGold layer, alB 12 A layer, wherein the surface of the martensitic steel matrix is hot dip plated with a Sn metal layer, a Sn-Bi-Cu alloy layer is welded on the Sn metal layer, and the Sn-Bi-Cu alloy layer is coated with AlB 12 The thickness of the coating layer, the martensitic steel matrix is 8mm, the thickness of the Sn metal layer is 200 mu m, the thickness of the Sn-Bi-Cu alloy layer is 2mm, and the AlB 12 The thickness of the coating is 100-120 mu m.
The specific preparation process comprises the following steps:
(1) Weighing Sn, bi and Cu according to the mass ratio of 80:10:10, adding the Sn, bi and Cu into an alloy smelting furnace for smelting at 1400 ℃, preserving heat for 3 hours to obtain an Sn-Bi-Cu intermediate alloy, and rolling the Sn-Bi-Cu intermediate alloy into a sheet shape with the thickness of 2mm after cooling;
(2) Sequentially carrying out sand blasting, oil removal and cosolvent treatment on the martensitic steel plate with the thickness of 8mm, wherein 10% sodium hydroxide by mass fraction is adopted as an oil removal agent for cleaning; the cosolvent treatment is to clean the martensitic steel plate by using sodium benzoate as cosolvent, and then hot dip plating Sn metal is carried out on the martensitic steel plate at 280 ℃ for 1min; the thickness of the Sn metal layer is 200 mu m;
(3) Mixing Al powder with B 2 O 3 Uniformly mixing the powder in a molar ratio of 14:6, adding the mixture into a ball mill, and performing high-energy mechanical ball milling for 12 hours to prepare AlB 12 -Al 2 O 3 Alloy mixed powder; the ball milling parameters are as follows: the rotating speed is 400r/min, and the ball-material ratio is 10:1;
(4) AlB produced 12 -Al 2 O 3 Coating the alloy mixed powder on the surface of a Sn-Bi-Cu thin plate, and preparing AlB by adopting a thermal spraying method 12 The coating is thermally sprayed by oxygen-acetylene flame spraying, and the main parameters of the thermal spraying are as follows: the spraying distance is 150mm, the oxygen pressure is 0.6MPa, and the acetylene pressure is 0.1MPa; alB (AlB) 12 The thickness of the coating is 100-120 mu m;
(5) Coating an Sn-plated layer of an Sn-plated martensitic steel matrix with AlB 12 Coated Sn-Bi-Cu sheet material is not coated with AlB 12 Compounding one side of the coating by a hot-press diffusion welding method, wherein the sintering temperature is 200 ℃, the time is 3 hours, and the applied pressure is 15MPa, so as to obtain martensitic steel/Sn/Sn-Bi-Cu/AlB 12 -Al 2 O 3 Layered composite nuclear screenA shielding material.
Example 4
A martensitic steel-based composite nuclear shielding material comprises a martensitic steel matrix, a Sn metal layer, a Sn-Bi-Cu alloy layer and AlB 12 A layer, wherein the surface of the martensitic steel matrix is hot dip plated with a Sn metal layer, a Sn-Bi-Cu alloy layer is welded on the Sn metal layer, and the Sn-Bi-Cu alloy layer is coated with AlB 12 The thickness of the coating layer, the martensitic steel matrix is 8mm, the thickness of the Sn metal layer is 220 mu m, the thickness of the Sn-Bi-Cu alloy layer is 4mm, and the AlB 12 The thickness of the coating is 110-140 mu m.
The specific preparation process comprises the following steps:
(1) Weighing Sn, bi and Cu according to the mass ratio of 89:10:1, adding the Sn, bi and Cu into an alloy smelting furnace for smelting at 1300 ℃, preserving heat for 2.5 hours to obtain an Sn-Bi-Cu intermediate alloy, and rolling the Sn-Bi-Cu intermediate alloy into a thin plate with the thickness of 4mm after cooling;
(2) Sequentially carrying out sand blasting, oil removal and cosolvent treatment on the martensitic steel plate with the thickness of 8mm, wherein 10% sodium hydroxide by mass fraction is adopted as an oil removal agent for cleaning; the cosolvent treatment is to clean the martensitic steel plate by using sodium benzoate as cosolvent, and then hot dip plating Sn metal is carried out on the martensitic steel plate at 280 ℃ for 2min; the thickness of the Sn metal layer is 220 mu m;
(3) Mixing Al powder with B 2 O 3 Uniformly mixing the powder in a molar ratio of 13:6, adding the mixture into a ball mill, and performing high-energy mechanical ball milling for 10 hours to prepare AlB 12 -Al 2 O 3 Alloy mixed powder; the ball milling parameters are as follows: the rotating speed is 400r/min, and the ball-material ratio is 10:1;
(4) AlB produced 12 -Al 2 O 3 Coating the alloy mixed powder on the surface of a Sn-Bi-Cu thin plate, and preparing AlB by adopting a thermal spraying method 12 The coating is thermally sprayed by oxygen-acetylene flame spraying, and the main parameters of the thermal spraying are as follows: the spraying distance is 160mm, the oxygen pressure is 0.6MPa, and the acetylene pressure is 0.11MPa; alB (AlB) 12 The thickness of the coating is 110-140 mu m;
(5) Coating an Sn-plated layer of an Sn-plated martensitic steel matrix with AlB 12 Coated Sn-Bi-Cu sheet material is not coated with AlB 12 One of the coatingsThe surfaces are compounded by a hot-pressing diffusion welding method, the sintering temperature is 200 ℃, the time is 4 hours, the applied pressure is 15MPa, and the martensitic steel/Sn/Sn-Bi-Cu/AlB is obtained 12 -Al 2 O 3 Layered composite nuclear shielding materials.
The nuclear shielding material in this embodiment is tested, wherein the absorption rate of the particles can reach 75% -85%, the nuclear shielding material has good nuclear shielding performance, and as can be seen from fig. 3, the nuclear shielding material prepared in this embodiment has excellent yield strength and guaranteed mechanical properties.
Example 5
In this example, the mass ratio of Sn, bi, and Cu in the sn—bi—cu master alloy in example 4 was basically adjusted to be: 84:15:1, martensitic steel/Sn/Sn-Bi-Cu/AlB was prepared in the same manner as in example 4 12 -Al 2 O 3 Layered composite nuclear shielding materials.
FIG. 3 is a graph showing the comparison of the yield strengths of Sn-Bi-Cu master alloys prepared in examples 2, 4 and 5, wherein the Bi content has a significant effect on the yield strengths of the Sn-Bi-Cu master alloys under the same Cu content, and the alloy yield strengths reach peaks when the Bi content reaches 10% (example 4) and slightly decrease when the Bi content continues to increase (example 5), probably because small amounts of Bi particles are added to be distributed in the alloy matrix, grain refinement and dispersion strengthening are facilitated, so that the yield strengths of the alloys are improved, but the Bi content continues to increase, supersaturated Bi is continuously aggregated, and the coarsening segregation of Bi is caused, so that the alloy yield strengths are reduced.
Table 1 shows AlB prepared in examples 1, 2 and 3 12 As can be seen from Table 1, the bonding strength of the coating to the Sn-Bi-Cu master alloy is significantly lower in example 1 than in examples 2 and 3, due to AlB being formed with alcohol or acetone or the like 12 -Al 2 O 3 Compared with thermal spraying AlB (aluminum-zinc alloy) method for directly coating alloy after diluting alloy mixed powder 12 -Al 2 O 3 The method of (2) is poor in bonding strength and the thermal spraying effect is better.
TABLE 1
The composite material takes the martensitic steel as a supporting matrix, plays roles of absorbing or attenuating part of gamma rays and slowing neutrons, and has the effects of improving the strength of the material and resisting high temperature; the Sn metal layer and the Sn-Bi-Cu alloy layer are martensitic steel and AlB 12 An intermediate medium transition metal layer between the coatings, and simultaneously Bi and Cu replace the shielding effect of Pb so as to absorb gamma rays; due to AlB 12 -Al 2 O 3 The Al and Sn, bi in the alloy have good intersolubility, and are AlB 12 AlB in coating 12 -Al 2 O 3 The high-content large-section B is an excellent element for swallowing the moderated thermal neutrons, and the prepared martensitic steel-based composite nuclear shielding material has the advantages of small weight and high strength, has a wide application range, and is particularly suitable for being applied to mobile reactors and transport facility devices of nuclear fuels.

Claims (10)

1. A martensitic steel-based composite material is characterized by comprising a martensitic steel matrix, a Sn metal layer, a Sn-Bi-Cu alloy layer and AlB 12 The surface of the martensitic steel matrix is coated with a Sn metal layer, the Sn-Bi-Cu alloy layer is arranged on the Sn metal layer, and the AlB is arranged on the Sn-Bi-Cu alloy layer 12 A coating layer of AlB 12 The coating is AlB 12 -Al 2 O 3 And coating the alloy mixed powder on the surface of the Sn-Bi-Cu alloy layer.
2. The martensitic steel-based composite material according to claim 1, wherein the martensitic steel matrix has a thickness of 6 to 8mm, the Sn metal layer has a thickness of 200 to 250 μm, the Sn-Bi-Cu alloy layer has a thickness of 2 to 6mm, and the alb 12 The thickness of the coating is 80-150 mu m.
3. The martensitic steel-based composite material according to claim 1, characterized in thatThe Sn-Bi-Cu alloy layer comprises the following components: the mass percentage content of Bi is 5% -15%, the mass percentage content of Cu is 1% -10%, and the balance is Sn; alB (AlB) 12 The coating is AlB 12 And Al 2 O 3 The molar percentage content of aluminum element in the mixture is 60% -70%.
4. The method for preparing the martensitic steel-based composite material according to claim 1, which is characterized by comprising the following steps:
(1) Weighing Sn, bi and Cu according to the ratio, mixing, smelting, cooling to obtain an Sn-Bi-Cu intermediate alloy, and rolling into an Sn-Bi-Cu sheet material;
(2) Sand blasting, degreasing and cosolvent treatment are carried out on the martensitic steel plate, and then Sn metal plating is carried out on the surface of the martensitic steel plate through a hot dip plating method;
(3) Al powder and B 2 O 3 After the powder is uniformly mixed, preparing AlB by high-energy mechanical ball milling 12 -Al 2 O 3 Alloy mixed powder;
(4) AlB is to 12 -Al 2 O 3 Coating the alloy mixed powder on the surface of the Sn-Bi-Cu thin plate to obtain AlB 12 A coating;
(5) Coating the Sn-plated layer of the Sn-plated martensitic steel matrix with an Sn-Bi-Cu thin plate material without AlB 12 One side of the coating is compounded by a hot-press diffusion welding method to obtain martensitic steel/Sn/Sn-Bi-Cu/AlB 12 -Al 2 O 3 Layered composite materials.
5. The method for preparing the martensitic steel-based composite material according to claim 4, wherein the smelting temperature in the step (1) is 1100-1400 ℃ and the time is 2-4 hours, and the smelting is performed under the protection of argon atmosphere.
6. The method for preparing the martensitic steel-based composite material according to claim 4, wherein the degreasing in the step (2) is performed by cleaning with 10% sodium hydroxide by mass fraction; the cosolvent treatment is cleaning with sodium benzoate.
7. The method for producing a martensitic steel-based composite material according to claim 4, wherein the hot dip coating method in step (2) is carried out at a temperature of 250 to 280 ℃ for a time of 1 to 5 minutes.
8. The method for preparing a martensitic steel-based composite material according to claim 4, wherein the ball milling parameters in the step (3) are as follows: the rotating speed is 400-600 r/min, the time is 6-12 h, and the ball-material ratio is 10:1.
9. The method of producing a martensitic steel-matrix composite according to claim 4, wherein step (4) AlB 12 -Al 2 O 3 The specific operation of coating the alloy mixed powder on the surface of the Sn-Bi-Cu thin plate is as follows: alB is prepared by extracting with alcohol or acetone 12 -Al 2 O 3 The alloy mixed powder is diluted and then directly coated on the surface of the Sn-Bi-Cu thin plate; or thermal spraying method, wherein the thermal spraying adopts oxygen-acetylene flame spraying, the spraying distance is 150-180mm, the oxygen pressure is 0.5-0.6MPa, and the acetylene pressure is 0.10-0.12MPa.
10. The method for preparing a martensitic steel-based composite material according to claim 4, wherein the hot-press diffusion welding process in step (5) has the process parameters of: the temperature is 200-220 ℃, the heat preservation time is 2-4 hours, and the pressure is 5-15 MPa.
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