CN113308621B - Copper-based resistance material and preparation method and application thereof - Google Patents
Copper-based resistance material and preparation method and application thereof Download PDFInfo
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- CN113308621B CN113308621B CN202110580635.3A CN202110580635A CN113308621B CN 113308621 B CN113308621 B CN 113308621B CN 202110580635 A CN202110580635 A CN 202110580635A CN 113308621 B CN113308621 B CN 113308621B
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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
- C22C9/05—Alloys based on copper with manganese as the next major constituent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
- B21B1/22—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling plates, strips, bands or sheets of indefinite length
- B21B1/24—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling plates, strips, bands or sheets of indefinite length in a continuous or semi-continuous process
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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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
Abstract
The invention belongs to the technical field of preparation of resistance materials, and particularly relates to a copper-based resistance material and a preparation method and application thereof. The copper-based resistance material comprises manganese, aluminum, nickel, iron and silicon, and the balance of copper and impurities. The manganese and the nickel can obviously reduce the conductivity of the copper-based resistance material, so that the material has higher resistivity. The compound addition of the trace elements of aluminum, iron and silicon effectively regulates and controls the structural characteristics of the copper-based resistance material, the elements enter the crystal lattice of copper through solid solution, the influence of temperature on atomic vibration is reduced, and the resistance temperature coefficient of the copper-based resistance material is improved, so that the lower resistance temperature coefficient and the more stable resistivity are obtained. By reasonably adding the iron element, the alloy structure in the material is effectively refined, and the component uniformity is improved. The addition of the aluminum element with specific dosage can improve the alloy melt fluidity of the resistance material and improve the component uniformity and the yield of the copper-based resistance material up-drawn continuous casting blank.
Description
Technical Field
The invention belongs to the technical field of preparation of resistance materials, and particularly relates to a copper-based resistance material and a preparation method and application thereof.
Background
The precision resistor material is a metal material used for manufacturing precision resistors, and the precision resistor material is a material having resistance value characteristics as main characteristics, which are small in absolute value of temperature coefficient of resistance and absolute value of thermal electromotive force to copper, and good in stability. The temperature stability of the alloy material for the precision resistor is higher than that of the material of the common resistor, and the error requirement of the precision resistor is much smaller than that of the common resistor in a certain temperature range. The copper-based precision resistance material is the resistance material which has the most application value in the non-high temperature field, the application occasions are the most extensive, and the core part of the copper-based precision resistance material is resistance copper alloy. For a long time, a plurality of single alloy grades are adopted all over the world, mainly including manganin, constantan and new constantan, wherein the manganin alloy is taken as the main material in the field of intelligent electric meters. The resistance copper alloy mainly contains two alloy elements of nickel and manganese, and the beneficial or harmful effects on other elements are not deeply concerned. In addition, under the existing smelting technical conditions, the sealing performance of the casting equipment is poor, the temperature is difficult to control and the like, and because the nickel content in the existing alloy mark is high, the smelting temperature is high, the manganese and nickel elements are extremely easy to oxidize in the smelting process, the element burning loss is difficult to control, and the content of specific elements such as manganese, nickel and the like in the material is not up to the standard. In addition, manganese oxide slag and the like generated by oxidation burning are impurities which are easy to exist in the material, so that the material has defects. Until now, the above problems have been difficult to overcome in the preparation process of the existing materials, and innovative improvements in the material composition and preparation method are needed.
With the coming of the comprehensive replacement era of mechanical instruments by intelligent instruments and the improvement of the precision, service life and stability of the intelligent instruments, the existing independently produced copper alloy material for the resistor is more and more difficult to meet the use requirements, great inconvenience is brought to shunt and electrician instrument manufacturing enterprises, manual meter adjusting time is greatly increased, production efficiency is seriously affected, and after-sale service cost is also greatly increased.
Meanwhile, the preparation method for producing the copper alloy resistance material mainly adopts a power frequency induction smelting furnace to melt and prepare the alloy, then uses a continuous casting or semi-continuous casting mode to carry out ingot casting, and finally combines cold rolling and annealing to complete forming. The existing smelting process cannot avoid the oxidation of alloy elements by air at high temperature, so that the components of the alloy are difficult to guarantee, the burning loss of manganese and nickel elements is serious, and the air suction of a melt is serious; the casting blank needs to mill the oxide layer on the surface, so that material waste is caused; the later stage of the forming procedure needs to be stripped and trimmed, which causes a great deal of waste of materials. The whole process lacks control on alloy texture, so that severe anisotropy is caused, and the performance of the alloy is influenced. In addition, the existing process has long production flow, high energy consumption, low cost rate and high comprehensive cost.
Disclosure of Invention
Therefore, the technical problems to be solved by the invention are to overcome the defects of high resistance temperature coefficient, poor stability, serious manganese and nickel element burning loss, serious melt gas suction, long production flow, high energy consumption and the like caused by difficult alloy component guarantee of a copper-based material process in the prior art, so that the copper-based resistance material and the preparation method and application thereof are provided.
Therefore, the invention provides the following technical scheme.
The invention provides a copper-based resistance material, which comprises, by mass, 10-14% of manganese, 1-3% of aluminum, 0.5-1.5% of nickel, 0.5-1.5% of iron, 0.5-1.5% of silicon and the balance of copper; among them, since the raw material inevitably contains a certain amount of impurities, the copper-based resistive material contains inevitable many impurity elements.
The total content of impurities in the copper-based resistance material is less than 50ppm, and the content of a single impurity element is less than 10 ppm; the oxygen content in the copper-based resistance material is less than 5 ppm.
The invention also provides a preparation method of the copper-based resistance material, which comprises the following steps,
(1) preheating: respectively heating the raw materials to a first temperature, and preserving heat;
(2) melting: heating the copper raw material obtained in the step (1) to a second temperature, adding the iron raw material, the nickel raw material, the silicon raw material, the manganese raw material and the aluminum raw material obtained in the step (1) after the copper raw material is melted, and standing to form a mixed melt;
(3) casting: controlling the mixed melt to a third temperature, continuously upward casting and coiling to obtain a continuous casting billet;
(4) rolling: continuously rolling the continuous casting billet for multiple times, and simultaneously coiling; wherein the total rolling processing amount is 60-80%, and the single-pass rolling amount is not more than 25%;
(5) annealing: and (4) annealing the material obtained in the step (4), and performing cold drawing to obtain the copper-based resistance material.
Specification of continuous casting billets: the thickness is 4-8mm, the width is 5-16mm, and the width-thickness ratio is less than 3.
Furthermore, when the copper-based resistance material is prepared, the nickel, the silicon and the iron are all prepared from granular, flaky or rodlike raw materials; the volume of iron particles is not more than 0.05cm3(ii) a The volume of each particle of nickel and silicon is not more than 1cm3。
Further, ensuring that the liquid level height change of the mixed melt in the step (3) is less than 50 mm; adding new raw materials according to the mass proportion of each component in the step (1) to form a new mixed melt, supplementing the formed new mixed melt to the casting step through a submerged flow communication device in the step (3), thereby ensuring that the liquid level height change of the mixed melt in the step (3) is less than 50mm, the total mass of the added new raw materials is not more than 5% of the total mass of the melt each time, the melt temperature is not influenced by the addition of the new raw materials, and the overall uniformity of the supplemented mixed melt is good. When the casting is started, the temperature of the mixed melt is raised to the third temperature, and then the mixed melt is kept for at least 20min, and after the normal production, the production process is a continuous process, and the third temperature is kept, so that the heat preservation is not needed.
A step (3) of upward casting by dipping a mold in the mixed melt;
the height difference between the tail end of the crystallizer and the liquid level of the mixed melt is more than 100 mm.
In the step (3), the drawing speed of continuous upward casting is 200-300 mm/min;
the outlet water temperature of the cooling water in the crystallizer is less than 50 ℃.
In the step (2) and the step (3), the upper surface of the mixed melt is covered with a covering agent;
the covering agent comprises (18-22) by volume: 1, crystalline flake graphite and sodium calcium silicate;
the thickness covered by the covering agent is 50-60 mm.
The first temperature is 120-200 ℃;
the second temperature is 1200-1220 ℃;
the third temperature is 1160-1180 ℃.
The annealing is carried out under a mixed atmosphere of nitrogen and hydrogen;
the volume concentration of hydrogen in the mixed atmosphere is not less than 1%;
the annealing temperature is 500-550 ℃. The average grain size of the annealed material is 1-20 μm.
And cold drawing is to continuously draw the annealed material at room temperature, so as to accurately control the size and the surface quality, wherein the cold working amount is 8-15%, and the cold drawing speed is not more than 60 m/min.
In the step (1), the heat preservation time is not less than 2 h;
in the step (2), standing for 30-60min during initial furnace drawing; the initial furnace start refers to that when the continuous production is started, because the production process is a continuous process and the temperature of the mixed melt is not influenced by the addition of new raw materials, the mixed melt does not need to stand after the production is started, and the mixed melt is formed after the raw materials are added.
In the step (5), the annealing time is 2-4 h.
In addition, the invention also provides an application of the copper-based resistance material or the copper-based resistance material prepared by the method in instruments, and particularly the copper-based resistance material is used for preparing a current divider, a thermocouple or a precision resistor in the instruments.
The technical scheme of the invention has the following advantages:
1. the copper-based resistance material comprises, by mass, 10-14% of manganese, 1-3% of aluminum, 0.5-1.5% of nickel, 0.5-1.5% of iron, 0.5-1.5% of silicon, and the balance of copper and impurities. The manganese and the nickel can obviously reduce the conductivity of the copper-based resistance material, so that the material has higher resistivity. The compound addition of the trace elements of aluminum, iron and silicon effectively regulates and controls the structural characteristics of the copper-based resistance material, the elements enter the crystal lattice of copper through solid solution, the influence of temperature on atomic vibration is reduced, and the resistance temperature coefficient of the copper-based resistance material is improved, so that the lower resistance temperature coefficient and the more stable resistivity are obtained. By reasonably adding the iron element, the alloy structure in the material is effectively refined, and the component uniformity is improved. The addition of the aluminum element with specific dosage can improve the alloy melt fluidity of the resistance material and improve the component uniformity and the yield of the copper-based resistance material up-drawn continuous casting blank.
The copper-based resistance material comprises manganese, aluminum, nickel, iron, silicon and copper with specific components, so that the resistance performance of the copper-based resistance material is more stable, the obtained material is a single-phase solid solution, namely a face-centered cubic structure with copper as a matrix, other alloy elements form a substitutional solid solution in a substitutional element mode, the resistance temperature coefficient is lower, the structure is compact, the crystal grains are fine, and the anisotropy is small. When the dosage of each component exceeds the range of the invention, a plurality of second phase particles can be formed in the resistance material, such as nickel-silicon phase, manganese-silicon phase and the like, so that the material composition is complicated, the material composition and the resistance stability of the resistance material are influenced, and the temperature coefficient of resistance of the material is further improved.
2. The preparation method of the copper-based resistance material provided by the invention comprises the steps of preheating, melting, casting, rolling, annealing and the like. By controlling the total processing amount and the pass processing amount of rolling, microcracks and large anisotropy of the material can be avoided in the rolling process. The total rolling processing amount of 60-80% of passes is adopted, the alloy crystal grains can be sufficiently crushed by more than 60%, the total rolling processing amount of the passes within 80% is controlled, the single-pass processing amount is less than 25%, the generation of an alloy texture can be effectively avoided, the alloy is prevented from forming large anisotropy after annealing, the influence of the anisotropy on the resistivity of the resistance material is reduced, the stability of the resistance material is improved, and the resistance performance of the copper-based resistance material is further ensured.
By controlling the total processing amount of rolling and the single-pass processing amount, the total deformation amount of the material in the pass can be enabled not to exceed a specified range, the low anisotropy degree of the alloy is ensured, and the resistance tested in the length direction is consistent with the actual transverse resistance when the shunt is used. Therefore, the situation that the resistance of the material in practical application is inconsistent with the test resistance value due to overhigh or overlow total processing amount and single-pass processing amount is avoided.
3. According to the preparation method provided by the invention, by controlling the traction speed in the casting step, the mixed melt can be ensured to form a material with regular size and compact structure, the traction speed is too high, the problem of untimely liquid supplement or incapability of being cooled and followed up in the crystallization process can occur, and the problems of irregular size and loose structure of the material after the mixed melt is crystallized can be caused. By controlling the temperature of the casting and melting steps, all raw materials can be fully melted, and the nickel and iron can not have hard point structures; when the melting is too high, the phenomenon of gas absorption occurs, and hydrogen is absorbed in the copper liquid, and bubbles are released in the casting process, so that the material forms pores, because the copper can dissolve hydrogen in the molten state.
4. According to the preparation method provided by the invention, the covering agent comprises flake graphite and sodium calcium silicate, the covering agent covers the surface of the mixed melt, so that the melt can be always in a micro-reducing atmosphere, the oxidation burning loss of elements such as manganese, aluminum and the like is prevented, the softening point of the sodium calcium silicate is low, the covering agent can be matched with the flake graphite to be used as the covering agent to completely cover the surface of the melt, oxygen is further isolated, and the oxidation burning loss rate is reduced.
The raw materials are preheated, so that water vapor, oil content and the like can be prevented from entering the melt, the defect of the melt is avoided, and the quality of the melt is improved. The continuous ingot casting by the up-drawing method can greatly improve the surface quality, and the finished product rate can be greatly improved without a face milling process.
The preparation method of the copper-based resistance material provided by the invention does not need edge cutting, face milling and continuous roll production, the comprehensive yield of the copper-based resistance material can reach more than 95% and is far higher than 60% of that of the traditional process, and the copper-based resistance material has the advantages of uniform and consistent product performance, compact and uniform tissue and the like, and has obvious technical advantages compared with the similar products in the prior art.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Example 1
The embodiment provides a copper-based resistance material, which comprises the following components, by mass, 14 wt% of manganese, 2 wt% of aluminum, 0.5 wt% of nickel, 1.5 wt% of iron and 1 wt% of silicon, and the balance of copper and inevitable impurities, wherein the content of the impurities is less than 50ppm, and the content of oxygen is less than 5 ppm.
The preparation method of the copper-based resistance material comprises the following steps:
(1) preheating: selecting a graphite crucible furnace as smelting equipment, wherein the smelting equipment comprises a smelting bin and a casting bin, the bottoms of the two bins are communicated through a subsurface flow communication device, and whether the bottoms of the two bins are communicated is controlled through a stopper rod; the smelting bin is used for heating to melt the raw materials to form a melt; the casting bin is used for upward casting, and the crystallizer is arranged above the casting bin. The heating electrodes are positioned at the bottom and the side surface of the crucible, the smelting bin and the casting bin are respectively provided with an independent control heating system, and the graphite crucible and the graphite electrodes are in inert atmosphere protection.
Weighing 14kg of manganese raw material, 2kg of aluminum raw material, 0.5kg of nickel raw material, 1.5kg of iron raw material, 1kg of silicon raw material and 81kg of copper raw material respectively; wherein the nickel raw material, the silicon raw material and the iron raw material are all small-particle raw materials, and the single particle volume of the iron raw material is not more than 0.05cm3The volume of each particle of the nickel material and the silicon material is not more than 1cm3. Then putting the six raw materials into a preheating furnace with an opening respectively, and preheating for 4 hours at 180 ℃.
(2) Melting: controlling a stopper rod to seal a channel between a smelting bin and a casting bin, putting a preheated copper raw material into the smelting bin in a graphite crucible furnace, adjusting the temperature in the smelting bin to 1200 ℃, melting the copper raw material in the furnace to form a melt, and covering the surface of the melt in the smelting bin with a covering agent (comprising crystalline flake graphite and sodium calcium silicate in a volume ratio of 20: 1), wherein the thickness of the covering agent is 50 mm; adding the preheated iron raw material, nickel raw material, silicon raw material, manganese raw material and aluminum raw material into a smelting bin, and standing for 30min to melt the raw materials to form a mixed melt; and meanwhile, controlling the temperature of the casting bin to be 1160 ℃. After continuous production, all raw materials are added into a smelting bin and do not need to stand, and the formed mixed melt is introduced into a casting step.
(3) Casting: the stopper rod is pulled out, the mixed melt in the smelting bin enters a casting bin, a covering agent (comprising crystalline flake graphite and sodium calcium silicate with the volume ratio of 20: 1) is adopted to cover the mixed melt in the casting bin, and the thickness of the covering agent is 50 mm; and (3) dipping the crystallizer into the mixed melt of the casting bin to ensure that the height difference between the tail end of the crystallizer mould and the liquid level of the mixed solution is 140mm, keeping the temperature for 20min, starting continuous upward casting and coiling to obtain a continuous casting blank with the thickness of 6 +/-0.05 mm and the width of 14.5 +/-0.1 mm. Wherein the drawing speed of the upward continuous casting is 250 mm/min; a cooling water channel is arranged in the crystallizer and used for cooling the mixed melt to be solid, and the outlet water temperature of the cooling water of the crystallizer is less than 50 ℃; along with the casting step, the liquid level of the mixed solution in the casting bin can be reduced, the raw materials are added into the preheating furnace according to the mass proportion of the raw materials in the step (1), the raw materials are dried and then are introduced into the smelting bin to form a mixed melt, the total mass of the added raw materials is 3% of the total mass of the mixed melt every time, the temperature of the mixed melt is not influenced by the temperature of the added raw materials, the integral uniformity of the mixed melt is ensured, and the liquid level height change of the mixed melt in the casting bin is ensured to be less than 50 mm. Wherein, when casting is started, the temperature needs to be preserved for 20min, the continuous operation is carried out after the production is started, and the temperature preservation of the mixed melt is not carried out.
(4) Rolling: and (3) performing multi-pass roll rolling on the continuous casting slab obtained in the step (3), wherein the continuous casting slab is finally rolled to 1.7 multiplied by 14.2mm, the total reduction of area (reduction of area) of the rolling is 72.25%, the number of the rolling passes is 6, the continuous casting slab is respectively rolled to 4.7 multiplied by 14.2mm, 3.6 multiplied by 14.2mm, 2.9 multiplied by 14.2mm, 2.4 multiplied by 14.2mm, 2.0 multiplied by 14.2mm and 1.7 multiplied by 14.2mm in the first pass, the second pass, the third pass, the fourth pass, the fifth pass and the sixth pass, and the corresponding processing amounts are 23.29%, 23.4%, 19.4%, 17.24%, 16.67% and 15% respectively. And rolling and coiling are carried out simultaneously in each pass.
(5) Annealing: annealing the rolled material at 500 ℃ for 3 h; wherein, the mixed gas of nitrogen and hydrogen is used as a protective atmosphere, the volume concentration of the hydrogen in the protective atmosphere is 2 percent, and the average grain diameter of the annealed material is 12 mu m.
Continuously cold-drawing and finishing the annealed material to obtain a copper-based resistance material with the specification of 1.5mm multiplied by 6 mm; wherein the cold drawing speed is 50m/min, and the cold working amount is 10.58%.
The resistivity of the copper-based resistance material is 0.44 +/-0.02 mu omega.m, the applicable temperature range is 0-100 ℃, the thickness tolerance is +/-0.01 mm, the yield reaches 97 percent, and the resistance temperature coefficient alpha is 30 multiplied by 10-6At/° C, the temperature coefficient of resistance beta is-0.4 x 10-6The average thermal electromotive force rate of copper is 0.6 muV/DEG C, and the comprehensive energy consumption of the process for preparing the copper-based resistance material is about 900 KWh/t.
Compared with the performances specified by the alloy wires, sheets and strips of the manganin and constantan precision resistance alloy in GB/T6145-2010, the copper-based resistance material obtained by the invention has obvious advantages, wherein the comparison of the performances of the copper-based resistance material obtained by the invention and the performances required by the national standard is shown in Table 1.
TABLE 1 comparison of the performance of the copper-based resistance material obtained by the invention and national standard
Example 2
This example provides a copper-based resistive material having a composition, in mass fractions, including 12 wt% manganese, 3 wt% aluminum, 0.5 wt% nickel, 0.5 wt% iron, 0.5 wt% silicon, and the balance copper and unavoidable impurities, wherein the impurities are less than 50ppm and the oxygen content is less than 5 ppm.
The preparation method of the copper-based resistance material comprises the following steps:
(1) preheating: selecting a graphite crucible furnace as smelting equipment, wherein the smelting equipment comprises a smelting bin and a casting bin, the bottoms of the two bins are communicated through a subsurface flow communication device, and whether the bottoms of the two bins are communicated is controlled through a stopper rod; the smelting bin is used for heating to melt the raw materials to form a melt; the casting bin is used for upward casting, and the crystallizer is arranged above the casting bin. The heating electrodes are positioned at the bottom and the side surface of the crucible, the smelting bin and the casting bin are respectively provided with an independent control heating system, and the graphite crucible and the graphite electrodes are in inert atmosphere protection.
Weighing 12kg of manganese raw material, 3kg of aluminum raw material, 0.5kg of nickel raw material, 0.5kg of iron raw material, 0.5kg of silicon raw material and 83.5kg of copper raw material respectively; wherein the nickel raw material, the silicon raw material and the iron raw material are all small-particle raw materials, and the single particle volume of the iron raw material is not more than 0.05cm3The volume of each particle of the nickel material and the silicon material is not more than 1cm3. Then mixing the above raw materialsThe materials are respectively put into a preheating furnace with an opening and preheated for 4 hours at 180 ℃.
(2) Melting: controlling a stopper rod to seal a channel between a smelting bin and a casting bin, putting a preheated copper raw material into the smelting bin in a graphite crucible furnace, adjusting the temperature in the smelting bin to 1220 ℃, melting the copper raw material in the furnace to form a melt, and covering the surface of the melt in the smelting bin with a covering agent (comprising crystalline flake graphite and sodium calcium silicate with a volume ratio of 20: 1), wherein the thickness of the covering agent is 60 mm; adding the preheated iron raw material, nickel raw material, silicon raw material, manganese raw material and aluminum raw material into a smelting bin, and standing for 60min to melt the raw materials to form a mixed melt; and simultaneously controlling the temperature of the casting bin to be 1180 ℃. Wherein, after the continuous production, the formed mixed melt is directly introduced into the casting step without standing.
(3) Casting: the stopper rod is pulled out, the mixed melt in the smelting bin enters a casting bin, a covering agent (comprising crystalline flake graphite and sodium calcium silicate with the volume ratio of 20: 1) is adopted to cover the mixed melt in the casting bin, and the thickness of the covering agent is 60 mm; and (3) dipping the crystallizer into the mixed melt of the casting bin to ensure that the height difference between the tail end of the crystallizer mould and the liquid level of the mixed solution is 140mm, keeping the temperature for 20min, starting continuous upward casting and coiling to obtain a continuous casting blank with the thickness of 7 +/-0.05 mm and the width of 8.5 +/-0.1 mm. Wherein the drawing speed of the upward continuous casting is 200 mm/min; the outlet water temperature of the cooling water of the crystallizer is less than 40 ℃; along with the casting step, the liquid level of the mixed solution in the casting bin can be reduced, raw materials are added into the preheating furnace according to the mass proportion of the raw materials in the step (1), the raw materials are dried and then are introduced into the smelting bin to form a mixed melt, the total mass of the added raw materials is 4% of the total mass of the mixed melt every time, the temperature of the mixed melt is not influenced by the temperature of the added raw materials, the integral uniformity of the mixed melt is ensured, and the liquid level height change of the mixed melt in the casting bin is ensured to be less than 50 mm.
(4) Rolling: and (3) performing multi-pass roll rolling on the continuous casting slab obtained in the step (3), wherein the continuous casting slab is finally rolled to 2.2 × 8.2mm, the total rolling processing amount is 69.68%, the rolling passes are 5, each pass is coiled, the first, second, third, fourth and fifth passes respectively roll the continuous casting slab to 5.6 × 8.2mm, 4.3 × 8.2mm, 3.4 × 8.2mm, 2.7 × 8.2mm and 2.2 × 8.2mm, and the corresponding processing amounts are 22.82%, 23.21%, 20.93%, 20.59% and 18.5%. And rolling and coiling are simultaneously carried out.
(5) Annealing: annealing the rolled material at 500 ℃ for 2 h; wherein, the mixed gas of nitrogen and hydrogen is used as a protective atmosphere, the volume concentration of the hydrogen in the protective atmosphere is 2 percent, and the average grain diameter of the annealed material is 10 mu m.
Continuously cold-drawing and finishing the annealed material to obtain a copper-based resistance material with the specification of 2mm multiplied by 8 mm; wherein the cold drawing speed is 50m/min, and the cold working amount is 11.31%.
The resistivity of the copper-based resistance material is 0.44 +/-0.02 mu omega.m, the applicable temperature range is 0-100 ℃, the thickness tolerance is +/-0.01 mm, the yield reaches 96 percent, and the resistance temperature coefficient alpha is 25 multiplied by 10-6At/° C, the temperature coefficient of resistance beta is-0.3 × 10-6The average thermal electromotive force rate of copper is 0.5 muV/DEG C, and the comprehensive energy consumption of the process for preparing the copper-based resistance material is about 1100 KWh/t.
Example 3
This example provides a copper-based resistive material having a composition, in mass fractions, including 11 wt% manganese, 3 wt% aluminum, 0.5 wt% nickel, 1.5 wt% iron, 1.5 wt% silicon, and the balance copper and unavoidable impurities, wherein the impurities are present in an amount less than 50ppm and the oxygen content is less than 5 ppm.
The preparation method of the copper-based resistance material comprises the following steps:
(1) preheating: selecting a graphite crucible furnace as smelting equipment, wherein the smelting equipment comprises a smelting bin and a casting bin, the bottoms of the two bins are communicated through a subsurface flow communication device, and whether the bottoms of the two bins are communicated is controlled through a stopper rod; the smelting bin is used for heating to melt the raw materials to form a melt; the casting bin is used for upward casting, and the crystallizer is arranged above the casting bin. The heating electrodes are positioned at the bottom and the side surface of the crucible, the smelting bin and the casting bin are respectively provided with an independent control heating system, and the graphite crucible and the graphite electrodes are in inert atmosphere protection.
Weighing 11kg of manganese respectivelyRaw materials, 3kg of aluminum raw material, 0.5kg of nickel raw material, 1.5kg of iron raw material, 1.5kg of silicon raw material and 82.5kg of copper raw material; wherein the nickel raw material, the silicon raw material and the iron raw material are all small-particle raw materials, and the single particle volume of the iron raw material is not more than 0.05cm3The volume of each particle of the nickel material and the silicon material is not more than 1cm3. Then the raw materials are respectively put into a preheating furnace with an opening and preheated for 3 hours at 200 ℃.
(2) Melting: controlling a stopper rod to seal a channel between a smelting bin and a casting bin, putting a preheated copper raw material into the smelting bin in a graphite crucible furnace, adjusting the temperature in the smelting bin to 1210 ℃, melting the copper raw material in the furnace to form a melt, and covering the surface of the melt in the smelting bin with a covering agent (comprising crystalline flake graphite and sodium calcium silicate in a volume ratio of 20: 1), wherein the thickness of the covering agent is 60 mm; adding the preheated iron raw material, nickel raw material, silicon raw material, manganese raw material and aluminum raw material into a smelting bin, and standing for 30min to melt the raw materials to form a mixed melt; while controlling the temperature of the casting bin to 1170 ℃. Wherein, after the continuous production, the formed mixed melt is directly introduced into the casting step without standing.
(3) Casting: the stopper rod is pulled out, the mixed melt in the smelting bin enters a casting bin, a covering agent (comprising crystalline flake graphite and sodium calcium silicate with the volume ratio of 20: 1) is adopted to cover the mixed melt in the casting bin, and the thickness of the covering agent is 55 mm; and (3) dipping the crystallizer into the mixed melt of the casting bin to ensure that the height difference between the tail end of the crystallizer mould and the liquid level of the mixed solution is 140mm, keeping the temperature for 20min, starting continuous upward casting and coiling to obtain a continuous casting blank with the thickness of 8 +/-0.05 mm and the width of 12.5 +/-0.1 mm. Wherein the drawing speed of the upward continuous casting is 200 mm/min; the outlet water temperature of the cooling water of the crystallizer is less than 40 ℃; along with the casting step, the liquid level of the mixed solution in the casting bin can be reduced, the raw materials are added into the preheating furnace according to the mass proportion of the raw materials in the step (1), the raw materials are dried and then are introduced into the smelting bin to form a mixed melt, the total mass of the added raw materials is 3% of the total mass of the mixed melt every time, the temperature of the mixed melt is not influenced by the temperature of the added raw materials, the integral uniformity of the mixed melt is ensured, and the liquid level height change of the mixed melt in the casting bin is ensured to be less than 50 mm.
(4) Rolling: and (3) performing multi-pass roll rolling on the continuous casting slab obtained in the step (3), wherein the continuous casting slab is finally rolled to 2.2 multiplied by 6.1mm, the total rolling processing amount is 66.4%, the rolling pass is 5 passes, the continuous casting slab is respectively rolled to 6.5 multiplied by 12mm, 5.0 multiplied by 12mm, 4.0 multiplied by 12mm, 3.3 multiplied by 12mm and 2.8 multiplied by 12mm in the first, second, third, fourth and fifth rolling passes, and the corresponding processing amounts are respectively 22%, 23.08%, 20%, 17.5% and 15.15%. And rolling and coiling are simultaneously carried out.
(5) Annealing: annealing the rolled material at 550 ℃ for 2 h; wherein, the mixed gas of nitrogen and hydrogen is used as a protective atmosphere, the volume concentration of the hydrogen in the protective atmosphere is 4 percent, and the average grain diameter of the annealed material is 14 mu m.
Continuously cold-drawing and finishing the annealed material to obtain a copper-based resistance material with the specification of 3mm multiplied by 12 mm; wherein the cold drawing speed is 40m/min, and the cold working amount is 10.71%.
The resistivity of the copper-based resistance material is 0.44 +/-0.02 mu omega.m, the applicable temperature range is 0-100 ℃, the thickness tolerance is +/-0.01 mm, the yield reaches 98 percent, and the resistance temperature coefficient alpha is 18 multiplied by 10-6At/° C, the temperature coefficient of resistance beta is-0.4 x 10-6The average thermal electromotive force rate of copper is 0.4 muV/DEG C, and the comprehensive energy consumption of the process for preparing the copper-based resistance material is about 1200 KWh/t.
Example 4
This example provides a copper-based resistive material having a composition, in mass fractions, including 11.5 wt% manganese, 2.5 wt% aluminum, 1.1 wt% nickel, 0.9 wt% iron, 0.8 wt% silicon, and the balance copper and unavoidable impurities, wherein the impurities are less than 50ppm and the oxygen content is less than 5 ppm.
The preparation method of the copper-based resistance material comprises the following steps:
(1) preheating: selecting a graphite crucible furnace as smelting equipment, wherein the smelting equipment comprises a smelting bin and a casting bin, the bottoms of the two bins are communicated through a subsurface flow communication device, and whether the bottoms of the two bins are communicated is controlled through a stopper rod; the smelting bin is used for heating to melt the raw materials to form a melt; the casting bin is used for upward casting, and the crystallizer is arranged above the casting bin. The heating electrodes are positioned at the bottom and the side surface of the crucible, the smelting bin and the casting bin are respectively provided with an independent control heating system, and the graphite crucible and the graphite electrodes are in inert atmosphere protection.
Respectively weighing 11.5kg of manganese raw material, 2.5kg of aluminum raw material, 1.1kg of nickel raw material, 0.9kg of iron raw material, 0.8kg of silicon raw material and 83.2kg of copper raw material; wherein the nickel raw material, the silicon raw material and the iron raw material are all small-particle raw materials, and the single particle volume of the iron raw material is not more than 0.05cm3The volume of each particle of the nickel material and the silicon material is not more than 1cm3. Then the raw materials are respectively put into a preheating furnace with an opening and preheated for 4 hours at 180 ℃.
(2) Melting: controlling a stopper rod to seal a channel between a smelting bin and a casting bin, putting a preheated copper raw material into the smelting bin in a graphite crucible furnace, adjusting the temperature in the smelting bin to 1200 ℃, melting the copper raw material in the furnace to form a melt, and covering the surface of the melt in the smelting bin with a covering agent (comprising crystalline flake graphite and sodium calcium silicate in a volume ratio of 20: 1), wherein the thickness of the covering agent is 50 mm; adding the preheated iron raw material, nickel raw material, silicon raw material, manganese raw material and aluminum raw material into a smelting bin, and standing for 30min to melt the raw materials to form a mixed melt; and meanwhile, controlling the temperature of the casting bin to be 1160 ℃.
(3) Casting: the stopper rod is pulled out, the mixed melt in the smelting bin enters a casting bin, a covering agent (comprising crystalline flake graphite and sodium calcium silicate with the volume ratio of 20: 1) is adopted to cover the mixed melt in the casting bin, and the thickness of the covering agent is 50 mm; and (3) dipping the crystallizer into the mixed melt of the casting bin to ensure that the height difference between the tail end of the crystallizer mould and the liquid level of the mixed solution is 140mm, keeping the temperature for 20min, starting continuous upward casting and coiling to obtain a continuous casting blank with the thickness of 6 +/-0.05 mm and the width of 14.5 +/-0.1 mm. Wherein the drawing speed of the upward continuous casting is 250 mm/min; a cooling water channel is arranged in the crystallizer and used for cooling the mixed melt to be solid, and the outlet water temperature of the cooling water of the crystallizer is less than 50 ℃; along with the casting step, the liquid level of the mixed solution in the casting bin can be reduced, raw materials are added into the preheating furnace according to the mass proportion of the raw materials in the step (1), the raw materials are dried and then are introduced into the smelting bin to form a mixed melt, the total mass of the added raw materials is 5% of the total mass of the mixed melt every time, the temperature of the mixed melt is not influenced by the temperature of the added raw materials, the integral uniformity of the mixed melt is ensured, and the liquid level height change of the mixed melt in the casting bin is ensured to be less than 50 mm.
(4) Rolling: and (3) performing multi-pass roll rolling on the continuous casting slab obtained in the step (3), wherein the continuous casting slab is finally rolled to 1.7 multiplied by 14.2mm, the total reduction of area (reduction of area) of the rolling is 72.25%, the number of the rolling passes is 6, the continuous casting slab is respectively rolled to 4.7 multiplied by 14.2mm, 3.6 multiplied by 14.2mm, 2.9 multiplied by 14.2mm, 2.4 multiplied by 14.2mm, 2.0 multiplied by 14.2mm and 1.7 multiplied by 14.2mm in the first pass, the second pass, the third pass, the fourth pass, the fifth pass and the sixth pass, and the corresponding processing amounts are 23.29%, 23.4%, 19.4%, 17.24%, 16.67% and 15% respectively. And rolling and coiling are carried out simultaneously in each pass.
(5) Annealing: annealing the rolled material at 500 ℃ for 3 h; wherein, the mixed gas of nitrogen and hydrogen is used as a protective atmosphere, the volume concentration of the hydrogen in the protective atmosphere is 2 percent, and the average grain diameter of the annealed material is 12 mu m.
Continuously cold-drawing and finishing the annealed material to obtain a copper-based resistance material with the specification of 1.5mm multiplied by 6 mm; wherein the cold drawing speed is 50m/min, and the cold working amount is 10.58%.
The resistivity of the copper-based resistance material is 0.46 +/-0.02 mu omega.m, the applicable temperature range is 0-100 ℃, the thickness tolerance is +/-0.01 mm, the yield reaches 97 percent, and the resistance temperature coefficient alpha is-3 multiplied by 10-6At/° C, the temperature coefficient of resistance beta is-0.6 x 10-6The average thermal electromotive force rate of copper is 0.5 muV/DEG C, and the comprehensive energy consumption of the process for preparing the copper-based resistance material is about 900 KWh/t.
Comparative example 1
The comparative example provides a copper-based resistive material having a composition comprising, in mass fractions, 18 wt% manganese, 0.5 wt% aluminum, 2.5 wt% nickel, 1.5 wt% iron, 1 wt% silicon, and the balance copper and unavoidable impurities, wherein the content of impurities is less than 50ppm, and the content of oxygen is less than 5 ppm. This comparative example prepared a copper-based resistive material in the same manner as in example 1.
The resistivity of the copper-based resistance material is 59 +/-0.05 mu omega.m, and the temperature coefficient of resistance alpha is 36 multiplied by 10-6/° C, and the temperature coefficient of resistance beta is-0.8 x 10-6The average thermal electromotive force rate of copper is 1.6 mu V/DEG C, and the comprehensive energy consumption of the process for preparing the copper-based resistance material in the comparative example is about 900 KWh/t. The material of the component is easy to have second phase particles at room temperature, has high processing hardness rate and high hardness, and is difficult to form. Since the temperature coefficient of resistance is too large, it is not suitable for manufacturing precision resistors.
Comparative example 2
The comparative example provides a copper-based resistive material having a composition comprising, in mass fractions, 2 wt% aluminum, 0.5 wt% nickel, 1.5 wt% iron, 1 wt% silicon, and the balance copper and unavoidable impurities, wherein the content of impurities is less than 50ppm and the content of oxygen is less than 5 ppm. This comparative example prepared a copper-based resistive material in the same manner as in example 1.
The resistivity of the copper-based resistance material is 0.01 mu omega.m, and the temperature coefficient of resistance alpha is 1600 multiplied by 10-6The properties of/° c, cannot be used to make resistive alloys.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.
Claims (9)
1. The copper-based resistance material is characterized by comprising, by mass, 10-14% of manganese, 1-3% of aluminum, 0.5-1.5% of nickel, 0.5-1.5% of iron, 0.5-1.5% of silicon and the balance of copper;
the total content of impurities in the copper-based resistance material is less than 50ppm, and the content of single impurity elements is less than 10 ppm.
2. The method for producing a copper-based resistive material according to claim 1, comprising the steps of,
(1) preheating: respectively heating the raw materials to a first temperature, and preserving heat;
(2) melting: heating the copper raw material obtained in the step (1) to a second temperature, adding the iron raw material, the nickel raw material, the silicon raw material, the manganese raw material and the aluminum raw material obtained in the step (1) after the copper raw material is melted, and standing to form a mixed melt;
(3) casting: controlling the mixed melt to a third temperature, continuously upward casting and coiling to obtain a continuous casting billet;
(4) rolling: continuously rolling the continuous casting billet and simultaneously coiling; wherein the total rolling processing amount is 60-80%, and the single-pass rolling amount is not more than 25%;
(5) annealing: and (4) annealing the material obtained in the step (4), and performing cold drawing to obtain the copper-based resistance material.
3. The production method according to claim 2, wherein the height variation of the liquid level of the mixed melt in the step (3) is ensured to be less than 50 mm.
4. The production method according to claim 2 or 3, characterized in that, in the step (3), the upward casting is performed by dipping a mold in the mixed melt;
the height difference between the tail end of the crystallizer and the liquid level of the mixed melt is more than 100 mm.
5. The method as claimed in claim 4, wherein in the step (3), the drawing speed of the continuous up-casting is 200-300 mm/min;
the outlet water temperature of the cooling water in the crystallizer is less than 50 ℃.
6. The production method according to claim 2, wherein in the step (2) and the step (3), the upper surface of the mixed melt is covered with a covering agent;
the covering agent comprises (18-22) by volume: 1, crystalline flake graphite and sodium calcium silicate;
the thickness covered by the covering agent is 50-60 mm.
7. The method as claimed in claim 2, wherein the first temperature is 120-200 ℃;
the second temperature is 1200-1220 ℃;
the third temperature is 1160-1180 ℃.
8. The production method according to claim 2, wherein the annealing is performed under a mixed atmosphere of nitrogen and hydrogen;
the volume concentration of hydrogen in the mixed atmosphere is not less than 1%;
the annealing temperature is 500-550 ℃.
9. Use of a copper-based electrical resistance material according to claim 1 or prepared according to any one of claims 2 to 8 in a meter.
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| DE2107391C3 (en) * | 1971-02-16 | 1975-10-23 | Wsesojusny Nautschno-Issledowatelskij Institut Metrologii Imeni D. I. Mendeleewa, Leningrad (Sowjetunion) | Alloy for precision resistors |
| US20060158304A1 (en) * | 2002-12-16 | 2006-07-20 | Satoshi Moriya | Resistive material, resistive element, resistor, and method for manufacturing resistor |
| JP2005298952A (en) * | 2004-04-15 | 2005-10-27 | Chuo Spring Co Ltd | Damping material and its production method |
| CN101619780B (en) * | 2009-07-27 | 2011-04-13 | 赵玉 | Technological method for upwardly continuously casting, rolling, drawing and producing copper alloy tubes |
| JP6109329B2 (en) * | 2014-03-14 | 2017-04-05 | 古河電気工業株式会社 | Cu-Al-Mn alloy material, method for producing the same, and bar or plate material using the same |
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