CN113215438A - Micro-alloyed copper-based wire for electric heating of floor and preparation method thereof - Google Patents
Micro-alloyed copper-based wire for electric heating of floor and preparation method thereof Download PDFInfo
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- CN113215438A CN113215438A CN202110449060.1A CN202110449060A CN113215438A CN 113215438 A CN113215438 A CN 113215438A CN 202110449060 A CN202110449060 A CN 202110449060A CN 113215438 A CN113215438 A CN 113215438A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/02—Alloys based on copper with tin as the next major constituent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/001—Continuous casting of metals, i.e. casting in indefinite lengths of specific alloys
- B22D11/004—Copper alloys
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/005—Continuous casting of metals, i.e. casting in indefinite lengths of wire
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- 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
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
- E04F15/00—Flooring
- E04F15/02—Flooring or floor layers composed of a number of similar elements
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- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
- E04F2290/00—Specially adapted covering, lining or flooring elements not otherwise provided for
- E04F2290/02—Specially adapted covering, lining or flooring elements not otherwise provided for for accommodating service installations or utility lines, e.g. heating conduits, electrical lines, lighting devices or service outlets
- E04F2290/023—Specially adapted covering, lining or flooring elements not otherwise provided for for accommodating service installations or utility lines, e.g. heating conduits, electrical lines, lighting devices or service outlets for heating
Abstract
The invention discloses a microalloyed copper-based wire for electric heating of a floor and a preparation method thereof, wherein the microalloyed copper-based wire comprises the following components in percentage by mass: 0.2-0.4% of Ni, 0.4-0.5% of Sn, 0.16-0.18% of Mn, 0.05-0.10% of Zr, and the balance of Cu and other impurity elements. Putting electrolytic copper into a heating furnace to be melted to obtain copper liquid, and when the temperature of the copper liquid is raised to a preset temperature, sequentially adding Ni, Sn, Mn and Zr into the copper liquid to be melted to obtain molten copper alloy liquid; after the temperature of the molten copper alloy liquid rises to a preset temperature, keeping the constant temperature; and then inserting the graphite crystallizer into the molten copper alloy liquid for continuous casting by an up-drawing method, and then carrying out drawing forming and aging annealing to obtain the microalloyed copper-based wire. The resistivity and the meter resistance can be accurately controlled.
Description
Technical Field
The invention belongs to the technical field of heating wires, relates to a microalloyed copper-based wire for electric heating of floors, and further relates to a preparation method of the microalloyed copper-based wire.
Background
With the development of economy and the improvement of life quality, winter heating is more and more. Indoor heating may have been used more in the north in the past, but more and more southern people have started to use cheer in recent years. Besides the common radiator, the geothermal heating of hot water pipeline is laid under the floor. The radiator is the most conventional heating mode, but the radiator takes up space, and has the hidden danger of leaking moreover, and heat exchange efficiency is low. The geothermal heating is also a common method, the conventional method is to lay a hot water pipeline under the floor tiles, the hot water pipeline is laid at a certain distance and is in a grid mode, the heating mode can cause uneven heating of the floor tiles and overhigh local temperature, and in addition, a water pipe is buried under the floor tiles or the wood floor, so that the risk of water leakage is caused, and great difficulty is brought to maintenance. In addition, the heating by adopting the heating radiator or the geothermal heating also needs a special heating power company to provide a heat source or a special heat exchange station to provide a heating heat source.
In recent years, on the basis of geothermal heating, the electric heating floor becomes a new fashion, not only saves indoor space, but also avoids heating devices such as heating radiators and the like, improves heating efficiency and greatly reduces laying cost. The conventional electric heating floor is a product which is formed by combining a carbon-based electric heating film as a heating body with a novel PVC floor and a reflecting film. The carbon-based electrothermal film is a main body of a low-temperature radiation heating mode, and is a novel heating mode which uses electric power as an energy source and is carried out through infrared radiation. The electrothermal film has more than 40 years of application history in the United states, and the application is very wide. The electric heating floor has the advantages that (1) the electric heating floor is healthy and environment-friendly, and the electric heating film radiates heat like the sun. People feel comfortable, indoor dryness and heat, skin dehydration and mouth and tongue dryness cannot be caused, air pollution cannot be caused, and the comfortable feeling of the human body is met. (2) The electric heating floor is efficient and economical, one-time investment of the electric heating floor is lower than that of other heating equipment, the surface of the heating body is rapidly heated within several seconds of power-on, the ground is thermally radiated at constant temperature, and the running cost is low. (3) The installation is convenient, long service life, and humanized, the specialized design becomes the most simple and convenient product of installation, debugging on the existing market for electric heat membrane ground heating. And long service life and simple maintenance. (4) Can be disassembled for secondary use, and is convenient to be disassembled for reuse because concrete is not poured. If the movable furniture is moved, the movable furniture can be disassembled for repeated use, and basically cannot be damaged due to disassembly.
People have taken a long way on floor heating, and floor heating floors, self-heating floors and the like are popular floor heating modes at present. The electric heating wood floor is a new technology in recent years, namely, a layer of electric heating plate is placed below the electric heating wood floor, and the wood floor is laid above the electric heating wood floor. The wood floor laid on the wood floor is usually thinner than common household wood floors, so that heat conduction is convenient, and common wood floors can be laid, but heat conduction is slow. In addition, the heating wire with a certain low resistance value is embedded in the high-end wood floor or the composite floor, so that the heating effect can be achieved, and meanwhile, potential safety hazards caused by local overheating or short circuit of the heating wire can be avoided. Different floors can be compositely manufactured, such as electric heating floors, electric heating wood floors, electric floor heating, multi-layer floors, bamboo floors and laminate floors.
However, as a low-temperature precision heating component, the resistance value and the meter resistance of the heating wire must be precisely controlled to meet the requirements of safety and high efficiency, which is the key problem in the first place. Therefore, cheap low-resistance wires are expected to be used as the core of floor heating in the market to meet the actual production requirements of safe, rapid and efficient heating, and special electric heating copper alloy wires which are low in cost, simple in preparation process and microalloyed are urgently needed.
Disclosure of Invention
The invention aims to provide a microalloyed copper-based wire for electric heating of a floor, which solves the problems that the resistivity meter and the resistance of a resistance wire for the floor can not be accurately controlled in the prior art.
The invention adopts the technical scheme that a microalloyed copper-based wire for floor electric heating comprises the following components in percentage by mass:
0.2 to 0.4 percent of Ni, 0.4 to 0.5 percent of Sn, 0.16 to 0.18 percent of Mn, 0.05 to 0.10 percent of Zr, the balance of Cu and other impurity elements, and the content of other impurity elements is less than 0.03 percent.
The invention is also characterized in that:
the diameter of the microalloyed copper-based wire is 0.28-0.32mm, the resistivity is 0.1-0.15 omega.m, and the meter resistance is 1.5-1.6 omega.
Another object of the present invention is to provide a method for preparing a microalloyed copper-based wire for electric heating of a floor.
The invention adopts another technical scheme that the preparation method of the microalloyed copper-based wire for floor electric heating comprises the following steps:
step 1, putting electrolytic copper into a heating furnace to be melted to obtain copper liquid, when the temperature of the copper liquid is raised to a preset temperature, sequentially adding 0.2-0.4% of Ni, 0.4-0.5% of Sn, 0.16-0.18% of Mn and 0.05-0.10% of Zr into the copper liquid, and continuously heating and melting to obtain molten copper alloy liquid; after the temperature of the molten copper alloy liquid rises to a preset temperature, keeping the constant temperature; then inserting a graphite crystallizer into the molten copper alloy liquid for continuous casting by an upward drawing method to obtain a wire;
and 2, carrying out drawing forming and aging annealing on the wire to obtain the microalloyed copper-based wire.
The preset temperature in the step 1 is 1220-1250 ℃.
The specific process of the step 2 is as follows: and (3) carrying out multi-pass drawing on the wire, wherein the pass deformation in the drawing process is 5-10%, and the wire after each pass of drawing enters a tube furnace to carry out intermediate aging annealing in the hydrogen protective atmosphere at 800-900 ℃, wherein the intermediate aging annealing time is 1-3 min.
The diameter of the wire rod is phi 8-10 mm.
The Ni, Sn, Mn and Zr elements are respectively added in the form of intermediate alloys of Cu-50% Ni, Cu-30% Sn, Cu-30% Mn and Cu-30% Zr.
The invention has the beneficial effects that:
the microalloyed copper-based wire for electric heating of the floor, disclosed by the invention, has the advantages of low microalloying degree, low price of used alloy elements, low production cost, controllable process, environmental friendliness and high comprehensive mechanical property of the produced alloy, the diameter of the wire can be accurately controlled through a drawing process, and the resistivity and the meter resistance can be accurately controlled; the microalloyed copper-based wire is suitable for heating various floors, has high thermal efficiency and high safety and reliability, is not only suitable for household floors, but also can be applied to other fields. According to the preparation method of the microalloyed copper-based wire for electric heating of the floor, disclosed by the invention, the microalloyed wire is subjected to large plastic deformation by multi-pass drawing, the strength of the microalloyed wire is high, and the resistivity can be accurately controlled according to production requirements; can obtain the superfine diameter wire with uniform tissue, accurate resistance value, high toughness and easy moulding processing.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
A microalloyed copper-based wire for electric heating of a floor comprises the following components in percentage by mass:
0.2 to 0.4 percent of Ni, 0.4 to 0.5 percent of Sn, 0.16 to 0.18 percent of Mn, 0.05 to 0.10 percent of Zr, the balance of Cu and other impurity elements, and the content of other impurity elements is less than 0.03 percent.
The diameter of the microalloyed copper-based wire is 0.28-0.32mm, the resistivity is 0.1-0.15 omega.m, and the meter resistance is 1.5-1.6 omega.
A preparation method of a microalloyed copper-based wire for electric heating of a floor comprises the following steps:
step 1, firstly placing electrolytic copper with the mass purity of not less than 99.9% in a graphite crucible, then placing the crucible in a vacuum argon protection power frequency electric furnace for melting to obtain a copper liquid, when the temperature of the copper liquid rises to 1180-1200 ℃, sequentially adding intermediate alloys of 0.2-0.4% of Ni, 0.4-0.5% of Sn, 0.16-0.18% of Mn and 0.05-0.10% of Zr according to the mass percentage, namely Cu-50% of Ni, Cu-30% of Sn, Cu-30% of Mn and Cu-30% of Zr into the copper liquid, continuously heating and melting to obtain a molten copper alloy liquid, and melting and stirring by utilizing the electromagnetic induction stirring function of the electric furnace; when the temperature of the molten copper alloy liquid rises to 1220-1250 ℃, reducing the power of the power frequency electric furnace to keep the temperature of the copper alloy liquid at 1220-1250 ℃; then inserting the water-cooled graphite crystallizer into molten copper alloy liquid for continuous casting by an up-drawing method to obtain a wire rod with the diameter of phi 8-10 mm;
and 2, carrying out multi-pass drawing on the wire at room temperature, wherein the pass deformation in the drawing process is 5-10%, and after each pass of drawing, feeding the wire into a tube furnace to carry out intermediate aging annealing in the hydrogen protective atmosphere at the temperature of 800-900 ℃, wherein the intermediate aging annealing time is 1-3min, so as to obtain the CuNiSnMnZr microalloyed copper-based wire with the diameter of 0.28-0.32mm and the tensile strength of 280-400 MPa.
Through the mode, the microalloyed copper-based wire material for electric heating of the floor, disclosed by the invention, is prepared by adding trace amounts of Ni, Sn, Mn and Zr into copper for microalloying and adjusting the components of the copper alloy so as to improve the mechanical property of the copper alloy and ensure the resistivity, the meter resistance and the plastic processability of the copper alloy; the invention relates to a preparation method of a microalloyed copper-based wire material for electric heating of a floor, which is characterized in that a vacuum argon protection and electromagnetic stirring fusion casting process can ensure that the components of a melt are uniform, so that trace elements are uniformly distributed on a copper matrix or are dissolved in the matrix, and the improvement of the uniformity of a structure is facilitated to improve the processing performance of an alloy; the continuous casting process by the up-drawing method can ensure that the crystal grains of the copper matrix are fine and uniform because of cooling and solidification in the water-cooled graphite crystallizer, and a great amount of trace alloy elements are dissolved in the copper matrix in a solid solution manner, thereby playing the roles of solid solution strengthening effect and electric conductivity adjustment; in the continuous casting process, the inlet of the crystallizer is always embedded below the liquid level of the copper alloy, and the melting crucible is equivalent to a large riser, so that the feeding effect is good although the diameter of the wire is smaller, and the defects of shrinkage holes, shrinkage porosity and the like do not exist in the structure; meanwhile, the wire rod obtained is compact in structure and fine in crystal grains due to cooling and solidification in the water-cooled graphite crystallizer, and precipitation of trace alloying elements and precipitation of a large amount of intermetallic compounds are avoided. Therefore, precise control of resistivity and resistance per meter is achieved by utilizing precise control of microalloying, solid solution alloys and wire diameters. Meanwhile, the capability of improving the comprehensive mechanical property of the copper alloy is achieved by utilizing the microalloying effect. In addition, because the content of the added alloy elements is very low, the influence on the large plastic deformation processing capacity of the copper alloy is small, and the subsequent drawing processing forming can be ensured.
Example 1
Step 1, firstly placing electrolytic copper with the mass purity of not less than 99.9% in a graphite crucible, then placing the crucible in a vacuum argon protection power frequency electric furnace for melting to obtain copper liquid, adding intermediate alloys of Cu-50% of Ni, Cu-30% of Sn, Cu-30% of Mn and Cu-30% of Zr into the copper liquid according to the mass percentages of 0.2% of Ni, 0.4% of Sn, 0.16% of Mn and 0.05% of Zr when the temperature of the copper liquid rises to 1200 ℃, continuously heating and melting to obtain molten copper alloy liquid, and melting and stirring by utilizing the electromagnetic induction stirring function of the electric furnace; when the temperature of the molten copper alloy liquid rises to 1220 ℃, reducing the power of the power frequency electric furnace to keep the temperature of the copper alloy liquid at 1220 ℃; then inserting the water-cooled graphite crystallizer into molten copper alloy liquid for continuous casting by an up-drawing method to obtain a wire rod with the diameter of 8 mm;
and 2, carrying out multi-pass drawing on the wire at room temperature, wherein the pass deformation in the drawing process is 5%, and the wire after each pass of drawing enters a tubular furnace to carry out intermediate aging annealing in a hydrogen protective atmosphere at 800 ℃ for 1min to obtain the microalloyed copper-based wire.
The microalloyed copper-based wire obtained in the example had a diameter of 0.28mm, a tensile strength of 280MPa, a resistivity of 0.105. omega. m, and a meter resistance of 1.52. omega.
Example 2
Step 1, firstly placing electrolytic copper with the mass purity of not less than 99.9% in a graphite crucible, then placing the crucible in a vacuum argon protection power frequency electric furnace for melting to obtain copper liquid, when the temperature of the copper liquid rises to 1200 ℃, sequentially adding intermediate alloys of Cu-50% of Ni, Cu-30% of Sn, Cu-30% of Mn and Cu-30% of Zr into the copper liquid according to the mass percentage of 0.4% of Ni, 0.5% of Sn, 0.18% of Mn and 0.10% of Zr, continuously heating for melting to obtain molten copper alloy liquid, and melting and stirring by utilizing the electromagnetic induction stirring function of the electric furnace; when the temperature of the molten copper alloy liquid rises to 1250 ℃, reducing the power of the power frequency electric furnace to keep the temperature of the copper alloy liquid at 1250 ℃; then inserting the water-cooled graphite crystallizer into molten copper alloy liquid for continuous casting by an up-drawing method to obtain a wire rod with the diameter of 10 mm;
and 2, carrying out multi-pass drawing on the wire at room temperature, wherein the pass deformation in the drawing process is 6%, feeding the wire subjected to each pass drawing into a tubular furnace, and carrying out intermediate aging annealing in a hydrogen protective atmosphere at 900 ℃ for 3min to obtain the microalloyed copper-based wire.
The microalloyed copper-based wire obtained in the example has the diameter of 0.32mm, the tensile strength of 400MPa, the resistivity of 0.15 omega-m and the meter resistance of 1.6 omega.
Example 3
Step 1, firstly placing electrolytic copper with the mass purity of not less than 99.9% in a graphite crucible, then placing the crucible in a vacuum argon protection power frequency electric furnace for melting to obtain copper liquid, when the temperature of the copper liquid rises to 1200 ℃, sequentially adding intermediate alloys of Cu-50% of Ni, Cu-30% of Sn, Cu-30% of Mn and Cu-30% of Zr into the copper liquid according to the mass percentage of 0.3% of Ni, 0.45% of Sn, 0.17% of Mn and 0.08% of Zr, continuously heating for melting to obtain molten copper alloy liquid, and melting and stirring by utilizing the electromagnetic induction stirring function of the electric furnace; when the temperature of the molten copper alloy liquid rises to 1230 ℃, reducing the power of a power frequency electric furnace to keep the temperature of the copper alloy liquid at 1230 ℃; then inserting the water-cooled graphite crystallizer into molten copper alloy liquid for continuous casting by an up-drawing method to obtain a wire rod with the diameter of 9 mm;
and 2, carrying out multi-pass drawing on the wire at room temperature, wherein the pass deformation in the drawing process is 9%, and the wire after each pass of drawing enters a tubular furnace to carry out intermediate aging annealing in a hydrogen protective atmosphere at 850 ℃ for 1.5min to obtain the microalloyed copper-based wire.
The microalloyed copper-based wire obtained in the example had a diameter of 0.30mm, a tensile strength of 355MPa, a resistivity of 0.12. omega. m, and a meter resistance of 1.55. omega.
Example 4
Step 1, firstly placing electrolytic copper with the mass purity of not less than 99.9% in a graphite crucible, then placing the crucible in a vacuum argon protection power frequency electric furnace for melting to obtain copper liquid, when the temperature of the copper liquid rises to 1200 ℃, sequentially adding intermediate alloys of Cu-50% of Ni, Cu-30% of Sn, Cu-30% of Mn and Cu-30% of Zr into the copper liquid according to the mass percentage of 0.25% of Ni, 0.45% of Sn, 0.175% of Mn and 0.09% of Zr, continuously heating for melting to obtain molten copper alloy liquid, and melting and stirring by utilizing the electromagnetic induction stirring function of the electric furnace; when the temperature of the molten copper alloy liquid rises to 1240 ℃, reducing the power of the power frequency electric furnace to keep the temperature of the copper alloy liquid at 1240 ℃; then inserting the water-cooled graphite crystallizer into molten copper alloy liquid for continuous casting by an up-drawing method to obtain a wire rod with the diameter of 8.5 mm;
and 2, carrying out multi-pass drawing on the wire at room temperature, wherein the pass deformation in the drawing process is 8%, feeding the wire subjected to each pass of drawing into a tubular furnace, and carrying out intermediate aging annealing in a hydrogen protective atmosphere at 875 ℃ for 2min to obtain the microalloyed copper-based wire.
The microalloyed copper-based wire obtained in the example has the diameter of 0.29mm, the tensile strength of 365MPa, the resistivity of 0.125 omega-m and the meter resistance of 1.55 omega.
Example 5
Step 1, firstly placing electrolytic copper with the mass purity of not less than 99.9% in a graphite crucible, then placing the crucible in a vacuum argon protection power frequency electric furnace for melting to obtain a copper liquid, when the temperature of the copper liquid rises to 1200 ℃, sequentially adding intermediate alloys of Cu-50% of Ni, Cu-30% of Sn, Cu-30% of Mn and Cu-30% of Zr into the copper liquid according to the mass percentage of 0.35% of Ni, 0.465% of Sn, 0.178% of Mn and 0.085% of Zr, continuously heating for melting to obtain a molten copper alloy liquid, and melting and stirring by utilizing the electromagnetic induction stirring function of the electric furnace; when the temperature of the molten copper alloy liquid rises to 1225 ℃, reducing the power of the power frequency electric furnace to keep the temperature of the copper alloy liquid at 1225 ℃; then inserting the water-cooled graphite crystallizer into molten copper alloy liquid for continuous casting by an up-drawing method to obtain a wire rod with the diameter of 8 mm;
and 2, carrying out multi-pass drawing on the wire at room temperature, wherein the pass deformation in the drawing process is 10%, and the wire after each pass of drawing enters a tube furnace to carry out intermediate aging annealing in a hydrogen protective atmosphere at 880 ℃, wherein the intermediate aging annealing time is 1.75min, so as to obtain the microalloyed copper-based wire.
The microalloyed copper-based wire obtained in the example had a diameter of 0.31mm, a tensile strength of 370MPa, a resistivity of 0.135. omega. m, and a meter resistance of 1.58. omega.
Claims (7)
1. A microalloyed copper-based wire for electric heating of a floor is characterized by comprising the following components in percentage by mass:
0.2-0.4% of Ni, 0.4-0.5% of Sn, 0.16-0.18% of Mn, 0.05-0.10% of Zr, and the balance of Cu and other impurity elements, wherein the content of the other impurity elements is less than 0.03%.
2. A microalloyed copper-based wire for use in electric heating of floors as claimed in claim 1, wherein the microalloyed copper-based wire has a diameter of 0.28 to 0.32mm, a resistivity of 0.1 to 0.15 Ω -m, and a meter resistance of 1.5 to 1.6 Ω.
3. A preparation method of a microalloyed copper-based wire for electric heating of a floor is characterized by comprising the following steps:
step 1, putting electrolytic copper into a heating furnace to be melted to obtain copper liquid, when the temperature of the copper liquid is raised to a preset temperature, sequentially adding 0.2-0.4% of Ni, 0.4-0.5% of Sn, 0.16-0.18% of Mn and 0.05-0.10% of Zr into the copper liquid, and continuously heating and melting to obtain molten copper alloy liquid; after the temperature of the molten copper alloy liquid rises to a preset temperature, keeping the constant temperature; then inserting a graphite crystallizer into the molten copper alloy liquid for continuous casting by an upward drawing method to obtain a wire;
and 2, carrying out drawing forming and aging annealing on the wire to obtain the microalloyed copper-based wire.
4. A method for preparing a microalloyed copper-based wire for electric heating of floor slabs as claimed in claim 3, wherein the preset temperature in the step 1 is 1220-1250 ℃.
5. The method for preparing the microalloyed copper-based wire for the electric heating of the floor as claimed in claim 3, wherein the specific process of the step 2 is as follows: and (3) carrying out multi-pass drawing on the wire, wherein the pass deformation in the drawing process is 5-10%, and the wire after each pass of drawing enters a tube furnace to carry out intermediate aging annealing in the hydrogen protective atmosphere at 800-900 ℃, wherein the intermediate aging annealing time is 1-3 min.
6. A method for preparing a microalloyed copper-based wire for electric heating of floors as claimed in claim 3, wherein the diameter of the wire is Φ 8-10 mm.
7. The method of claim 3, wherein the Ni, Sn, Mn, Zr elements are added in the form of Cu-50% Ni, Cu-30% Sn, Cu-30% Mn, Cu-30% Zr master alloys, respectively.
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