CN116240425A - Manganese white copper material for precision resistor and preparation method thereof - Google Patents
Manganese white copper material for precision resistor and preparation method thereof Download PDFInfo
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- 239000011572 manganese Substances 0.000 title claims abstract description 171
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 154
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 154
- 229910000570 Cupronickel Inorganic materials 0.000 title claims abstract description 153
- 239000000463 material Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000000956 alloy Substances 0.000 claims abstract description 99
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 96
- 239000010949 copper Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 28
- 229910003289 NiMn Inorganic materials 0.000 claims abstract description 24
- 239000002245 particle Substances 0.000 claims abstract description 23
- 239000012535 impurity Substances 0.000 claims abstract description 20
- 238000009749 continuous casting Methods 0.000 claims abstract description 9
- 238000004321 preservation Methods 0.000 claims description 59
- 238000000137 annealing Methods 0.000 claims description 58
- 238000003723 Smelting Methods 0.000 claims description 49
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 46
- 238000005406 washing Methods 0.000 claims description 42
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 37
- 229910052802 copper Inorganic materials 0.000 claims description 28
- 239000002994 raw material Substances 0.000 claims description 28
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 27
- 238000005266 casting Methods 0.000 claims description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 230000032683 aging Effects 0.000 claims description 24
- 229910052786 argon Inorganic materials 0.000 claims description 23
- 239000002253 acid Substances 0.000 claims description 21
- 239000003513 alkali Substances 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 21
- 238000007127 saponification reaction Methods 0.000 claims description 21
- 238000005096 rolling process Methods 0.000 claims description 20
- 239000006104 solid solution Substances 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000010936 titanium Substances 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 239000012298 atmosphere Substances 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 230000001681 protective effect Effects 0.000 claims description 9
- 239000011159 matrix material Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 239000000498 cooling water Substances 0.000 claims description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- HPDFFVBPXCTEDN-UHFFFAOYSA-N copper manganese Chemical compound [Mn].[Cu] HPDFFVBPXCTEDN-UHFFFAOYSA-N 0.000 claims description 6
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- 238000001887 electron backscatter diffraction Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000005457 optimization Methods 0.000 abstract description 2
- 230000000930 thermomechanical effect Effects 0.000 abstract description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 10
- 239000011593 sulfur Substances 0.000 description 10
- 229910052717 sulfur Inorganic materials 0.000 description 10
- 239000012300 argon atmosphere Substances 0.000 description 5
- 238000005275 alloying Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
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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
- C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
-
- 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
- B22D11/14—Plants for continuous casting
- B22D11/143—Plants for continuous casting for horizontal casting
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/05—Alloys based on copper with manganese as the next major constituent
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Conductive Materials (AREA)
Abstract
The invention discloses a manganese cupronickel material for precision resistor and a preparation method thereof, wherein the material comprises the following components: 15-20wt% of Ni, 18-25wt% of Mn, 1.0-2.0wt% of Sn, 0.2-1.0 wt% of Ti, 1.5-2.5wt% of Ag and the balance of Cu plus unavoidable impurities, wherein the mass ratio of Mn to Ni is greater than 1.2. According to the invention, by adding micro-alloy elements such as Sn, ti, ag and the like and introducing NiMn phase particles with low resistance, the resistance temperature coefficient of the alloy is reduced; the structural uniformity of the manganese white copper finished product is further improved by adopting the modes of vacuum horizontal continuous casting technology, optimization of a thermomechanical treatment process and the like, and the performance stability of the alloy finished product is improved.
Description
Technical Field
The invention belongs to the field of nonferrous metal processing, and relates to a manganese white copper material for a precise resistor and a processing preparation method thereof.
Background
The manganese white copper is a copper-base alloy material with high resistance and high resistance temperature coefficient, is mainly used for manufacturing resistance components such as potential difference meters, current dividers, precision bridges and the like, and is widely applied to the fields of precision instruments, electronic and electric, information communication and the like.
Along with the development of high precision and high stability of precision resistor components, higher requirements are put on the resistance temperature coefficient and the performance stability of the precision resistor alloy material. How to reduce the resistance temperature coefficient of the manganese white copper has become the research important content of the material at present.
Disclosure of Invention
At present, alloying element addition is a main means for reducing the temperature coefficient of resistance of manganese copper. The addition of elements such as germanium, aluminum, silicon and the like can effectively reduce the resistance temperature coefficient of the manganese white copper and improve the performance stability of the manganese white copper.
The nickel and manganese elements in the manganese white copper are oxidized in the high-temperature smelting process, so that the content of the nickel and manganese elements in an alloy casting blank is difficult to control, and the composition and performance stability of the manganese white copper are greatly influenced; in addition, nickel and manganese oxides are liable to exist in the alloy cast stock in the form of impurities, and these coarse oxides seriously affect the plastic formability and strength of the manganese white copper product. Therefore, how to avoid the oxidation of nickel and manganese elements in the casting process of the manganese white copper so as to improve the quality of casting blanks is also a key problem to be solved by the current manganese white copper products.
From the above application data about manganese copper, it is known that the comprehensive performance and preparation process of manganese white copper are required to be further optimized in order to meet the increasingly complex service environment. The patent aims to design a novel manganese white copper material through micro-alloying element regulation and control, and further improve the structure and performance stability of the manganese white copper by adopting methods such as vacuum horizontal continuous casting technology, thermomechanical treatment process optimization and the like, so as to prepare the manganese white copper for precise resistance with high strength and low resistance temperature coefficient.
The invention aims to provide the manganese cupronickel material for the precise resistor, which has novel and unique structure, is convenient to use and can be organically matched with the packaged commodity; the specific technical scheme is as follows:
a low temperature coefficient of resistance, high strength manganese cupronickel material, the composition of which is: 15-20wt% of Ni, 18-25wt% of Mn, 1.5-2.5wt% of Ag, 1.0-2.0wt% of Sn, 0.2-1.0wt% of Ti and the balance of Cu plus unavoidable impurities, wherein the mass ratio of Mn to Ni is greater than 1.2.
The preparation method of the manganese white copper material comprises the following steps:
firstly, adding raw materials into a smelting furnace in a vacuum continuous smelting and casting system, vacuumizing the smelting furnace and a heat preservation furnace in the vacuum continuous smelting and casting system, and keeping the vacuum degree of the smelting furnace and the heat preservation furnace to be lower than 0.1 Pa; and then argon or nitrogen is introduced into the smelting furnace and the heat preservation furnace, so that the pressure in the furnace is 0.07-0.1 MPa.
Step two, the temperature in the smelting furnace in the step one is increased to 1150-1300 ℃, and after the raw materials are completely melted, the raw materials are poured into a heat preservation furnace for heat preservation, wherein the heat preservation temperature is 1100-1250 ℃; and (3) after the metal melt is insulated for 3-10 min in the heat preservation furnace, drawing out a manganese white copper alloy rod blank through horizontal continuous casting equipment.
And thirdly, carrying out grooved rolling on the manganese white copper cast ingot in the second step, wherein the rolling strain is 1.2-4.0.
And fourthly, annealing the manganese white copper in the third step, wherein the annealing is performed in a protective atmosphere of argon or nitrogen and the like, the annealing temperature is 500-800 ℃, and the annealing time is 10-60 min.
And fifthly, sequentially carrying out acid washing, alkali washing, saponification treatment and drying on the manganese white copper in the heat treatment state in the step four, and removing oxides on the surface of the alloy.
And step six, drawing the manganese white copper alloy in the step five, wherein the drawing strain is 2.0-5.0.
And step seven, annealing the manganese white copper alloy in the step six, wherein the annealing is performed under the protective atmosphere of argon or nitrogen and the like, the annealing temperature is 500-800 ℃, the annealing time is 10-60 min, and the cooling speed in the cooling process after heat preservation is 5-40 ℃/min.
And step eight, sequentially carrying out acid washing, alkali washing, saponification treatment and drying on the manganese white copper in the heat treatment state in the step seven, and removing oxides on the surface of the alloy.
And step nine, carrying out multi-pass drawing on the manganese white copper in the step eight, and drawing to the size of a finished product.
And step ten, carrying out aging treatment on the manganese white copper in the step nine, wherein the aging treatment is carried out under the protection of argon or nitrogen, the aging temperature is 300-450 ℃, and the heat preservation time is 0.5-8 h.
And step eleven, sequentially carrying out acid washing, alkali washing, saponification treatment and drying on the manganese white copper in the annealed state in the step ten to obtain a manganese white copper finished product.
In the first step, pure copper, pure manganese, pure nickel, pure titanium, pure silver and pure tin with the mass purity not lower than 99.95% are used as raw materials.
Further, in the drawing process of the manganese-copper alloy rod blank in the second step, the horizontal drawing speed is 3-10 mm/s, the pause time is 0.1-0.4 s, and the cooling water flow is 100-300L/min; the diameter of the prepared manganese white copper alloy rod blank is 8-20 mm, and the oxygen content of the rod blank is less than 8ppm.
Further, the manganese white copper in the step seven is mainly composed of a copper-based solid solution, and the volume fraction of the copper-based solid solution phase is more than 99%; at this time, the elongation of the alloy is more than 35%.
Further, the volume fraction of discontinuous desolventized structure formed in the manganese white copper alloy in the step ten is less than 20%; the KAM value of the longitudinal section of the manganese white copper alloy measured by adopting an EBSD method is between 0.8 and 2.8; a large amount of NiMn phase particles are dispersed in the alloy matrix, the average particle size of the NiMn phase particles is 3-32 nm, and the volume fraction of the NiMn phase is about 3% -20%.
Strain in the present inventionηAccording to the formulaη=ln(A 0 Calculated according to A), wherein A 0 The cross-sectional area of the alloy before deformation is shown as A, and the cross-sectional area of the alloy after deformation is shown as A.
The KAM (Kernel Average Misorientation) value of the manganese copper provided by the invention can reflect the average orientation difference of the local micro-areas inside the material. The dislocation density inside the alloy can be effectively reacted by counting the Kernel average orientation difference of the micro-area, and the higher the KAM value is, the higher the dislocation density is. In the present invention KAM values are obtained using EBSD measurements. In addition, the average grain size of the alloy is derived from the statistical results of EBSD.
The invention has the following beneficial effects:
(1) According to the invention, by adding alloying elements such as Ti, ag, sn and the like, the three microalloying elements can be dissolved in a copper matrix in the form of solid solution atoms to form a substitutional solid solution, and particularly under the condition that the mass ratio of Mn to Ni is greater than 1.2, the manganese-cupronickel alloy has higher resistivity and lower resistance temperature coefficient; in addition, the addition of Ti, ag, sn and other alloy elements can effectively inhibit the formation of discontinuous desolventizing tissues, so that the tissue uniformity of the manganese white copper product is improved, the performance stability of the manganese white copper is improved, and meanwhile, the temperature coefficient of resistance of the manganese white copper is reduced.
(2) According to the invention, the vacuum continuous smelting and casting technology is adopted to prepare the manganese white copper casting blank, and as the casting is carried out under the atmosphere protection condition, the oxygen content in the alloy can be effectively reduced; in addition, the vacuum continuous smelting and casting technology can be adopted to prepare manganese white copper alloy casting blanks with multiple sizes and specifications.
(3) The preparation method of the manganese white copper comprises the working procedures of roller rolling, drawing, recrystallization annealing, aging and the like. Dislocation density in the crystal grains can be effectively controlled by controlling the drawing strain quantity, so that the resistivity of the alloy is improved; the manganese white copper can undergo a recovery recrystallization reaction in the annealing process, so that a recrystallization structure is formed, the grain size of the alloy can be controlled to a certain extent, and the anisotropy of the alloy performance is weakened; the Mn-white copper can introduce NiMn phase with low temperature resistivity and high hardness in the aging process, so that the temperature resistivity and the strength of the alloy are further improved.
(4) The manganese white copper has the advantages of low resistance temperature coefficient, high strength, high elastic modulus and the like, the tensile strength of the manganese white copper is 600-1100 MPa, the elastic modulus is 128-138 GPa, the elongation is 1.5-12%, and the resistance temperature coefficient alpha is-3.0x10 -5 ℃ -1 ~2.1×10 -5 ℃ -1 The temperature coefficient of resistance beta is-8 multiplied by 10 -7 ℃ -1 ~-1×10 -7 ℃ -1 Average temperature coefficient of resistance alpha in the range of 20 ℃ to 120 DEG C 20,120 Is-60×10 -6 ℃ -1 ~-5.0×10 -6 ℃ -1 The comprehensive performance is excellent.
Drawings
FIG. 1 shows nano-scale NiMn phase particles precipitated during aging of the manganese white copper material for precision resistors of the present invention;
FIG. 2 shows a discontinuous desolventized structure of the manganese white copper material for precision resistor, which is formed at the grain boundary.
Description of the embodiments
In order to further illustrate the invention, preferred embodiments of the invention are described below in connection with examples. The examples are presented for further illustration of features and advantages of the present invention and should not be construed as limiting the invention in any way.
Examples
The manganese white copper with high strength and low resistance temperature coefficient comprises the following components in percentage by mass: 15. 15 wt% of Ni element, 20. 20wt% of Mn element, 1.5. 1.5 wt% of Sn element, 0.4. 0.4 wt% of Ti element, 1.5. 1.5 wt% of Ag element, and the balance of copper and unavoidable impurities, wherein the total content of impurities is less than 50ppm. The mass ratio of Mn to Ni was 1.33. The preparation method of the manganese white copper comprises the following specific process steps:
firstly, taking pure copper, pure manganese, pure nickel, pure titanium, pure silver and pure tin with the mass purity not lower than 99.95% as raw materials, adding the raw materials into a smelting furnace in a vacuum continuous smelting and casting system, vacuumizing the smelting furnace and a heat preservation furnace in the vacuum continuous smelting and casting system, and keeping the vacuum degree of the smelting furnace and the heat preservation furnace lower than 0.1 Pa; subsequently, argon gas was introduced into the melting furnace and the holding furnace to set the pressure in the furnace to 0.095 MPa.
Step two, raising the temperature in the smelting furnace in the step one to 1200 ℃, pouring the melted raw materials into a heat preservation furnace for heat preservation when the raw materials are completely melted, wherein the heat preservation temperature is 1150 ℃; after the metal melt is preserved for 5 min in a heat preservation furnace, a manganese white copper alloy rod blank with the diameter of phi 12mm is pulled out by horizontal continuous casting equipment. In the drawing process of the manganese white copper alloy rod blank, the horizontal drawing speed is 4 mm/s, the dwell time is 0.2 s, and the cooling water flow rate is 120L/min. The impurity elements in the drawn alloy casting blank comprise oxygen and sulfur, wherein the oxygen content is 4.2ppm, and the sulfur content is 16ppm.
And thirdly, carrying out grooved rolling on the manganese cupronickel cast ingot in the second step, and rolling into a wire rod with the diameter of phi 6 mm, wherein the rolling strain is 1.38.
And fourthly, annealing the manganese white copper in the third step, wherein the annealing is performed in an argon atmosphere, the annealing temperature is 700 ℃, and the annealing time is 60 minutes.
And fifthly, sequentially carrying out acid washing, alkali washing, saponification treatment and drying on the manganese white copper in the heat treatment state in the step four, and removing oxides on the surface of the alloy.
And step six, drawing the manganese white copper alloy in the step five until the diameter is phi 2mm and the drawing strain is 2.2.
And step seven, annealing the manganese white copper alloy in the step six, wherein the annealing is performed under the protective atmosphere of argon or nitrogen and the like, the annealing temperature is 700 ℃, the annealing time is 60min, and the cooling speed in the cooling process after heat preservation is 10 ℃/min. The annealed manganese white copper mainly comprises a copper-based solid solution, and the volume fraction of the copper-based solid solution phase is more than 99%; at this time, the elongation of the alloy was 42%.
And step eight, sequentially carrying out acid washing, alkali washing, saponification treatment and drying on the manganese white copper in the heat treatment state in the step seven, and removing oxides on the surface of the alloy.
And step nine, carrying out multi-pass drawing on the manganese white copper in the step eight, and drawing to obtain an alloy finished product with the diameter phi of 1.5 and mm, wherein the drawing strain is 0.58.
And step ten, carrying out aging treatment on the manganese white copper in the step nine, wherein the aging treatment is carried out under the protection of argon, the aging temperature is 430 ℃, and the heat preservation time is 16 h. At this time, as shown in FIG. 2, the volume fraction of the discontinuous desolventized structure formed in the manganese-white copper alloy was 4.0%, and the KAM value of the longitudinal section of the alloy was 0.86; as shown in FIG. 1, a large amount of NiMn phase particles were dispersed in the alloy matrix, the average particle size of the NiMn phase particles was 24.2 nm, and the volume fraction of the NiMn phase was about 12.4%.
And step eleven, sequentially carrying out acid washing, alkali washing, saponification treatment and drying on the manganese white copper in the annealed state in the step ten to obtain a manganese white copper finished product. At this time, the room temperature tensile strength of the manganese white copper was 926 MPa, the elastic modulus was 134 GPa, the elongation was 2.5%, and the temperature coefficient of resistance α was 1.6X10 -5 ℃ -1 The temperature coefficient of resistance beta is-3.4X10 -7 ℃ -1 Average temperature coefficient of resistance alpha in the range of 20 ℃ to 120 DEG C 20,120 is-1.7X10 -5 ℃ -1 。
Examples
The manganese white copper with high strength and low resistance temperature coefficient comprises the following components in percentage by mass: 15. 15 wt% of Ni element, 25% by weight of Mn element, 1.8% wt% of Sn element, 0.8% wt% of Ti element, 2.0% wt% of Ag element, and the balance of copper and unavoidable impurities, wherein the total content of impurities is less than 50ppm. The mass ratio of Mn to Ni was 1.66. The preparation method of the manganese white copper comprises the following specific process steps:
firstly, taking pure copper, pure manganese, pure nickel, pure titanium, pure silver and pure tin with the mass purity not lower than 99.95% as raw materials, adding the raw materials into a smelting furnace in a vacuum continuous smelting and casting system, vacuumizing the smelting furnace and a heat preservation furnace in the vacuum continuous smelting and casting system, and keeping the vacuum degree of the smelting furnace and the heat preservation furnace lower than 0.1 Pa; subsequently, argon is introduced into the smelting furnace and the holding furnace, so that the pressure in the furnace is 0.09 MPa.
Step two, raising the temperature in the smelting furnace in the step one to 1200 ℃, pouring the melted raw materials into a heat preservation furnace for heat preservation when the raw materials are completely melted, wherein the heat preservation temperature is 1150 ℃; after the metal melt is preserved for 5 min in a heat preservation furnace, a manganese white copper alloy rod blank with the diameter of phi 12mm is pulled out by horizontal continuous casting equipment. In the drawing process of the manganese white copper alloy rod blank, the horizontal drawing speed is 4 mm/s, the dwell time is 0.2 s, and the cooling water flow rate is 120L/min. The impurity elements in the drawn alloy casting blank comprise oxygen and sulfur, wherein the oxygen content is 5.6ppm, and the sulfur content is 14 ppm.
And thirdly, carrying out grooved rolling on the manganese cupronickel cast ingot in the second step, and rolling into a wire rod with the diameter of phi 6 mm, wherein the rolling strain is 1.38.
And fourthly, annealing the manganese white copper in the third step, wherein the annealing is performed in an argon atmosphere, the annealing temperature is 700 ℃, and the annealing time is 60 minutes.
And fifthly, sequentially carrying out acid washing, alkali washing, saponification treatment and drying on the manganese white copper in the heat treatment state in the step four, and removing oxides on the surface of the alloy.
And step six, drawing the manganese white copper alloy in the step five until the diameter is phi 2mm and the drawing strain is 2.2.
And step seven, annealing the manganese white copper alloy in the step six, wherein the annealing is performed under the protective atmosphere of argon or nitrogen and the like, the annealing temperature is 650 ℃, the annealing time is 60min, and the cooling speed in the cooling process after heat preservation is 8 ℃/min. The annealed manganese white copper mainly comprises a copper-based solid solution, and the volume fraction of the copper-based solid solution phase is more than 99%; at this time, the elongation of the alloy was 44%.
And step eight, sequentially carrying out acid washing, alkali washing, saponification treatment and drying on the manganese white copper in the heat treatment state in the step seven, and removing oxides on the surface of the alloy.
And step nine, carrying out multi-pass drawing on the manganese white copper in the step eight, and drawing to obtain an alloy finished product with the diameter of phi 1 mm, wherein the drawing strain is 1.39.
And step ten, carrying out aging treatment on the manganese white copper in the step nine, wherein the aging treatment is carried out under the protection of argon, the aging temperature is 450 ℃, and the heat preservation time is 10 h. At this time, the volume fraction of the discontinuous desolventized structure formed in the manganese white copper alloy was 1.6%, and the KAM value of the longitudinal section of the alloy was 1.2; a large amount of NiMn phase particles are dispersed in the alloy matrix, the average particle size of the NiMn phase particles is 19.3 nm, and the volume fraction of the NiMn phase is about 10.5%.
And step eleven, sequentially carrying out acid washing, alkali washing, saponification treatment and drying on the manganese white copper in the annealed state in the step ten to obtain a manganese white copper finished product. At this time, the room temperature tensile strength of the manganese white copper was 1142 MPa, the elastic modulus was 134 GPa, the elongation was 4.5%, and the temperature coefficient of resistance α was 1.3X10 -5 ℃ -1 The temperature coefficient of resistance beta is-2.1 multiplied by 10 -7 ℃ -1 Average temperature coefficient of resistance alpha in the range of 20 ℃ to 120 DEG C 20,120 is-1.4X10 -5 ℃ -1 。
Examples
The manganese white copper with high strength and low resistance temperature coefficient comprises the following components in percentage by mass: 16. 16 wt% of Ni, 25. 25wt% of Mn, 2.0. 2.0 wt% of Sn, 1.0. 1.0 wt% of Ti, 2.5. 2.5 wt% of Ag, and the balance of copper and unavoidable impurities, wherein the total content of impurities is less than 50ppm. The mass ratio of Mn to Ni was 1.56. The preparation method of the manganese white copper comprises the following specific process steps:
firstly, taking pure copper, pure manganese, pure nickel, pure titanium, pure silver and pure tin with the mass purity not lower than 99.95% as raw materials, adding the raw materials into a smelting furnace in a vacuum continuous smelting and casting system, vacuumizing the smelting furnace and a heat preservation furnace in the vacuum continuous smelting and casting system, and keeping the vacuum degree of the smelting furnace and the heat preservation furnace lower than 0.1 Pa; subsequently, argon gas was introduced into the melting furnace and the holding furnace to set the pressure in the furnace to 0.095 MPa.
Step two, raising the temperature in the smelting furnace in the step one to 1200 ℃, pouring the melted raw materials into a heat preservation furnace for heat preservation when the raw materials are completely melted, wherein the heat preservation temperature is 1150 ℃; after the metal melt is preserved for 5 min in a heat preservation furnace, a manganese white copper alloy rod blank with the diameter phi of 16 mm is pulled out by horizontal continuous casting equipment. In the drawing process of the manganese white copper alloy rod blank, the horizontal drawing speed is 4 mm/s, the pause time is 0.2 s, and the cooling water flow rate is 260L/min. The impurity elements in the drawn alloy casting blank comprise oxygen and sulfur, wherein the oxygen content is 4.8ppm, and the sulfur content is 21ppm.
And thirdly, carrying out grooved rolling on the manganese cupronickel cast ingot in the second step, and rolling into a wire rod with the diameter of phi 6 mm, wherein the rolling strain is 1.96.
And fourthly, annealing the manganese white copper in the third step, wherein the annealing is performed in an argon atmosphere, the annealing temperature is 650 ℃, and the annealing time is 60 minutes.
And fifthly, sequentially carrying out acid washing, alkali washing, saponification treatment and drying on the manganese white copper in the heat treatment state in the step four, and removing oxides on the surface of the alloy.
And step six, drawing the manganese white copper alloy in the step five until the diameter is phi 2mm and the drawing strain is 2.2.
And step seven, annealing the manganese white copper alloy in the step six, wherein the annealing is performed under the protective atmosphere of argon or nitrogen and the like, the annealing temperature is 650 ℃, the annealing time is 60min, and the cooling speed in the cooling process after heat preservation is 10 ℃/min. The annealed manganese white copper mainly comprises a copper-based solid solution, and the volume fraction of the copper-based solid solution phase is more than 99%; at this time, the elongation of the alloy was 45%.
And step eight, sequentially carrying out acid washing, alkali washing, saponification treatment and drying on the manganese white copper in the heat treatment state in the step seven, and removing oxides on the surface of the alloy.
And step nine, carrying out multi-pass drawing on the manganese white copper in the step eight, and drawing to obtain an alloy finished product with the diameter phi of 0.9 and mm, wherein the drawing strain is 1.6.
And step ten, carrying out aging treatment on the manganese white copper in the step nine, wherein the aging treatment is carried out under the protection of argon, the aging temperature is 450 ℃, and the heat preservation time is 12 h. At this time, the volume fraction of the discontinuous desolventized structure formed in the manganese white copper alloy was 0%, and the KAM value of the longitudinal section of the alloy was 1.6; a large amount of NiMn phase particles are dispersed in the alloy matrix, the average particle size of the NiMn phase particles is 16.8 nm, and the volume fraction of the NiMn phase is about 13.9%.
And step eleven, sequentially carrying out acid washing, alkali washing, saponification treatment and drying on the manganese white copper in the annealed state in the step ten to obtain a manganese white copper finished product. At this time, the room temperature tensile strength of the manganese white copper was 1134 MPa, the elastic modulus was 134 GPa, the elongation was 8.6%, and the temperature coefficient of resistance α was 1.1X10 -5 ℃ -1 The temperature coefficient of resistance beta is-2.6X10 -7 ℃ -1 Average temperature coefficient of resistance alpha in the range of 20 ℃ to 120 DEG C 20,120 is-1.5X10 -5 ℃ -1 。
Examples
The manganese white copper with high strength and low resistance temperature coefficient comprises the following components in percentage by mass: 20. 20wt% of Ni element, 24% of Mn element, 1.5% of wt% of Sn element, 0.2% of wt% of Ti element, 1.5% of wt% of Ag element, and the balance of copper and unavoidable impurities, wherein the total content of impurities is less than 50ppm. The mass ratio of Mn to Ni was 1.22. The preparation method of the manganese white copper comprises the following specific process steps:
firstly, taking pure copper, pure manganese, pure nickel, pure titanium, pure silver and pure tin with the mass purity not lower than 99.95% as raw materials, adding the raw materials into a smelting furnace in a vacuum continuous smelting and casting system, vacuumizing the smelting furnace and a heat preservation furnace in the vacuum continuous smelting and casting system, and keeping the vacuum degree of the smelting furnace and the heat preservation furnace lower than 0.1 Pa; subsequently, argon is introduced into the smelting furnace and the holding furnace, so that the pressure in the furnace is 0.09 MPa.
Step two, raising the temperature in the smelting furnace in the step one to 1200 ℃, pouring the melted raw materials into a heat preservation furnace for heat preservation when the raw materials are completely melted, wherein the heat preservation temperature is 1150 ℃; after the metal melt is preserved for 10min in a heat preservation furnace, a manganese white copper alloy rod blank with the diameter of phi 20mm is pulled out through horizontal continuous casting equipment. In the drawing process of the manganese white copper alloy rod blank, the horizontal drawing speed is 4 mm/s, the pause time is 0.2 s, and the cooling water flow rate is 240L/min. The impurity elements in the drawn alloy casting blank comprise oxygen and sulfur, wherein the oxygen content is 5.8ppm, and the sulfur content is 24 ppm.
And thirdly, carrying out grooved rolling on the manganese cupronickel cast ingot in the second step, and rolling into a wire rod with the diameter of phi 8mm, wherein the rolling strain is 1.83.
And fourthly, annealing the manganese white copper in the third step, wherein the annealing is performed in an argon atmosphere, the annealing temperature is 600 ℃, and the annealing time is 60 minutes.
And fifthly, sequentially carrying out acid washing, alkali washing, saponification treatment and drying on the manganese white copper in the heat treatment state in the step four, and removing oxides on the surface of the alloy.
And step six, drawing the manganese white copper alloy in the step five until the diameter is phi 3 mm, wherein the drawing strain is 1.96.
And step seven, annealing the manganese white copper alloy in the step six, wherein the annealing is performed under the protective atmosphere of argon or nitrogen and the like, the annealing temperature is 650 ℃, the annealing time is 60min, and the cooling speed in the cooling process after heat preservation is 6 ℃/min. The annealed manganese white copper mainly comprises a copper-based solid solution, and the volume fraction of the copper-based solid solution phase is more than 99%; at this time, the elongation of the alloy was 42%.
And step eight, sequentially carrying out acid washing, alkali washing, saponification treatment and drying on the manganese white copper in the heat treatment state in the step seven, and removing oxides on the surface of the alloy.
And step nine, carrying out multi-pass drawing on the manganese white copper in the step eight, and drawing to obtain an alloy finished product with the diameter of phi 1 mm, wherein the drawing strain is 2.1.
And step ten, carrying out aging treatment on the manganese white copper in the step nine, wherein the aging treatment is carried out under the protection of argon, the aging temperature is 400 ℃, and the heat preservation time is 4 h. At this time, the volume fraction of the discontinuous desolventized structure formed in the manganese white copper alloy was 5.8%, and the KAM value of the longitudinal section of the alloy was 2.4; a large amount of NiMn phase particles are dispersed in the alloy matrix, the average particle size of the NiMn phase particles is 6.4 nm, and the volume fraction of the NiMn phase is about 8.5%.
And step eleven, sequentially carrying out acid washing, alkali washing, saponification treatment and drying on the manganese white copper in the annealed state in the step ten to obtain a manganese white copper finished product. At this time, the room temperature tensile strength of the manganese white copper was 856 MPa, the elastic modulus was 131 GPa, the elongation was 2.5%, and the temperature coefficient of resistance α was-1.7X10 -5 ℃ -1 The temperature coefficient of resistance beta is-3.8X10 -7 ℃ -1 Average temperature coefficient of resistance alpha in the range of 20 ℃ to 120 DEG C 20,120 is-2.1X10 -5 ℃ -1 。
Comparative example
The manganese white copper comprises Cu, ni, mn and other elements and unavoidable impurities, wherein the components account for the following mass proportion: the Ni element is 20wt%, the Mn element is 20wt%, and the balance is copper and unavoidable impurities, wherein the total content of impurities is less than 50ppm. The mass ratio of Mn to Ni was 1. The preparation method of the manganese white copper comprises the following specific process steps:
firstly, taking pure copper, pure manganese and pure nickel with the mass purity not lower than 99.95% as raw materials, adding the raw materials into a smelting furnace in a vacuum continuous smelting and casting system, vacuumizing the smelting furnace and a heat preservation furnace in the vacuum continuous smelting and casting system, and keeping the vacuum degree of the smelting furnace and the heat preservation furnace lower than 0.1 Pa; subsequently, argon gas was introduced into the melting furnace and the holding furnace to set the pressure in the furnace to 0.095 MPa.
Step two, raising the temperature in the smelting furnace in the step one to 1200 ℃, pouring the melted raw materials into a heat preservation furnace for heat preservation when the raw materials are completely melted, wherein the heat preservation temperature is 1150 ℃; after the metal melt is preserved for 5 min in a heat preservation furnace, a manganese white copper alloy rod blank with the diameter of phi 12mm is pulled out by horizontal continuous casting equipment. In the drawing process of the manganese white copper alloy rod blank, the horizontal drawing speed is 4 mm/s, the dwell time is 0.2 s, and the cooling water flow rate is 120L/min. The impurity elements in the drawn alloy casting blank comprise oxygen and sulfur, wherein the oxygen content is 7.4 ppm, and the sulfur content is 20 ppm.
And thirdly, carrying out grooved rolling on the manganese cupronickel cast ingot in the second step, and rolling into a wire rod with the diameter of phi 6 mm, wherein the rolling strain is 1.38.
And fourthly, annealing the manganese white copper in the third step, wherein the annealing is performed in an argon atmosphere, the annealing temperature is 700 ℃, and the annealing time is 60 minutes.
And fifthly, sequentially carrying out acid washing, alkali washing, saponification treatment and drying on the manganese white copper in the heat treatment state in the step four, and removing oxides on the surface of the alloy.
And step six, drawing the manganese white copper alloy in the step five until the diameter is phi 2mm and the drawing strain is 2.2.
And step seven, annealing the manganese white copper alloy in the step six, wherein the annealing is performed under the protective atmosphere of argon or nitrogen and the like, the annealing temperature is 700 ℃, the annealing time is 60min, and the cooling speed in the cooling process after heat preservation is 10 ℃/min. The annealed manganese white copper mainly comprises a copper-based solid solution, and the volume fraction of the copper-based solid solution phase is more than 99%; at this time, the elongation of the alloy was 35%.
And step eight, sequentially carrying out acid washing, alkali washing, saponification treatment and drying on the manganese white copper in the heat treatment state in the step seven, and removing oxides on the surface of the alloy.
And step nine, carrying out multi-pass drawing on the manganese white copper in the step eight, and drawing to obtain an alloy finished product with the diameter phi of 1.5 and mm, wherein the drawing strain is 0.58.
And step ten, carrying out aging treatment on the manganese white copper in the step nine, wherein the aging treatment is carried out under the protection of argon, the aging temperature is 430 ℃, and the heat preservation time is 16 h. At this time, the volume fraction of the discontinuous desolventized structure formed in the manganese white copper alloy was 24%, and the KAM value of the longitudinal section of the alloy was 0.8; a large amount of NiMn phase particles are dispersed in the alloy matrix, the average particle size of the NiMn phase particles is 34.2 nm, and the volume fraction of the NiMn phase is about 16.1%.
And step eleven, sequentially carrying out acid washing, alkali washing, saponification treatment and drying on the manganese white copper in the annealed state in the step ten to obtain a manganese white copper finished product. At this time, the room temperature tensile strength of the manganese white copper was 839 MPa, the elastic modulus was 134 GPa, the elongation was 1.0%, and the temperature coefficient of resistance α was 2.0X10 -5 ℃ -1 The temperature coefficient of resistance beta is-4.4X10 -7 ℃ -1 Between 20 ℃ and 120 DEG CThe average temperature coefficient of resistance alpha of (a) 20,120 is-2.4X10 -5 ℃ -1 。
TABLE 1 tissue Properties and Performance index of the composite Material of the invention
The above examples are for illustration of the invention only and, in addition, there are many different embodiments which will be apparent to those skilled in the art after having the insight into the present invention and are not explicitly recited herein.
Claims (6)
1. The manganese white copper material for the precision resistor is characterized by comprising the following components: 15-20wt% of Ni, 18-25wt% of Mn, 1.5-2.5wt% of Ag, 1.0-2.0wt% of Sn, 0.2-1.0wt% of Ti and the balance of Cu plus unavoidable impurities, wherein the mass ratio of Mn to Ni is greater than 1.2.
2. The method for preparing the manganese white copper material for the precision resistor according to claim 1, comprising the following steps:
firstly, adding raw materials into a smelting furnace in a vacuum continuous smelting and casting system, vacuumizing the smelting furnace and a heat preservation furnace in the vacuum continuous smelting and casting system, and keeping the vacuum degree of the smelting furnace and the heat preservation furnace to be lower than 0.1 Pa; then, argon or nitrogen is introduced into the smelting furnace and the heat preservation furnace, so that the pressure in the furnace is 0.07-0.1 MPa;
step two, the temperature in the smelting furnace in the step one is increased to 1150-1300 ℃, and after the raw materials are completely melted, the raw materials are poured into a heat preservation furnace for heat preservation, wherein the heat preservation temperature is 1100-1250 ℃; drawing out a manganese white copper alloy rod blank from the metal melt through horizontal continuous casting equipment after the metal melt is subjected to heat preservation for 3-10 min in a heat preservation furnace;
step three, carrying out grooved rolling on the manganese white copper cast ingot in the step two, wherein the rolling strain is 1.2-4.0;
fourthly, annealing the manganese white copper in the third step, wherein the annealing is performed in a protective atmosphere of argon or nitrogen and the like, the annealing temperature is 500-800 ℃, and the annealing time is 10-60 min;
step five, sequentially carrying out acid washing, alkali washing, saponification treatment and drying on the manganese white copper in the heat treatment state in the step four, and removing oxides on the surface of the alloy;
step six, drawing the manganese white copper alloy in the step five, wherein the drawing strain is 2.0-5.0;
step seven, annealing the manganese white copper alloy in the step six, wherein the annealing is performed under the protective atmosphere of argon or nitrogen and the like, the annealing temperature is 500-800 ℃, the annealing time is 10-60 min, and the cooling speed in the cooling process after heat preservation is 5-40 ℃/min;
step eight, sequentially carrying out acid washing, alkali washing, saponification treatment and drying on the manganese white copper in the heat treatment state in the step seven, and removing oxides on the surface of the alloy;
step nine, carrying out multi-pass drawing on the manganese white copper in the step eight, and drawing to the size of a finished product;
step ten, aging treatment is carried out on the manganese white copper in the step nine, aging is carried out under the protection of argon or nitrogen, the aging temperature is 300-450 ℃, and the heat preservation time is 0.5-8 h;
and step eleven, sequentially carrying out acid washing, alkali washing, saponification treatment and drying on the manganese white copper in the annealed state in the step ten to obtain a manganese white copper finished product.
3. The method for producing a manganese white copper material for precision resistors according to claim 2, wherein in the first step, pure copper, pure manganese, pure nickel, pure titanium, pure silver, and pure tin having a mass purity of not less than 99.95% are used as raw materials.
4. The method for preparing the manganese-copper alloy material for the precise resistor according to claim 2, wherein in the drawing process of the manganese-copper alloy rod blank in the second step, the horizontal drawing speed is 3-10 mm/s, the pause time is 0.1-0.4 s, and the cooling water flow is 100-300L/min.
5. The method for producing a manganese white copper material for precision resistors according to claim 2, wherein the manganese white copper in the seventh step mainly consists of a copper-based solid solution, and the volume fraction of the copper-based solid solution phase is more than 99%; the elongation percentage of the alloy is more than 35 percent.
6. The method for producing a manganese white copper material for precision resistors according to claim 2, wherein the discontinuous desolventized structure formed in the manganese white copper alloy in the step ten has a volume fraction of less than 20%; the KAM value of the longitudinal section of the manganese white copper alloy measured by adopting an EBSD method is between 0.8 and 2.8; a large amount of NiMn phase particles are dispersed in the alloy matrix, the average particle size of the NiMn phase particles is 3-32 nm, and the volume fraction of the NiMn phase is about 3% -20%.
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