CN115404413B - Iron-chromium-aluminum alloy, preparation method thereof and electric heating element - Google Patents

Iron-chromium-aluminum alloy, preparation method thereof and electric heating element Download PDF

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CN115404413B
CN115404413B CN202211008486.4A CN202211008486A CN115404413B CN 115404413 B CN115404413 B CN 115404413B CN 202211008486 A CN202211008486 A CN 202211008486A CN 115404413 B CN115404413 B CN 115404413B
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chromium
iron
aluminum alloy
oxide film
heating element
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CN115404413A (en
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胡静
陶科
王刚
李刚
杨庆松
韩鹏
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BEIJING SHOUGANG GITANE NEW MATERIALS CO LTD
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/06Ferrous alloys, e.g. steel alloys containing aluminium
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00Heat treatment of ferrous alloys
    • C21D6/002Heat treatment of ferrous alloys containing Cr
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05BELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00Ohmic-resistance heating
    • H05B3/10Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
    • H05B3/12Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material

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  • Engineering & Computer Science (AREA)
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  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
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  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Resistance Heating (AREA)

Abstract

The application relates to an iron-chromium-aluminum alloy, a preparation method thereof and an electric heating element, wherein the iron-chromium-aluminum alloy comprises an iron-chromium-aluminum alloy matrix and an oxide film, the oxide film is coated on the outer side of the iron-chromium-aluminum alloy matrix, and Al in the oxide film 2 O 3 The mass content of (2) exceeds 90%. The alumina content in the oxide film structure on the surface of the iron-chromium-aluminum alloy is high, and the corrosion resistance and oxidation resistance of the alumina in the oxide film are strongest, so that the corrosion resistance and oxidation resistance of the iron-chromium-aluminum alloy are enhanced, and the service life of the iron-chromium-aluminum alloy is prolonged.

Description

Iron-chromium-aluminum alloy, preparation method thereof and electric heating element
Technical Field
The application relates to the field of iron-chromium-aluminum alloy preparation, in particular to an iron-chromium-aluminum alloy, a preparation method thereof and an electric heating element.
Background
The metal type electrothermal material is the most widely used heating element for domestic and industrial heater at home and abroad, especially Fe-Cr-Al type alloy. The iron-chromium-aluminum alloy is widely applied in various fields by virtue of the advantages of excellent high-temperature oxidation resistance and the like.
The Fe-Cr-Al alloy can form stable, compact, protective and slow-growing oxide film to make it work normally in 1300 deg.c high temperature environment. The prior iron-chromium-aluminum alloy forms an extremely thin oxide film after continuous annealing, and Al 2 O 3 Low content of Fe 3 O 4 The content is more, so that the corrosion resistance and the antioxidation are not strong, and the service life is not long.
Disclosure of Invention
The application provides an iron-chromium-aluminum alloy, a preparation method thereof and an electric heating element, which are used for solving the technical problems of weak corrosion resistance and oxidation resistance of an oxide film on the surface of the existing iron-chromium-aluminum alloy.
In a first aspect, the present application provides an iron-chromium-aluminum alloy comprising an iron-chromium-aluminum alloy substrate, and an oxide film attached to at least a portion of the surface of the iron-chromium-aluminum alloy substrate;
the oxide film comprises the following chemical components in percentage by mass: al (Al) 2 O 3 >90%。
Further, the thickness of the oxide film is 5 to 7 μm.
Further, the chemical composition of the oxide film further includes: fe and Cr.
Further, the iron-chromium-aluminum alloy matrix comprises the following chemical components in percentage by mass: cr: 25-28%, al:4.7 to 5.1 percent.
Further, the iron-chromium-aluminum alloy matrix is an iron-chromium-aluminum alloy wire with the diameter of 3.0-8.0 mm.
In a second aspect, an embodiment of the present application provides a method for preparing the iron-chromium-aluminum alloy according to the first aspect, where the method includes:
obtaining an iron-chromium-aluminum alloy matrix;
and (3) continuously annealing the iron-chromium-aluminum alloy matrix under the set oxidizing atmosphere and the set air pressure, and cooling to obtain the iron-chromium-aluminum alloy.
Further, the chemical composition of the oxidizing atmosphere includes oxygen; the oxygen concentration is > 80%.
Further, the set air pressure is 1.5 to 2.5 atmospheres.
Further, the process parameters of the continuous annealing include: the temperature is 800-1000 ℃.
In a third aspect, embodiments of the present application provide an electrical heating element, at least some of the structural members of which comprise the iron-chromium-aluminum alloy of the first aspect, and/or at least some of the structural members of which are made of the iron-chromium-aluminum alloy of the first aspect.
Compared with the prior art, the technical scheme provided by the embodiment of the application has the following advantages:
the embodiment of the application provides an iron-chromium-aluminum alloy, which comprises an iron-chromium-aluminum alloy matrix and an oxide film, wherein the oxide film is coated on the outer side of the iron-chromium-aluminum alloy matrix, and Al in the oxide film 2 O 3 The mass content of (2) exceeds 90%. The oxide film structure on the surface of the iron-chromium-aluminum alloy has high alumina content, and the corrosion resistance and oxidation resistance of the alumina in the oxide film are strongest, so that the corrosion resistance and oxidation resistance of the oxide film on the surface of the iron-chromium-aluminum alloy are enhanced, and the technical problem that the corrosion resistance and oxidation resistance of the oxide film on the surface of the existing iron-chromium-aluminum alloy are not strong is solved.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the application and together with the description, serve to explain the principles of the application.
In order to more clearly illustrate the embodiments of the application or the technical solutions of the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, and it will be obvious to a person skilled in the art that other drawings can be obtained from these drawings without inventive effort.
Fig. 1 is a diagram of oxide film thickness of an iron-chromium-aluminum alloy according to an embodiment of the present application.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present application more apparent, the technical solutions of the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present application, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments of the present application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present application are commercially available or may be prepared by existing methods.
The metal type electrothermal material is the most widely used heating element for domestic and industrial heater at home and abroad, especially Fe-Cr-Al type alloy. The iron-chromium-aluminum alloy is widely applied in various fields by virtue of the advantages of excellent high-temperature oxidation resistance and the like.
The Fe-Cr-Al alloy can form stable, compact, protective and slow-growing oxide film to make it work normally in 1300 deg.c high temperature environment. The prior iron-chromium-aluminum alloy forms an extremely thin oxide film after continuous annealing, and Al 2 O 3 Low content of Fe 3 O 4 The content is more, so that the corrosion resistance and the antioxidation are not strong, and the service life is not long.
The technical scheme provided by the embodiment of the application aims to solve the technical problems, and the overall thought is as follows:
in a first aspect, the present application provides an iron-chromium-aluminum alloy comprising an iron-chromium-aluminum alloy substrate, and an oxide film attached to at least a portion of the surface of the iron-chromium-aluminum alloy substrate;
the oxide film comprises the following chemical components in percentage by mass: al (Al) 2 O 3 >90%。
The embodiment of the application provides an iron-chromium-aluminum alloy, which comprises an iron-chromium-aluminum alloy matrix and an oxide film, wherein the iron-chromium-aluminum alloy matrix comprises a metal alloy and an oxide filmThe oxide film is coated on the outer side of the Fe-Cr-Al alloy matrix, and Al in the oxide film 2 O 3 The mass content of (2) exceeds 90%. The oxide film structure on the surface of the iron-chromium-aluminum alloy has high alumina content, and the corrosion resistance and oxidation resistance of the alumina in the oxide film are strongest, so that the corrosion resistance and oxidation resistance of the oxide film on the surface of the iron-chromium-aluminum alloy are enhanced, and the technical problem that the corrosion resistance and oxidation resistance of the oxide film on the surface of the existing iron-chromium-aluminum alloy are not strong is solved.
As an implementation mode of the embodiment of the application, the thickness of the oxide film is 5-7 μm.
In the application, the thickness of the oxide film is 5-7 mu m, and the thicker oxide film can make the corrosion resistance and oxidation resistance of the oxide film stronger.
As an implementation manner of the embodiment of the present application, the chemical composition of the oxide film further includes: fe and Cr.
In the application, metallic elements Fe and Cr in the Fe-Cr-Al alloy do not gather towards the surface, and oxygen atoms are directly oxidized with metallic Al on the surface of the Fe-Cr-Al alloy to generate compact Al 2 O 3 Is formed on the substrate.
As an implementation mode of the embodiment of the application, the chemical components of the iron-chromium-aluminum alloy matrix in mass fraction include: cr: 25-28%, al:4.7 to 5.1 percent.
In the application, the iron-chromium-aluminum alloy matrix comprises a small amount of rare earth elements (La, ce, Y and the like) besides Fe, cr and Al elements. The contents of Cr and Al are controlled, so that the composition of the surface oxide film can be controlled.
As an implementation mode of the embodiment of the application, the iron-chromium-aluminum alloy matrix is an iron-chromium-aluminum alloy wire with the diameter of 3.0-8.0 mm.
In a second aspect, an embodiment of the present application provides a method for preparing the iron-chromium-aluminum alloy according to the first aspect, where the method includes:
obtaining an iron-chromium-aluminum alloy matrix;
and (3) continuously annealing the iron-chromium-aluminum alloy matrix under the set oxidizing atmosphere and the set air pressure, and cooling to obtain the iron-chromium-aluminum alloy.
In the application, the iron-chromium-aluminum alloy matrix is iron-chromium-aluminum alloy obtained according to the prior art scheme.
In the application, the oxidation speed is improved by controlling the oxidizing atmosphere and the air pressure, so that metallic elements Fe and Cr in the iron-chromium-aluminum alloy are not more aggregated to the surface, and oxygen atoms are directly oxidized with metallic element Al on the surface of the iron-chromium-aluminum alloy. Since Al has the fastest migration speed, al is preferentially oxidized under the condition of sufficient oxygen, and surface Al metal atoms are combined with oxygen to generate compact Al 2 O 3 And (3) an oxide film. Surface-formed large amounts of Al 2 O 3 The oxide film suppresses the formation of the oxide film of other elements. Al has a partial polymerization energy of-1.599, cr has a partial polymerization energy of-0.648, iron has the highest partial polymerization energy, and metal atoms tend to be partially polymerized to the surface as the partial polymerization energy is lower, so that the partial polymerization force of Al is strongest, and the partial polymerization speed of Al to the surface is higher than that of Cr and Fe, so that a large amount of Al is formed on the surface 2 O 3 And (3) an oxide film.
As an implementation of the embodiment of the present application, the chemical composition of the oxidizing atmosphere includes oxygen; the oxygen concentration is > 80%.
In the application, the oxidizing atmosphere is oxygen, which can improve the oxygen content, ensure the oxygen is sufficient, further ensure the preferential oxidation of Al and form compact Al 2 O 3 And (3) an oxide film.
As an embodiment of the present application, the set air pressure is 1.5 to 2.5 atmospheres.
In the application, the oxidizing gas is sent into the continuous annealing furnace through the blowing device, the pressure of the oxidizing gas is controlled to be 1.5-2.5 atmospheres, the flow speed of the oxidizing gas can be accelerated, the oxidation speed is further accelerated, and an oxide film is accelerated to be formed. Meanwhile, aluminum element is preferentially oxidized, so that aluminum oxide is preferentially formed, the compactness of the aluminum oxide is good, and the corrosion resistance is good. However, when the air pressure and the air flow rate are too high, the air flow rate is too high, the surface temperature of the iron-chromium-aluminum alloy cannot be reached, and the oxidation speed can be reduced.
As an implementation manner of the embodiment of the present application, the process parameters of the continuous annealing include: the temperature is 800-1000 ℃.
In the application, the annealing temperature is directly related to the mechanical properties of the iron-chromium-aluminum alloy, the temperature is high or low, the mechanical properties are reduced, and the optimal mechanical properties can be ensured by controlling the temperature. The annealing time is conventional and is not the focus of the present application.
In a third aspect, embodiments of the present application provide an electrical heating element, at least some of the structural members of which comprise the iron-chromium-aluminum alloy of the first aspect, and/or at least some of the structural members of which are made of the iron-chromium-aluminum alloy of the first aspect.
In the application, the content of alumina in the oxide film on the surface of the iron-chromium-aluminum alloy is higher, so that the iron-chromium-aluminum alloy has the characteristics of strong corrosion resistance and high temperature resistance, is favorable for prolonging the service life of the alloy, can prolong the service life of the alloy by about 50 percent, and can be used as a material for producing electric heating elements.
In the application, the iron-chromium-aluminum alloy can be used as a high-temperature insulating film, a resistance wire material and the like of the electric heating element.
The application will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. The experimental procedures, which are not specified in the following examples, are generally determined according to national standards. If the corresponding national standard does not exist, the method is carried out according to the general international standard, the conventional condition or the condition recommended by the manufacturer.
Example 1
An iron-chromium-aluminum alloy and a preparation method thereof are characterized by comprising the following steps:
(1) Raw material selection: an iron-chromium-aluminum alloy wire with a diameter of 5mm, the chemical composition of which is shown in Table 1 (balance Fe and unavoidable impurities);
(2) Preparing an oxide film: and continuously annealing the iron-chromium-aluminum alloy wire at 900 ℃ under the oxygen atmosphere with the blowing pressure of 2 atmospheres, and cooling to obtain the iron-chromium-aluminum alloy.
Example 2
An iron-chromium-aluminum alloy and a preparation method thereof are characterized by comprising the following steps:
(1) Raw material selection: an iron-chromium-aluminum alloy wire with a diameter of 3.0mm, the chemical composition of which is shown in Table 1 (balance Fe and unavoidable impurities);
(2) Preparing an oxide film: and continuously annealing the iron-chromium-aluminum alloy wire at 800 ℃ under the oxygen atmosphere with the blowing pressure of 1.5 atmospheres, and cooling to obtain the iron-chromium-aluminum alloy.
Example 3
An iron-chromium-aluminum alloy and a preparation method thereof are characterized by comprising the following steps:
(1) Raw material selection: an iron-chromium-aluminum alloy wire with a diameter of 8.0mm, the chemical composition of which is shown in Table 1 (balance Fe and unavoidable impurities);
(2) Preparing an oxide film: and continuously annealing the iron-chromium-aluminum alloy wire at 1000 ℃ under the oxygen atmosphere with the blowing pressure of 2.5 atmospheres, and cooling to obtain the iron-chromium-aluminum alloy.
Example 4
An iron-chromium-aluminum alloy and a preparation method thereof are characterized by comprising the following steps:
(1) Raw material selection: an iron-chromium-aluminum alloy wire with a diameter of 6mm, the chemical composition of which is shown in Table 1 (the balance being Fe and unavoidable impurities);
(2) Preparing an oxide film: and (3) continuously annealing the iron-chromium-aluminum alloy wire at 950 ℃ under the oxygen atmosphere with the blowing pressure of 1.8 atmospheres, and cooling to obtain the iron-chromium-aluminum alloy.
Example 5
An iron-chromium-aluminum alloy and a preparation method thereof are characterized by comprising the following steps:
(1) Raw material selection: an iron-chromium-aluminum alloy wire with a diameter of 4mm, the chemical composition of which is shown in Table 1 (balance Fe and unavoidable impurities);
(2) Preparing an oxide film: and continuously annealing the iron-chromium-aluminum alloy wire at 850 ℃ under the oxygen atmosphere with the blowing pressure of 2.2 atmospheres, and cooling to obtain the iron-chromium-aluminum alloy.
Comparative example 1
The oxygen atmosphere in example 1 was changed to air atmosphere, the air pressure was changed to 1 atmosphere, the continuous annealing temperature was changed to 750 ℃, and the rest was the same as in example 1.
The iron-chromium-aluminum alloys prepared in examples and comparative examples were subjected to oxide film composition detection using an X-ray diffractometer as shown in table 2, and oxide film thickness detection was performed as shown in table 3.
TABLE 1 chemical composition of iron-chromium-aluminum alloy wire (in mass percent)
Numbering device Cr Al Ti Ni Mn Si C
Example 1 27.17% 4.9% 0.135% 0.168% 0.198% 0.47% 0.109%
Example 2 25.2% 4.7% 0.135% 0.168% 0.198% 0.47% 0.109%
Example 3 28% 5.1% 0.135% 0.168% 0.198% 0.47% 0.109%
Example 4 26.4% 4.8% 0.135% 0.168% 0.198% 0.47% 0.109%
Example 5 27.5% 5.0% 0.135% 0.168% 0.198% 0.47% 0.109%
Comparative example 1 27.17% 4.9% 0.135% 0.168% 0.198% 0.47% 0.109%
TABLE 2 composition of oxide film on iron-chromium-aluminum alloy surface
Numbering device Composition of the components Proportion of Composition of the components Proportion of Composition of the components Proportion of
Example 1 Fe 4.45% Al 2 O 3 95.49% Cr 0.5%
Example 2 Fe 9.25% Al 2 O 3 90.28% Cr 0.47%
Example 3 Fe 3.36% Al 2 O 3 96.12% Cr 0.52%
Example 4 Fe 5.77% Al 2 O 3 93.75% Cr 0.48%
Example 5 Fe 3.6% Al 2 O 3 95.89% Cr 0.51%
Comparative example 1 Fe 77.65% Al 2 O 3 4.89% Fe 3 O 4 17.46%
TABLE 3 thickness of oxide film on iron-chromium-aluminum alloy surface
Numbering device Oxide film thickness (μm)
Example 1 7
Example 2 6.1
Example 3 6.7
Example 4 5.4
Example 5 5.7
Comparative example 1 3.4
According to the oxidation principle of piling-Bedworth, oxides with a volume ratio of less than 1 do not cover the metal enough and do not have a protective effect. When the ratio is far greater than 1, the internal stress of the oxide film is increased, the adhesion force with the matrix is poor, cracking and peeling can occur, and the oxide film has no good oxidation resistance. Therefore, the optimal ratio is close to 1.Al has an oxidation volume ratio of 1.28, cr has an oxidation volume ratio of 1.99, and Fe has an oxidation volume ratio of 1.77, thus Al 2 O 3 The formed continuous compact oxide protective film can prevent oxygen from diffusing into the matrix, prevent the alloy from being oxidized continuously and greatly improve the oxidation resistance. Therefore, al in the oxide film on the surface of the iron-chromium-aluminum alloy provided by the embodiment of the application 2 O 3 The content is higher than that of the comparative example, and the corrosion resistance is better than that of the comparative example.
Various embodiments of the application may exist in a range of forms; it should be understood that the description in a range format is merely for convenience and brevity and should not be construed as a rigid limitation on the scope of the application; it is therefore to be understood that the range description has specifically disclosed all possible sub-ranges and individual values within that range. For example, it should be considered that a description of a range from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2, 3, 4, 5, and 6, wherever applicable. In addition, whenever a numerical range is referred to herein, it is meant to include any reference number (fractional or integer) within the indicated range.
In the present application, unless otherwise specified, terms such as "upper" and "lower" are used specifically to refer to the orientation of the drawing in the figures. In addition, in the description of the present specification, the terms "include", "comprising" and the like mean "including but not limited to". Relational terms such as "first" and "second", and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Herein, "and/or" describing an association relationship of an association object means that there may be three relationships, for example, a and/or B, may mean: a alone, a and B together, and B alone. Wherein A, B may be singular or plural. Herein, "at least one" means one or more, and "a plurality" means two or more. "at least one", "at least one" or the like refer to any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (individual) of a, b, or c," or "at least one (individual) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, c may be single or multiple, respectively.
The foregoing is only a specific embodiment of the application to enable those skilled in the art to understand or practice the application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (5)

1. The iron-chromium-aluminum alloy is characterized by comprising an iron-chromium-aluminum alloy matrix and an oxide film attached to at least part of the surface of the iron-chromium-aluminum alloy matrix, wherein the thickness of the oxide film is 5-7 mu m;
the oxide film comprises the following chemical components in percentage by mass: al (Al) 2 O 3 >90%;
The iron-chromium-aluminum alloy matrix comprises the following chemical components in percentage by mass: cr: 25-28%, al:4.7 to 5.1 percent;
the preparation method of the iron-chromium-aluminum alloy comprises the following steps:
obtaining an iron-chromium-aluminum alloy matrix;
continuously annealing the iron-chromium-aluminum alloy matrix under a set oxidizing atmosphere and a set air pressure, and cooling to obtain the iron-chromium-aluminum alloy, wherein the chemical components of the oxidizing atmosphere comprise oxygen; the oxygen concentration is more than 80 percent, and the set air pressure is 1.5-2.5 atmospheres.
2. The iron-chromium-aluminum alloy according to claim 1, wherein the oxide film further comprises the chemical composition: fe and Cr.
3. The iron-chromium-aluminum alloy according to claim 1, wherein the iron-chromium-aluminum alloy matrix is an iron-chromium-aluminum alloy wire with a diameter of 3.0-8.0 mm.
4. The iron-chromium-aluminum alloy according to claim 1, wherein the process parameters of the continuous annealing include: the temperature is 800-1000 ℃.
5. An electric heating element, characterized in that at least part of the structural members of the electric heating element comprises an iron-chromium-aluminum alloy according to any one of claims 1-4 and/or that at least part of the structural members of the electric heating element is made of an iron-chromium-aluminum alloy according to any one of claims 1-4.
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