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CN118186312B - Alloy ingot, alloy with insulating properties on the surface and preparation method thereof - Google Patents

Alloy ingot, alloy with insulating properties on the surface and preparation method thereof Download PDF

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Publication number
CN118186312B
CN118186312B CN202410607764.0A CN202410607764A CN118186312B CN 118186312 B CN118186312 B CN 118186312B CN 202410607764 A CN202410607764 A CN 202410607764A CN 118186312 B CN118186312 B CN 118186312B
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alloy
alloy ingot
aluminum
chromium
iron
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CN118186312A (en
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李道乾
马中钢
逯红果
王雷
崔彬
贾成建
范英慧
张光柱
赵国才
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SHANDONG ROITIE NEW MATERIAL SCIENCE AND TECHNOLOGY CO LTD
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SHANDONG ROITIE NEW MATERIAL SCIENCE AND TECHNOLOGY CO LTD
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/28—Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/04—Removing impurities by adding a treating agent
    • C21C7/06—Deoxidising, e.g. killing
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/04—Making ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/24—Ferrous alloys, e.g. steel alloys containing chromium with vanadium
    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • C23C8/10—Oxidising

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

本发明涉及合金技术领域，具体涉及一种合金锭、表面具有绝缘性能的合金及其制备方法。表面具有绝缘性能的合金的制备方法包括：在空气中，将合金锭于900~1300℃下，保温2~8小时，使合金锭表面氧化，在合金锭的表面形成一层氧化铝绝缘层；合金锭的化学成分质量百分比为铬10%~30%、铝2%~8%、硅0.01%~0.5%、锰0.01%~0.8%、钛0.3%~1.0%、钒≤0.5%、锆0.05%~2.0%，余量为铁和不可避免的杂质。本发明合金锭在热处理过程中能在表面形成一层致密的氧化铝陶瓷绝缘层，该绝缘层具有合适的表面硬度，因此耐磨能力好，解决了现有产品表面硬度不高的问题。

The present invention relates to the field of alloy technology, and specifically to an alloy ingot, an alloy with insulating properties on the surface, and a preparation method thereof. The preparation method of the alloy with insulating properties on the surface comprises: in air, keeping the alloy ingot at 900-1300°C for 2-8 hours, oxidizing the surface of the alloy ingot, and forming an aluminum oxide insulating layer on the surface of the alloy ingot; the chemical composition mass percentage of the alloy ingot is 10%-30% chromium, 2%-8% aluminum, 0.01%-0.5% silicon, 0.01%-0.8% manganese, 0.3%-1.0% titanium, ≤0.5% vanadium, 0.05%-2.0% zirconium, and the remainder is iron and unavoidable impurities. The alloy ingot of the present invention can form a dense aluminum oxide ceramic insulating layer on the surface during the heat treatment process, and the insulating layer has a suitable surface hardness, so it has good wear resistance, solving the problem of low surface hardness of existing products.

Description

Alloy ingot, alloy with insulating property on surface and preparation method thereof
Technical Field
The invention relates to the technical field of alloys, in particular to an alloy ingot, an alloy with insulating property on the surface and a preparation method thereof.
Background
Alloy workpieces with insulating properties on the surfaces are widely applied in the important fields of electronic industry, automobile manufacturing, aerospace and the like. The method for producing the workpiece with the insulating surface comprises the following steps: firstly smelting to obtain a master alloy ingot, forging, rolling and machining the master alloy ingot by a lathe to prepare a workpiece meeting the requirement of the dimension specification, then performing heat treatment on the workpiece to generate an oxide film on the surface of the workpiece, wherein the thickness and compactness of the oxide film on the surface of the workpiece determine the insulating property and the service life of the workpiece.
Patent CN 102409255A discloses an alloy with insulating property on the surface, which comprises the following chemical components in percentage by mass: 10% -35% of chromium, 2% -10% of aluminum, 0% -0.5% of silicon, 0.1% -1.0% of manganese, 0.2% -0.5% of cobalt, 0.1% -0.7% of vanadium, 0.1% -0.8% of tungsten, 0.2% -0.8% of niobium, 0.1% -1.2% of nickel and the balance of iron and unavoidable impurities. The alloy has a main application environment of-10-100 ℃. The alloy product has various elements and complex components. Meanwhile, the insulating layer thickness of the product after heat treatment is poor.
Patent CN 108950415A discloses an alloy with high-temperature insulation performance on the surface, which comprises the following chemical components in percentage by mass: 10% -35% of chromium, 2% -10% of aluminum, 0.01% -0.5% of silicon, 0.01% -1.0% of manganese, 0.01% -5% of zirconium, 0.2% -0.5% of cobalt, 0.01% -0.7% of vanadium, 0.3% -1.2% of titanium, 0.01% -0.8% of tungsten, 0.01% -0.8% of niobium, 0.01% -1.2% of nickel, 0.02% -3.0% of molybdenum, 0.01% -1% of tantalum, 0.01% -1% of yttrium and 0.01% -1% of hafnium, and the balance of iron and unavoidable impurities. According to the technical scheme, on the basis of CN 102409255A, metal tantalum, metal yttrium, metal zirconium, metal titanium, metal molybdenum and metal hafnium are added, and the addition of the elements is beneficial to improving the high-temperature strength of the alloy and forming mixed oxides such as yttrium oxide, so that the alloy has good insulating performance in a high-temperature environment at 580-645 ℃, and the application field of the alloy is mainly the aerospace field. However, the addition of metal elements further increases the component variety, which in turn increases the complexity of smelting; moreover, the surface hardness is not high, the wear resistance of the insulating layer is poor, and the service life of the alloy is greatly influenced.
Disclosure of Invention
Aiming at the technical problems of multiple product element types and low surface hardness of the existing alloy with the insulating property on the surface, the invention provides an alloy ingot, the alloy with the insulating property on the surface and a preparation method thereof, by adding trace alloy elements on the basis of the iron-chromium-aluminum ferrite antioxidant alloy, after the heat treatment process, aluminum in the material can form a compact aluminum oxide insulating layer on the surface of the material in the heat treatment process, and the ceramic layer has proper surface hardness and good wear resistance while having higher resistance, so that the problem of low surface hardness of the existing product is solved.
In a first aspect, the invention provides an alloy ingot, which comprises the following chemical components in percentage by mass: 10% -30% of chromium, 2% -8% of aluminum, 0.01% -0.5% of silicon, 0.01% -0.8% of manganese, 0.3% -1.0% of titanium, less than or equal to 0.5% of vanadium, 0.05% -2.0% of zirconium, and the balance of iron and unavoidable impurities, wherein an aluminum oxide insulating layer can be formed on the surface of an alloy ingot after heat treatment.
Further, the preparation method of the alloy ingot comprises the following steps:
(1) Melting: melting iron, chromium and aluminum raw materials under vacuum;
(2) Refining: after the iron, chromium and aluminum raw materials are melted, degassing and refining are carried out under the protection of argon;
(3) Deoxidizing: adding deoxidizer for deoxidizing molten steel, wherein the deoxidizer is metal silicon, metal manganese, metal aluminum and titanium;
(4) Pouring: adding vanadium and zirconium trace element alloy bags for alloying, and finally pouring under the protection of argon.
Further, in the step (1), melting is carried out under the vacuum condition of 0.1-10 Pa by utilizing electromagnetic induction current, the frequency is 2950-3050 Hz, and the power is 40-100 kilowatts.
Further, in the step (2), degassing and refining are carried out for 10-30 minutes under the protection of argon partial pressure of 5-50 kilopascals.
Further, the deoxidizing time in the step (3) is 2-5 minutes.
And (3) pouring under the protection of argon partial pressure of 5-50 kilopascals in the step (4).
Further, the heat treatment method comprises the following steps:
In the air, the alloy ingot is kept at 900-1300 ℃ for 2-8 hours, so that the surface of the alloy ingot is oxidized.
In a second aspect, the present invention provides a method for preparing an alloy having insulating properties on a surface, comprising at least the steps of:
and (3) in the air, preserving the temperature of the alloy ingot at 900-1300 ℃ for 2-8 hours, oxidizing the surface of the alloy ingot, and forming an alumina insulating layer on the surface of the alloy ingot.
In a third aspect, the invention also provides an alloy with insulating properties on the surface, which is prepared by the preparation method.
Further, the use temperature of the alloy with the surface having the insulating property is-10-200 ℃.
The invention has the beneficial effects that:
According to the invention, trace alloy elements are added on the basis of the iron-chromium-aluminum ferrite antioxidant alloy to prepare an alloy ingot, aluminum in the material can form a compact aluminum oxide ceramic insulating layer on the surface of the alloy ingot in the heat treatment process, and the thickness of aluminum oxide can reach 38-60 mu m due to the addition of the trace alloy vanadium and zirconium elements. The research finds that: the addition of the appropriate zirconium element, which forms zirconium oxide distributed at the grain boundaries, promotes oxygen aggregation to the zirconium oxide along the grain boundaries, and eventually forms aluminum oxide in the vicinity of the zirconium oxide.
The alloy with the insulating property on the surface has the service environment temperature of-10-200 ℃, and the aluminum oxide insulating layer of the alloy has higher resistance, proper surface hardness and good wear resistance under the service environment. Specifically, at room temperature and-10 ℃, the surface resistance of the alloy with the surface insulation performance can reach 2800-4200 megaohms, and the insulation resistance can reach 480-650 megaohms; at 200 ℃, the surface resistance of the alloy with the surface insulation performance can be kept at 2000-4000 megaohms, and the insulation resistance can reach 400-600 megaohms.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the description of the embodiments or the prior art will be briefly described below, and it will be obvious to those skilled in the art that other drawings can be obtained from these drawings without inventive effort.
FIG. 1 is a cross-sectional SEM photograph of an alloy of example 1 of the present invention.
FIG. 2 is a cross-sectional SEM photograph of an alloy prepared by prior art CN 102409255A.
FIG. 3 is an XRD contrast pattern of the alloy prepared in example 1 of the present invention and the alloy prepared in prior art CN 102409255A.
Detailed Description
In order to make the technical solution of the present invention better understood by those skilled in the art, the technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
Example 1
The alloy ingot comprises the following chemical components in percentage by mass: 10% of chromium, 2% of aluminum, 0.01% of silicon, 0.01% of manganese, 0.3% of titanium, 0.1% of vanadium, 0.05% of zirconium, and the balance of iron and unavoidable impurities.
The preparation method of the alloy ingot comprises the following steps:
(1) Melting: melting iron, chromium and aluminum raw materials under a vacuum condition of 5 Pa by utilizing electromagnetic induction current, wherein the frequency is 3000 Hz, and the power is 75 kilowatts;
(2) Refining: after the iron, chromium and aluminum raw materials are melted, degassing and refining are carried out for 20 minutes under the protection of argon gas 35 kilopascals partial pressure;
(3) Deoxidizing: adding deoxidizer for deoxidizing the molten steel for 3 minutes, wherein the deoxidizer is silicon, manganese and aluminum alloy;
(4) Pouring: adding vanadium-zirconium trace element alloy bags for alloying, and finally casting under the protection of argon partial pressure of 35 kilopascals.
The alloy ingot is processed into round bars with the diameter of 13mm and the length of 1m, and then is processed into cylinders with the diameter of 12mm and the length of 20mm by a numerical control machine tool. Taking a cylinder obtained by processing an alloy ingot as an alloy parent metal, insulating the cylinder in air at 1250 ℃ for 6 hours, performing heat treatment, and then cooling along with a furnace to obtain the alloy with the aluminum oxide insulating layer on the surface.
The alloy obtained by heat treatment was observed, and the results are shown in fig. 1 and 2, with the alloy prepared in the prior art CN 102409255A as a control. In fig. 1, the dark gray region from top to bottom is an alloy surface insulating layer, the light gray region is an alloy base material, and it can be seen that the alloy surface obtained by the heat treatment of example 1 has a thicker insulating layer (more than 50 μm), because zirconium element forms zirconia at grain boundaries, promotes oxygen aggregation toward zirconia along the grain boundaries, and finally forms alumina in the vicinity of the zirconia (the uppermost granular region is the formed alumina). The far right side of fig. 2 is the mosaic material used for SEM test, and then the dark gray area gradually appearing to the left represents the surface insulation layer of the alloy gradually inward from the edge after the heat treatment in the prior art CN 102409255A, and the light gray area to the left is the alloy base material, because the zirconium oxide is not present in the grain boundary in the prior art CN 102409255A, oxygen atoms cannot be spread along the grain boundary during the heat treatment, resulting in a thinner thickness (about 30 μm) of the insulation layer. The difference of the insulating layer thicknesses in fig. 1 and 2 shows that the reasonable collocation of the alloy elements and the technical means of adding trace zirconium element in the invention lead to the increase of the insulating layer thickness.
XRD testing was performed on the alloy obtained by heat treatment in example 1, and the alloy prepared by prior art CN 102409255A was used as a control, and the results are shown in FIG. 3, and the comparison shows that Fe (Cr, al) 2O4 is more and thicker in the oxide layer on the surface of the alloy.
Example 2
The alloy ingot comprises the following chemical components in percentage by mass: 20% of chromium, 5% of aluminum, 0.25% of silicon, 0.4% of manganese, 0.65% of titanium, 0.25% of vanadium, 1.0% of zirconium, and the balance of iron and unavoidable impurities.
The preparation method of the alloy ingot is the same as that of example 1.
The alloy ingot is processed into round bars with the diameter of 13mm and the length of 1m, and then is processed into cylinders with the diameter of 12mm and the length of 20mm by a numerical control machine tool. The cylinder obtained by processing the alloy ingot was used as an alloy base material, and heat treatment was performed in the same manner as in example 1.
Example 3
The alloy ingot comprises the following chemical components in percentage by mass: 30% of chromium, 8% of aluminum, 0.5% of silicon, 0.8% of manganese, 1.0% of titanium, 0.5% of vanadium, 2.0% of zirconium and the balance of iron and unavoidable impurities.
The preparation method of the alloy ingot comprises the following steps:
(1) Melting: melting iron, chromium and aluminum raw materials under a vacuum condition of 0.5 Pa by utilizing electromagnetic induction current, wherein the frequency is 3050 Hz, and the power is 100 kilowatts;
(2) Refining: after the iron, chromium and aluminum raw materials are melted, degassing and refining are carried out for 10 minutes under the protection of argon partial pressure of 5 kilopascals;
(3) Deoxidizing: adding deoxidizer for deoxidizing the molten steel for 5 minutes, wherein the deoxidizer is silicon, manganese and aluminum alloy;
(4) Pouring: adding vanadium-zirconium trace element alloy bags for alloying, and finally casting under the protection of argon partial pressure of 5 kilopascals.
The alloy ingot is processed into round bars with the diameter of 13mm and the length of 1m, and then is processed into cylinders with the diameter of 12mm and the length of 20mm by a numerical control machine tool.
Taking a cylinder obtained by processing an alloy ingot as an alloy parent metal, preserving heat for 2.5 hours in air at 1300 ℃, performing heat treatment, and then cooling along with a furnace to obtain the alloy with the aluminum oxide insulating layer on the surface.
Example 4
The alloy ingot comprises the following chemical components in percentage by mass: 18% of chromium, 6% of aluminum, 0.1% of silicon, 0.2% of manganese, 0.5% of titanium, 1.35% of zirconium, and the balance of iron and unavoidable impurities.
The preparation method of the alloy ingot comprises the following steps:
(1) Melting: melting iron, chromium and aluminum raw materials under the vacuum condition of 10 Pa by utilizing electromagnetic induction current, wherein the frequency is 2950 Hz, and the power is 40 kilowatts;
(2) Refining: after the iron, chromium and aluminum raw materials are melted, degassing and refining are carried out for 30 minutes under the protection of 50 kilopascals partial pressure of argon;
(3) Deoxidizing: adding deoxidizer for deoxidizing the molten steel for 2 minutes, wherein the deoxidizer is silicon, manganese and aluminum alloy;
(4) Pouring: adding vanadium-zirconium trace element alloy bags for alloying, and finally casting under the protection of argon partial pressure of 50 kilopascals.
The alloy ingot is processed into round bars with the diameter of 13mm and the length of 1m, and then is processed into cylinders with the diameter of 12mm and the length of 20mm by a numerical control machine tool.
Taking a cylinder obtained by processing an alloy ingot as an alloy parent metal, preserving heat for 8 hours in air at 900 ℃, performing heat treatment, and then cooling along with a furnace to obtain the alloy with the aluminum oxide insulating layer on the surface.
Comparative example 1
The alloy ingot comprises the following chemical components in percentage by mass: 20% of chromium, 5% of aluminum, 0.25% of silicon, 0.4% of manganese, 0.65% of titanium, 0.1% of vanadium, 0.04% of zirconium, and the balance of iron and unavoidable impurities.
The preparation method of the alloy ingot is the same as that of example 1.
The alloy ingot is processed into round bars with the diameter of 13mm and the length of 1m, and then is processed into cylinders with the diameter of 12mm and the length of 20mm by a numerical control machine tool. The cylinder obtained by processing the alloy ingot was used as an alloy base material, and heat treatment was performed in the same manner as in example 1.
Comparative example 2
The alloy ingot comprises the following chemical components in percentage by mass: 20% of chromium, 5% of aluminum, 0.25% of silicon, 0.4% of manganese, 0.2% of titanium, 0.05% of vanadium, 0.01% of zirconium and the balance of iron and unavoidable impurities.
The preparation method of the alloy ingot is the same as that of example 1.
The alloy ingot is processed into round bars with the diameter of 13mm and the length of 1m, and then is processed into cylinders with the diameter of 12mm and the length of 20mm by a numerical control machine tool. The cylinder obtained by processing the alloy ingot was used as an alloy base material, and heat treatment was performed in the same manner as in example 1.
Comparative example 3
The alloy ingot comprises the following chemical components in percentage by mass: 20% of chromium, 5% of aluminum, 0.25% of silicon, 0.4% of manganese, 0.65% of titanium, 0.25% of vanadium, and the balance of iron and unavoidable impurities.
The preparation method of the alloy ingot is the same as that of example 1.
The alloy ingot is processed into round bars with the diameter of 13mm and the length of 1m, and then is processed into cylinders with the diameter of 12mm and the length of 20mm by a numerical control machine tool. The cylinder obtained by processing the alloy ingot was used as an alloy base material, and heat treatment was performed in the same manner as in example 1.
Comparative example 4
The alloy ingot comprises the following chemical components in percentage by mass: 20% of chromium, 5% of aluminum, 0.25% of silicon, 0.4% of manganese, 0.65% of titanium, 0.25% of vanadium, 3.0% of zirconium, and the balance of iron and unavoidable impurities.
The preparation method of the alloy ingot is the same as that of example 1.
The alloy ingot is processed into round bars with the diameter of 13mm and the length of 1m, and then is processed into cylinders with the diameter of 12mm and the length of 20mm by a numerical control machine tool. The cylinder obtained by processing the alloy ingot was used as an alloy base material, and heat treatment was performed in the same manner as in example 1.
Comparative example 5
The alloy ingot comprises the following chemical components in percentage by mass: 20% of chromium, 5% of aluminum, 0.25% of silicon, 0.4% of manganese, 1.2% of titanium, 0.25% of vanadium, 1.0% of zirconium, and the balance of iron and unavoidable impurities.
The preparation method of the alloy ingot is the same as that of example 1.
The alloy ingot is processed into round bars with the diameter of 13mm and the length of 1m, and then is processed into cylinders with the diameter of 12mm and the length of 20mm by a numerical control machine tool. The cylinder obtained by processing the alloy ingot was used as an alloy base material, and heat treatment was performed in the same manner as in example 1.
Comparative example 6
The alloy ingot comprises the following chemical components in percentage by mass: 20% of chromium, 5% of aluminum, 0.25% of silicon, 0.4% of manganese, 0.65% of titanium, 0.7% of vanadium, 1.0% of zirconium, and the balance of iron and unavoidable impurities.
The preparation method of the alloy ingot is the same as that of example 1.
The alloy ingot is processed into round bars with the diameter of 13mm and the length of 1m, and then is processed into cylinders with the diameter of 12mm and the length of 20mm by a numerical control machine tool. The cylinder obtained by processing the alloy ingot was used as an alloy base material, and heat treatment was performed in the same manner as in example 1.
According to GB/T13303-1991 method for measuring oxidation resistance of steel, vernier calipers and outside micrometer are adopted to measure thicknesses of aluminum oxide insulating layers on the surfaces of the alloys obtained by heat treatment of examples 1-4 and comparative examples 1-6; the surface insulation properties of the alloys obtained by heat treatment of examples 1 to 4 and comparative examples 1 to 6 were tested using an insulation withstand voltage tester (500V ac) and a multimeter. The above tests were all performed at five different locations on each sample and then averaged, with the results given in table 1 below.
Surface insulation layer thickness and surface insulation Properties of the alloys of Table 1
It can be seen that the alloy ingot with specific chemical composition designed by the invention has higher resistance at room temperature, -10 ℃ and 200 ℃ after heat treatment. In comparative examples 1,2 and 3, the thickness of the surface insulating layer formed by the heat treatment was also thinned due to the gradual decrease in zirconium content of the alloy ingot, and the insulating properties of the resulting alloy were remarkably deteriorated at room temperature, -10 ℃ and 200 ℃. The alloy ingot of comparative example 4 added with excessive zirconium, which preferentially formed zirconia during the heat treatment, affected the formation of alumina, resulting in a reduction in the thickness of the oxide film (i.e., insulating layer) on the alloy surface. The presence of more titanium and vanadium in the alloy ingots of comparative example 5 and comparative example 6 also affected the formation of the surface insulating layer, and the surface insulating properties were poor.
The hardness of the surface insulating layer of the alloy obtained by heat treatment of examples 1 to 4 and comparative examples 1 to 6 was measured, and the test method was performed with reference to GB/T230.1-2018 "metal Rockwell hardness test". The above test was performed at five different locations on each sample and then averaged. The results are shown in Table 2 below.
Table 2 surface insulation Hardness (HRC) of alloy
Compared with the prior art, the alloy ingot composed of specific chemical components designed by the invention has higher hardness at room temperature, 10 ℃ below zero and 200 ℃ after heat treatment, has stronger wear resistance and has longer service life in the same environment.
Comparative example 7
The alloy ingot comprises the following chemical components in percentage by mass: 20% of chromium, 5% of aluminum, 0.25% of silicon, 0.4% of manganese, 0.65% of titanium, 0.25% of vanadium, 1.0% of zirconium, 0.3% of cobalt, 0.2% of tungsten, 0.5% of niobium, 0.8% of nickel, 0.15% of molybdenum, 0.05% of tantalum, 0.02% of yttrium, 0.1% of hafnium and the balance of iron and unavoidable impurities.
The preparation method of the alloy ingot comprises the following steps:
(1) Melting: melting raw materials of iron, chromium, aluminum, cobalt, titanium, tungsten, niobium, nickel and molybdenum under a vacuum condition of 5 Pa by utilizing electromagnetic induction current, wherein the current frequency is 3000 Hz, and the power is 75 kilowatts;
(2) Refining: after raw materials of iron, chromium, aluminum, cobalt, titanium, tungsten, niobium, nickel and molybdenum are melted, degassing and refining are carried out for 20 minutes under the protection of partial pressure of argon of 35 kilopascals;
(3) Deoxidizing: adding deoxidizer for deoxidizing the molten steel for 3 minutes, wherein the deoxidizer is silicon, manganese and aluminum alloy;
(4) Pouring: adding trace element alloy bags of zirconium, tantalum, yttrium, vanadium and hafnium for alloying, and finally casting under the protection of argon partial pressure of 35 kilopascals.
The alloy ingot is processed into round bars with the diameter of 13mm and the length of 1m, and then is processed into cylinders with the diameter of 12mm and the length of 20mm by a numerical control machine tool. The cylinder is used as alloy parent material, heat treatment is carried out in air at 1250 ℃ for 6 hours, and then the alloy with the aluminum oxide insulating layer on the surface is obtained after furnace cooling.
The surface insulation performance of the alloy obtained by heat treatment of comparative example 7 was tested by using an insulation withstand voltage tester (500V ac) and a multimeter, and the hardness of the surface insulation layer of the alloy obtained by heat treatment of comparative example 7 was examined with reference to the method specified in GB/T230.1-2018, "metal rockwell hardness test". The above tests were all performed at five different locations on each sample and then averaged. The results are shown in Table 3 below.
Table 3 comparison of properties of the alloys of example 2 and comparative example 7
As can be seen from table 3, the insulating properties of comparative example 7 are better due to the use of various alloying elements such as tungsten, nickel, niobium, cobalt, tantalum, yttrium, molybdenum and hafnium, but correspondingly, the smelting process of comparative example 7 is complicated and the manufacturing cost is higher due to the addition of various rare noble metals; the insulating property of the alloy can meet the use requirements of most application scenes. Meanwhile, the addition of various alloy elements such as tungsten, nickel, niobium, cobalt, tantalum, yttrium, molybdenum and hafnium is extremely easy to consume oxygen elements in the solidification and heat treatment process to form oxides, and is unfavorable for the formation of surface oxide films, so that the alloy of the comparative example 7 has lower hardness and poor wear resistance. The insulation layer on the alloy surface obtained by heat treatment in example 2 has higher hardness, which is related to the control of the content of zirconium metal and the adoption of proper smelting process and heat treatment process, and the measures together promote the precipitation of thicker oxide film on the alloy surface, so that the thicker the oxide film on the alloy surface is, the higher the hardness is, and the service life of the alloy is longer.
Although the present invention has been described in detail by way of preferred embodiments with reference to the accompanying drawings, the present invention is not limited thereto. Various equivalent modifications and substitutions may be made in the embodiments of the present invention by those skilled in the art without departing from the spirit and scope of the present invention, and it is intended that all such modifications and substitutions be within the scope of the present invention/be within the scope of the present invention as defined by the appended claims.

Claims (8)

1. The preparation method of the alloy with the insulating property on the surface at least comprises the following steps:
in air, preserving heat of an alloy ingot for 2-8 hours at 900-1300 ℃ to oxidize the surface of the alloy ingot, and forming an alumina insulating layer on the surface of the alloy ingot, wherein the alumina insulating layer reaches 38-60 mu m;
The alloy ingot comprises the following chemical components in percentage by mass: 18-30% of chromium, 2-6% of aluminum, 0.01-0.5% of silicon, 0.01-0.8% of manganese, 0.3-1.0% of titanium, less than or equal to 0.5% of vanadium, 0.05-1.35% of zirconium and the balance of iron and unavoidable impurities;
At room temperature and-10 ℃, the surface resistance of the alloy with the surface insulation performance reaches 2800-4200 megaohm, and the insulation resistance reaches 480-650 megaohm; at 200 ℃, the surface resistance of the alloy with the surface insulation performance is kept at 2000-4000 megaohms, and the insulation resistance reaches 400-600 megaohms.
2. The method of producing as claimed in claim 1, wherein the method of producing the alloy ingot comprises the steps of:
(1) Melting: melting iron, chromium and aluminum raw materials under vacuum;
(2) Refining: after the iron, chromium and aluminum raw materials are melted, degassing and refining are carried out under the protection of argon;
(3) Deoxidizing: adding deoxidizer for deoxidizing molten steel, wherein the deoxidizer is metal silicon, metal manganese, metal aluminum and titanium;
(4) Pouring: adding vanadium and zirconium trace element alloy bags for alloying, and finally pouring under the protection of argon.
3. The method of claim 2, wherein the melting is performed by electromagnetic induction current under a vacuum condition of 0.1 to 10 Pa, the frequency is 2950 to 3050 Hz, and the power is 40 to 100 kilowatts.
4. The method according to claim 2, wherein the step (2) is performed for 10 to 30 minutes under the protection of argon gas at a partial pressure of 5 to 50 kpa.
5. The method of claim 2, wherein the deoxidizing time in step (3) is 2 to 5 minutes.
6. The method of claim 2, wherein the step (4) is performed under argon partial pressure protection of 5-50 kpa.
7. An alloy having insulating properties on the surface thereof, which is produced by the production method according to claim 1.
8. The alloy with insulating properties on the surface according to claim 7, wherein the alloy is used at a temperature of-10 to 200 ℃.
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