CN114875270B - Tin-phosphor bronze alloy and preparation method thereof - Google Patents
Tin-phosphor bronze alloy and preparation method thereof Download PDFInfo
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- CN114875270B CN114875270B CN202210510732.XA CN202210510732A CN114875270B CN 114875270 B CN114875270 B CN 114875270B CN 202210510732 A CN202210510732 A CN 202210510732A CN 114875270 B CN114875270 B CN 114875270B
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- 229910000906 Bronze Inorganic materials 0.000 title claims abstract description 32
- BSPSZRDIBCCYNN-UHFFFAOYSA-N phosphanylidynetin Chemical compound [Sn]#P BSPSZRDIBCCYNN-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims description 8
- 238000012545 processing Methods 0.000 claims abstract description 48
- 239000000463 material Substances 0.000 claims abstract description 33
- 238000005520 cutting process Methods 0.000 claims abstract description 22
- 239000012535 impurity Substances 0.000 claims abstract description 3
- 238000000137 annealing Methods 0.000 claims description 104
- 238000004321 preservation Methods 0.000 claims description 26
- 238000005266 casting Methods 0.000 claims description 19
- 206010040844 Skin exfoliation Diseases 0.000 claims description 15
- 239000000498 cooling water Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000003723 Smelting Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 9
- 238000009749 continuous casting Methods 0.000 claims description 7
- 238000010791 quenching Methods 0.000 claims description 6
- 230000000171 quenching effect Effects 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 2
- 238000000265 homogenisation Methods 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims 1
- 229910045601 alloy Inorganic materials 0.000 abstract description 28
- 239000000956 alloy Substances 0.000 abstract description 28
- 238000005728 strengthening Methods 0.000 abstract description 7
- 238000005482 strain hardening Methods 0.000 abstract description 6
- 239000002245 particle Substances 0.000 abstract description 4
- 239000006104 solid solution Substances 0.000 abstract description 4
- 230000036541 health Effects 0.000 abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 238000005554 pickling Methods 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 229910009038 Sn—P Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000000155 melt Substances 0.000 description 5
- 229910001096 P alloy Inorganic materials 0.000 description 4
- RIRXDDRGHVUXNJ-UHFFFAOYSA-N [Cu].[P] Chemical compound [Cu].[P] RIRXDDRGHVUXNJ-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 239000010974 bronze Substances 0.000 description 4
- 239000003610 charcoal Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052738 indium Inorganic materials 0.000 description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 238000004513 sizing Methods 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- 229910000881 Cu alloy Inorganic materials 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- -1 tin bronze series Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- 229910001215 Te alloy Inorganic materials 0.000 description 1
- 238000007545 Vickers hardness test Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- RUQACMGBLIBRPP-UHFFFAOYSA-N [Zn][Pb][Sn] Chemical compound [Zn][Pb][Sn] RUQACMGBLIBRPP-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/02—Alloys based on copper with tin as the next major constituent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/001—Continuous casting of metals, i.e. casting in indefinite lengths of specific alloys
- B22D11/004—Copper alloys
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23P—METAL-WORKING NOT OTHERWISE PROVIDED FOR; COMBINED OPERATIONS; UNIVERSAL MACHINE TOOLS
- B23P15/00—Making specific metal objects by operations not covered by a single other subclass or a group in this subclass
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/0075—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for rods of limited length
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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
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Abstract
The invention discloses a tin-phosphor bronze alloy, which is characterized in that: the tin-phosphor bronze alloy comprises the following components in percentage by mass: 8.0 to 10.0 percent; p:0.05 to 0.2 percent; in:0.2 to 1.0 percent; ni:0.05 to 0.2 percent; fe: less than or equal to 0.2 percent, and other impurities: less than or equal to 0.2 percent and the balance of Cu. The invention improves the machinability of the material by adding In element to form free-cutting particles. Compared with Pb, the In is environment-friendly and harmless to human health, the alloy still keeps good processing plasticity and mechanical property, and the conductivity of the alloy is indirectly improved, the tin-phosphor bronze alloy with excellent comprehensive performance is obtained through various modes such as solid solution strengthening, fine grain strengthening and work hardening, the tensile strength of the tin-phosphor bronze alloy is more than or equal to 1000MPa, the elongation is more than or equal to 3%, the cutting index is more than 70% of C36000, the conductivity is more than or equal to 15%.
Description
Technical Field
The invention belongs to the technical field of copper alloy, and particularly relates to a tin-phosphor bronze alloy and a preparation method thereof.
Background
The tin bronze has higher strength, elasticity and wear resistance due to the addition of tin element, and is widely applied to the fields of elastic elements, precision instrument parts, wear-resistant parts and the like. At present, the tin bronze is mainly Cu-Sn-P and Cu-Sn-Zn-P. Wherein the Cu-Sn-P series tin-phosphor bronze is strengthened by Sn element solid solution and Cu 3 The formation of the P phase significantly improves the strength, hardness and elasticity of the alloy. But the cutting performance of Cu-Sn-P series bronze is poor, turning chips are easy to curl and wrap a cutter during high-speed turning processing, the chips are difficult to break, the strength and the hardness of the material are greatly improved along with the increase of the Sn content, the higher hardness has larger abrasion degree to the cutter, and the cutter is greatly reducedThe service life of the tool is prolonged. The Cu-Sn-Zn-Pb series tin-zinc-lead bronzes improve the alloy cutting performance by adding zinc and lead elements aiming at the problem of poor cutting of the former series, but the alloy has poor cold and hot processing performance after the lead element is added, so that the alloy is not suitable for hot and cold processing forming with large processing rate, and the lead element is harmful to human health and is not environment-friendly, so the Cu-Sn-Zn-Pb series bronzes have good cutting performance, but the mechanical properties such as material strength, elasticity, hardness and the like are obviously lower than those of the Cu-Sn-P series.
The tin bronze series alloy is mainly used for increasing the strength of the material in a work hardening mode, and when the cold working rate is high, the high-temperature softening resistance of the material is poor, so that the material can still keep the high-strength characteristic under a certain high-temperature condition by adding a certain amount of Ni element.
Aiming at the limitations of the Cu-Sn-P and Cu-Sn-Zn-Pb series tin bronzes, the invention aims to develop a Cu-Sn-P series alloy with mechanical properties and easy cutting processability close to that of the Cu-Sn-Zn-Pb series alloy.
Disclosure of Invention
The first technical problem to be solved by the invention is to provide a tin-phosphor bronze alloy with excellent comprehensive properties of strength, elongation, cutting performance, electric conductivity and high-temperature softening resistance.
The technical scheme adopted by the invention for solving the first technical problem is as follows: a tin-phosphor bronze alloy characterized by: the tin-phosphor bronze alloy comprises the following components in percentage by mass: 8.0 to 10.0 percent; p:0.05 to 0.2 percent; in:0.2 to 1.0 percent; ni:0.05 to 0.2 percent; fe: less than or equal to 0.2 percent, and other impurities: less than or equal to 0.2 percent and the balance of Cu.
The alloy of the invention is based on Cu-Sn-P series, wherein Sn element plays a role in solid solution strengthening, the content range of Sn is controlled to be 8-10%, and the alloy can be ensured to have high strength and hardness. If the content of Sn is lower than 8%, the alloy strengthening effect is not obvious, and if the content of Sn is higher than 10%, the strength of the material is not obviously improved, and the brittleness of the material is further increased, so that the processing performance and the mechanical property of the material are reduced. Meanwhile, if the content of Sn is too high, the difficulty of alloy casting is further increased, and the structure segregation and the blank cracking are easily caused.
The addition of the P element plays roles of degassing and deoxidizing in the casting process on one hand, and can improve the strength of the alloy on the other hand. The upper limit of the P content is controlled to be below 0.2 percent, the purpose is to avoid reducing the processing plasticity and the conductivity of the alloy, and meanwhile, the material brittleness is increased and the mechanical property of the alloy is reduced due to the over-high P content.
The addition of the In element mainly plays a role In improving the cutting performance of the material. The low-melting-point In-delta phase is formed by cooperating with Sn element, the action of the In-delta phase is similar to that of Pb element, and the In-delta phase plays a role In reducing friction and lubricating during material machining, so that the alloy has good cutting performance. Meanwhile, the In element can increase the critical current density of the material, thereby improving the conductivity. Under certain processing conditions, the In element can promote the formation of gas mass dislocation to improve the strength of the material, and compared with Pb element, the In element has obvious brittleness characteristic, and the addition of the In element can not obviously reduce the strength of the material.
The Ni element is added to improve the strength of the alloy and further improve the high-temperature softening resistance of the alloy. The tin bronze series alloy is mainly used for increasing the strength of the material in a work hardening mode, and when the cold working rate is high, the high-temperature softening resistance of the material is poor, so that the material can still keep the high-strength characteristic under a certain high-temperature condition by adding a certain amount of Ni element.
Preferably, the microstructure of the tin-phosphor bronze alloy contains an In-delta phase, and the average size of the In-delta phase is controlled to be 0.1 to 2.0 [ mu ] m and 1mm 2 The number of In-delta phases precipitated per unit area is controlled to be 6000 or more. Good cutting performance is obtained by controlling the size and the number of the In-delta phases In unit area, and the strength of the material is not reduced.
Preferably, the tin-phosphor bronze alloy has a tensile strength of not less than 1000MPa, an elongation of not less than 3%, a cutting index of not less than 70% of C36000, an electric conductivity of not less than 15% IACS, and a high-temperature softening resistance temperature of not less than 370 ℃.
The second technical problem to be solved by the invention is to provide a preparation method of the tin-phosphor bronze alloy.
The technical scheme adopted by the invention for solving the second technical problem is as follows: a tin-phosphor bronze alloy characterized by: the preparation method comprises the following preparation steps:
1) Smelting: proportioning according to the required components;
2) Casting: adopting a horizontal continuous casting mode to cast a blank, wherein the traction speed is 0.2-1.0 m/min, the traction pitch is 1-3 mm, and the reverse thrust length is as follows: 0.1-0.5 mm, cooling water pressure: 0.5-0.8 Mpa, cooling water inlet temperature: 15-25 ℃, water outlet temperature: the casting temperature is controlled to be 1190 to 1220 ℃ at the temperature of 20 to 40 ℃;
3) Homogenizing and annealing: carrying out homogenization annealing treatment on the blank, wherein the annealing temperature range is as follows: 680-720 ℃, the heat preservation time is 6-10 h, quenching treatment is carried out on the homogenized blank after the heat preservation time is reached, and the water inlet time after discharging is controlled within 30 s;
4) First stretching: stretching the blank after the homogenizing annealing, wherein the processing rate is controlled to be 10-35%; after the stretching is finished, peeling treatment is carried out, and the peeling amount is 0.2-1 mm;
5) Intermediate high-temperature annealing: annealing the stretched blank, wherein the annealing temperature range is as follows: keeping the temperature at 520-600 ℃ for 2-5 h;
6) And (3) second stretching: stretching the blank after intermediate high-temperature annealing, wherein the second-pass stretching processing rate is controlled to be 30-60%;
7) Intermediate low-temperature annealing: annealing the stretched blank, wherein the annealing temperature range is as follows: keeping the temperature at 350-450 ℃ for 3-10 h;
8) Stretching a finished product: and (3) stretching the blank subjected to intermediate low-temperature annealing, wherein the finished product stretching is carried out in 2-4 passes, and the processing rate of each pass is controlled as follows: 10 to 30 percent, and the total stretching processing rate is 40 to 70 percent;
9) Stress relief annealing: and (3) performing stress relief annealing on the finished bar, and performing atmosphere protection, wherein the heating speed is controlled to be 5-10 ℃/min, the heat preservation temperature is controlled to be 150-200 ℃, and the heat preservation time is 4-12 h.
The casting process of the steps controls the lower traction speed, increases the pressure of the cooling water and strictly controls the temperature of the cooling water inlet and outlet water, so that the thickness of the solidified shell is continuously thickened, and the solidified shell has enough strength to be led out from the crystallizer. The reverse thrust is set and the reverse thrust amount is set to be 0.1-0.5 mm, so that the melt is compressed when being solidified, and the crystalline structure is more compact; and secondly, the vibration effect is achieved during crystallization, crystal grains are refined, the number of radial columnar crystals is reduced, so that the strength and plasticity of the casting blank are improved, the area percentage of the finally obtained horizontal continuous casting blank radial columnar crystals is controlled to be below 50%, the smaller the number of the radial columnar crystals is, the higher the plasticity of the casting blank is, the tensile strength and the elongation of the casting blank can respectively reach above 400MPa and 20%, and the good subsequent cold processing performance is achieved.
The steps are homogenized and annealed, and the purpose is as follows: because the Sn content of the alloy is high, the Sn element segregation problem needs to be eliminated by adopting high homogenizing annealing temperature, and the lower limit temperature of 680 ℃ is set to ensure that the Sn content deviation of the center and the edge of the blank is controlled within 0.3 percent. Purpose two: greatly improves the processing plasticity of the blank, has the elongation rate of more than 70 percent and meets the requirement of the subsequent large processing rate stretching. The upper limit temperature of 720 ℃ is set to avoid excessive growth of crystal grains due to overhigh temperature, which causes uneven structure, and material thermal cracking due to overhigh temperature. After reaching the holding time, the homogenized blank is quenched to maintain a high-temperature phase, and the high-temperature phase is characterized in that: the alpha phase and the In-delta phase are distributed, wherein the In-delta phase is uniformly distributed In particle particles, the aggregation and growth of the In-delta phase are reduced as much as possible, and the In-delta phase is converted into a dendritic phase, and if the In-delta phase is distributed In a large-area dendritic phase, the improvement of the processing plasticity of the material is not facilitated.
The first stretching in the steps is carried out, the processing rate is controlled to be 10-35%, the material is subjected to certain processing hardening, the subsequent peeling procedure can be smoothly carried out, and the phenomenon of nonuniform peeling caused by high plasticity is avoided. After peeling off, the fine defects such as surface crystal grains and the like can be eliminated, and the surface quality of the blank is improved.
The high-temperature annealing in the middle of the steps enables the blank structure after the first drawing to be recrystallized, the longitudinal strip-shaped processing structure is effectively eliminated, the area proportion of 80 percent before the annealing is reduced to be within 10 percent, the uniformity of the structure is improved, the upper limit temperature of 600 ℃ is controlled, the average grain size of the structure is effectively controlled to be below 30 mu m, and the elongation is more than 60 percent. If the temperature is further increased, the plasticity is not obviously improved, so the annealing temperature is controlled within the range of 520-600 ℃ to ensure that the structure is recrystallized and the plasticity of the material keeps ideal processing conditions.
The intermediate low-temperature annealing in the steps can effectively improve the plasticity of the blank, the elongation after annealing can reach more than 50 percent, and the lower annealing temperature effectively controls the average grain size of the structure to be less than 5 mu m, thereby achieving the purpose of fine grain strengthening. If the temperature is further increased, the crystal grains tend to grow, and the effect of fine grains cannot be realized. The second drawing processing rate is controlled to be 30-60% in combination with the steps, and the recrystallization temperature can be reduced by a larger processing rate, so that the ideal conditions of fine grains and high plasticity can be realized under the annealing condition in a lower temperature range by the intermediate low-temperature annealing process in the step.
The finished product is stretched in 2-4 passes, and the processing rate of each pass is controlled as follows: 10 to 30 percent. The alloy is stretched in multiple passes, residual stress formed in the stretching process can be eliminated uniformly, the axial and radial residual stress values are controlled within 200MPa, and the phenomenon that the residual stress is overlarge after single-pass high-machining-rate machining is avoided. If the residual stress is too large, the strength and plasticity of the material are reduced. The total processing rate is controlled to be 40-70%, and the purpose is to fully utilize the processing hardening effect of the material and provide the tensile strength of the finished product.
The stress relief annealing in the steps aims to further eliminate the internal stress of the hard bar of the finished product, control the axial residual stress value and the radial residual stress value within 80MPa and improve the performance uniformity of the finished product. Meanwhile, the low-temperature long-time heat preservation annealing is beneficial to further improving the strength and the hardness of the material. After the stress relief annealing of the finished product, the tensile strength of the material is stabilized above 1000MPa, and the elongation is kept above 3%.
Preferably, in the step 2), the area ratio of the radial columnar crystals of the obtained ingot is controlled to be 50% or less.
Preferably, in the step 3), after annealing, the Sn content deviation of the center and edge parts of the blank is controlled within 0.3%, the In-delta phase is granular, and the elongation of the blank is more than 70%.
Preferably, in the step 5), the area ratio of the longitudinal long processed structure in the annealed blank is reduced to be within 10%, the average grain size of the structure is below 30 μm, and the elongation is above 60%.
Preferably, in the step 7), the average grain size of the structure after annealing is 5 μm or less, and the elongation is 50% or more.
Preferably, in the step 8), the axial residual stress value and the radial residual stress value of the bar after stretching are both controlled within 200 MPa.
Preferably, in the step 9), the axial residual stress value and the radial residual stress value of the bar after annealing are both controlled within 80 MPa.
Compared with the prior art, the invention has the advantages that: the invention improves the machinability of the material by adding In element to form free-cutting particles. Compared with Pb, the In is environment-friendly and harmless to human health, the alloy still keeps good processing plasticity and mechanical property, and the conductivity of the alloy is indirectly improved, the tin-phosphor bronze alloy with excellent comprehensive performance is obtained through various modes such as solid solution strengthening, fine grain strengthening and work hardening, the tensile strength of the tin-phosphor bronze alloy is more than or equal to 1000MPa, the elongation is more than or equal to 3%, the cutting index is more than 70% of C36000, the conductivity is more than or equal to 15%.
Drawings
FIG. 1 is a photograph of a metallographic structure of a sample of example 1 of the present invention.
FIG. 2 is a photograph of a metallographic structure of comparative example 1 of the present invention.
Detailed Description
The invention is described in further detail below with reference to the accompanying examples.
The invention provides 4 examples and 2 comparative examples, the specific components of which are shown in Table 1.
Example 1
1) Smelting: proportioning according to the component requirements, sequentially adding an electrolytic plate, a tin ingot, metal indium and a nickel ingot into an intermediate frequency furnace, heating, controlling the initial temperature to be 1220 ℃, adding a slag removing agent after the raw materials are completely melted, uniformly stirring for 4min, adding a copper-phosphorus alloy, controlling the smelting temperature to be 1200 ℃, and uniformly stirring the melt. And (4) sampling, testing and transferring to a holding furnace after the components are tested to be qualified, adding charcoal to cover, wherein the covering thickness is 50mm.
2) Casting: and (4) adopting a horizontal continuous casting mode to cast a blank. Wherein the traction speed is 0.3m/min, the traction pitch is 2mm, the reverse thrust length: 0.2mm, cooling water pressure: 0.6Mpa, cooling water inlet temperature: 18-25 ℃, water outlet temperature: 25-35 ℃, the casting temperature is controlled at 1200 ℃, and the traction blank specification is as follows:
3) Homogenizing and annealing: placing the blank in a well type furnace for homogenizing annealing treatment, wherein the annealing temperature is as follows: 690 ℃ and the heat preservation time is 8h. And quenching the homogenized blank after the heat preservation time is reached, and controlling the water inlet time within 30s after the blank is discharged from the furnace.
4) First stretching: pickling the blank after the homogenizing annealing, placing the blank in an inverted disc drawing machine for drawing, wherein the total processing rate of the first drawing is 34%, and peeling is carried out after the drawing is finished, wherein the peeling amount is 0.5mm, so that the blank is obtained
And (5) coiling a round bar blank.
5) Intermediate high-temperature annealing: placing the stretched hard blank in a pit furnace for annealing treatment, wherein the annealing temperature is as follows: keeping the temperature at 550 ℃ for 3h.
6) And (3) second stretching: pickling the blank subjected to intermediate high-temperature annealing, placing the blank in an inverted disc drawing machine for drawing, wherein the total processing rate of the second drawing is 52 percent, and obtaining the alloy
And (5) coiling a round bar blank.
7) Intermediate low-temperature annealing: and (3) placing the stretched hard blank in a pit furnace for annealing treatment, wherein the annealing temperature is as follows: keeping the temperature at 400 ℃ for 5h.
8) And (3) finished product stretching: and (4) pickling the blank subjected to intermediate low-temperature annealing, and then placing the blank in a drawing machine for drawing and straightening. The finished product is stretched in 4 passes, the processing rate of each pass is controlled within 30 percent, the total processing rate of stretching is 56 percent, and the finished product is stretched in 4 passesStretching, sizing, and sawing to obtain
And (5) finishing the bar.
9) Stress relief annealing: and (4) placing the finished bar material subjected to fixed-length saw cutting into a box-type furnace for stress relief annealing, and using an ammonia decomposition atmosphere to protect the annealing mode. The heating speed is 10 ℃/min, the heat preservation temperature is 200 ℃, and the heat preservation time is 5h.
10 Straightening): and (5) straightening the finished bar, and packaging and warehousing after the finished bar is detected to be qualified.
Example 2
1) Smelting: proportioning according to the component requirements, sequentially adding an electrolytic plate, a tin ingot, metal indium and a nickel ingot into an intermediate frequency furnace, heating, controlling the initial temperature to be 1240 ℃, adding a slag removing agent after the raw materials are completely melted, uniformly stirring for 4min, adding a copper-phosphorus alloy, controlling the smelting temperature to be 1200 ℃, and uniformly stirring the melt. And (4) sampling and testing, transferring to a heat preservation furnace after the components are tested to be qualified, adding charcoal to cover, and covering with the thickness of 50mm.
2) Casting: and (4) adopting a horizontal continuous casting mode to cast a blank. Wherein the traction speed is 0.4m/min, the traction pitch is 2mm, the reverse-thrust length: 0.1mm, cooling water pressure: 0.8Mpa, cooling water inlet temperature: 18-25 ℃, water outlet temperature: 25-35 ℃ and the casting temperature is controlled at 1200 ℃. The traction blank specification is as follows:
3) Homogenizing and annealing: placing the blank in a well type furnace for homogenizing annealing treatment, wherein the annealing temperature range is as follows: the temperature is 680 ℃, and the heat preservation time is 6h. And quenching the homogenized blank after the heat preservation time is reached, and controlling the water inlet time within 30s after the blank is discharged from the furnace.
4) First stretching: placing the blank after the homogenizing annealing in an inverted disc drawing machine for drawing after acid washing treatment, wherein the total processing rate of the first drawing is 29 percent, and peeling treatment is carried out after the drawing is finished, wherein the peeling amount is 0.5mm, thus obtaining the product
And (5) coiling a round bar blank.
5) Intermediate high-temperature annealing: placing the stretched hard blank in a pit furnace for annealing treatment, wherein the annealing temperature is as follows: keeping the temperature at 530 ℃ for 4h.
6) And (3) second stretching: pickling the blank subjected to intermediate high-temperature annealing, placing the blank in an inverted disc drawing machine for drawing, wherein the total processing rate of the second drawing is 45 percent, and obtaining the alloy
And (5) coiling a round bar blank.
7) Intermediate low-temperature annealing: and (3) placing the stretched hard blank in a pit furnace for annealing treatment, wherein the annealing temperature is as follows: keeping the temperature for 4h at 420 ℃.
8) And (3) finished product stretching: and (4) pickling the blank subjected to intermediate low-temperature annealing, and then placing the blank in a drawing machine for drawing and straightening. The finished product is stretched in 4 passes, the processing rate of each pass is controlled within 30 percent, the total processing rate of stretching is 64 percent, and the finished product is obtained by sizing and sawing after stretching
Finished bar
9) Stress relief annealing: and (4) placing the finished bar material subjected to fixed-length saw cutting into a box-type furnace for stress relief annealing, and using an ammonia decomposition atmosphere to protect the annealing mode. The heating speed is 10 ℃/min, the heat preservation temperature is 200 ℃, and the heat preservation time is 5h.
10 Straightening): and (5) straightening the finished bar, and packaging and warehousing after the finished bar is detected to be qualified.
Example 3
1) Smelting: proportioning according to the component requirements, sequentially adding an electrolytic plate, a tin ingot, metal indium and a nickel ingot into an intermediate frequency furnace, heating, controlling the initial temperature to be 1220 ℃, adding a slag removing agent after the raw materials are completely melted, uniformly stirring for 4min, adding a copper-phosphorus alloy, controlling the smelting temperature to be 1200 ℃, and uniformly stirring the melt. And (4) sampling and testing, transferring to a heat preservation furnace after the components are tested to be qualified, adding charcoal to cover, and covering with the thickness of 50mm.
2) Casting: and (4) adopting a horizontal continuous casting mode to cast a blank. Wherein the traction isThe speed is 0.3m/min, the traction pitch is 2mm, the reverse length: 0.2mm, cooling water pressure: 0.6Mpa, cooling water inlet temperature: 18-25 ℃, water outlet temperature: 25-35 ℃ and the casting temperature is controlled at 1200 ℃. The traction blank specification is as follows:
3) Homogenizing and annealing: placing the blank in a well type furnace for homogenizing annealing treatment, wherein the annealing temperature is as follows: the temperature is 700 ℃, and the heat preservation time is 8h. And quenching the homogenized blank after the heat preservation time is reached, and controlling the water inlet time after the homogenized blank is discharged from the furnace within 30 s.
4) First-pass stretching: pickling the blank after the homogenizing annealing, placing the blank in an inverted disc drawing machine for drawing, wherein the total processing rate of the first drawing is 34%, and peeling is carried out after the drawing is finished, wherein the peeling amount is 0.5mm, so that the blank is obtained
And (5) coiling a round bar blank.
5) Intermediate high-temperature annealing: and (3) placing the stretched hard blank in a pit furnace for annealing treatment, wherein the annealing temperature is as follows: keeping the temperature at 550 ℃ for 3h.
6) And (3) second stretching: pickling the blank subjected to intermediate high-temperature annealing, placing the blank in an inverted disc drawing machine for drawing, wherein the total processing rate of the second drawing is 52 percent, and obtaining the alloy
And (5) coiling a round bar blank.
7) Intermediate low-temperature annealing: and (3) placing the stretched hard blank in a pit furnace for annealing treatment, wherein the annealing temperature is as follows: keeping the temperature for 5h at 440 ℃.
8) And (3) finished product stretching: and (4) pickling the blank subjected to intermediate low-temperature annealing, and then placing the blank in a drawing machine for drawing and straightening. The finished product is stretched in 4 passes, the processing rate of each pass is controlled within 30 percent, the total processing rate of stretching is 63 percent, and the finished product is obtained by sizing and sawing after stretching
Finished bar
9) Stress relief annealing: and (4) placing the finished bar material subjected to fixed-length saw cutting into a box-type furnace for stress relief annealing, and using an ammonia decomposition atmosphere to protect the annealing mode. The heating speed is 10 ℃/min, the heat preservation temperature is 180 ℃, and the heat preservation time is 10h.
10 Straightening: and (5) straightening the finished bar, and packaging and warehousing after the finished bar is detected to be qualified.
Example 4
1) Smelting: proportioning according to the component requirements, sequentially adding an electrolytic plate, a tin ingot, metal indium and a nickel ingot into an intermediate frequency furnace, heating, controlling the initial temperature to be 1230 ℃, adding a slag removing agent after the raw materials are completely melted, uniformly stirring for 4min, adding a copper-phosphorus alloy, controlling the smelting temperature to be 1200 ℃, and uniformly stirring the melt. And (4) sampling and testing, transferring to a heat preservation furnace after the components are tested to be qualified, adding charcoal to cover, and covering with the thickness of 50mm.
2) Casting: and (4) adopting a horizontal continuous casting mode to cast a blank. Wherein the traction speed is 0.4m/min, the traction pitch is 2mm, the reverse-thrust length: 0.2mm, cooling water pressure: 0.6Mpa, cooling water inlet temperature: 20-25 ℃, water outlet temperature: 25-35 ℃ and the casting temperature is controlled at 1200 ℃. The traction blank specification is as follows:
3) Homogenizing and annealing: placing the blank in a well type furnace for homogenizing annealing treatment, wherein the annealing temperature is as follows: the temperature is 710 ℃, and the heat preservation time is 8h. And quenching the homogenized blank after the heat preservation time is reached, and controlling the water inlet time after the homogenized blank is discharged from the furnace within 30 s.
4) First stretching: placing the blank after the homogenizing annealing in an inverted disc drawing machine for drawing after acid washing treatment, wherein the total processing rate of the first drawing is 20%, and peeling treatment is carried out after the drawing is finished, wherein the peeling amount is 0.5mm, thus obtaining the product
And (5) coiling a round bar blank.
5) Intermediate high-temperature annealing: placing the stretched hard blank in a pit furnace for annealing treatment, wherein the annealing temperature is as follows: keeping the temperature at 540 ℃ for 3h.
6) And (3) second stretching: pickling the blank subjected to intermediate high-temperature annealing, placing the blank in an inverted disc drawing machine for drawing, wherein the total processing rate of the second drawing is 54 percent, and obtaining the alloy
And (5) coiling a round bar blank.
7) Intermediate low-temperature annealing: and (3) placing the stretched hard blank in a pit furnace for annealing treatment, wherein the annealing temperature is as follows: keeping the temperature at 420 ℃ for 5h.
8) Stretching a finished product: and (4) pickling the blank subjected to intermediate low-temperature annealing, and then placing the blank in a drawing machine for drawing and straightening. The finished product is stretched in 4 passes, the processing rate of each pass is controlled within 30 percent, the total stretching processing rate is 58 percent, and the finished product is obtained by sizing and sawing after stretching
Finished bar
9) Stress relief annealing: and (4) placing the finished bar material subjected to fixed-length saw cutting into a box-type furnace for stress relief annealing, and using an ammonia decomposition atmosphere to protect the annealing mode. The heating speed is 10 ℃/min, the heat preservation temperature is 180 ℃, and the heat preservation time is 10h.
10 Straightening: and (5) straightening the finished bar, and packaging and warehousing after the finished bar is detected to be qualified.
Comparative examples are C5240 and Cu-Sn-Zn-Pb alloys.
The obtained examples and comparative examples were subjected to mechanical property and/or microstructure detection, and specific detection indexes and detection standards were as follows:
1) Hardness HV5: GB/T4340.1-2009 Metal materials Vickers hardness test part 1: test methods.
2) Tensile strength and elongation: GB/T228.1-2010 Metal Material tensile test part 1: room temperature tensile test method.
3) And (3) metallographic microscopic test: YS/T449-2002 copper and copper alloy casting and processing product microstructure inspection method.
4) And (3) softening temperature test: GB/T33370-2016 method for measuring the softening temperature of copper and copper alloy.
5) Cutting index: the cutting index of C36000 (HPb 63-3) is set to be 100 percent according to the evaluation of a cutting performance detection method in appendix B of YS-T647-2007 copper-zinc-bismuth-tellurium alloy bar.
6) Conductivity: GB/T351-2019 metal material resistivity measurement method.
Table 1 examples and comparative examples ingredients/wt%
TABLE 2 examples intermediate stage Performance and microstructure
TABLE 3 microstructural properties of the finished bars of the examples and comparative examples
TABLE 4 Performance of the finished bars of the examples and comparative examples
Claims (8)
1. A tin-phosphor bronze alloy characterized by: the tin-phosphor bronze alloy comprises the following components in percentage by mass: 8.0 to 10.0 percent; p:0.05 to 0.2 percent; in:0.2 to 1.0 percent; ni:0.05 to 0.2 percent; fe: less than or equal to 0.2 percent, and other impurities: less than or equal to 0.2 percent, and the balance of Cu; the tin-phosphor bronze alloy is a bar material, the microstructure of the tin-phosphor bronze alloy contains an In-delta phase, and the average size of the In-delta phase is controlled to be 0.1-2.0 mu m and 1mm 2 The precipitation quantity of In-delta phases In unit area is controlled to be more than 6000; the tensile strength of the tin-phosphor bronze alloy is more than or equal to 1000MPa, the elongation is more than or equal to 3 percent, and the cutting index is C36Over 70% of 000, more than or equal to 15% of conductivity IACS, and high-temperature softening resistance temperature more than or equal to 370 ℃.
2. A tin-phosphor bronze alloy according to claim 1, wherein: the preparation method comprises the following preparation steps:
1) Smelting: proportioning according to the required components;
2) Casting: adopting a horizontal continuous casting mode to cast a blank, wherein the traction speed is 0.2-1.0 m/min, the traction pitch is 1-3 mm, and the reverse thrust length is as follows: 0.1-0.5 mm, cooling water pressure: 0.5-0.8 MPa, cooling water inlet temperature: 15-25 ℃, water outlet temperature: the casting temperature is controlled to be 1190 to 1220 ℃ at the temperature of 20 to 40 ℃;
3) Homogenizing and annealing: carrying out homogenization annealing treatment on the blank, wherein the annealing temperature range is as follows: 680-720 ℃, keeping the temperature for 6-10 h, quenching the homogenized blank after the temperature is kept, and controlling the water inlet time after discharging to be within 30 s;
4) First-pass stretching: stretching the blank after the homogenizing annealing, wherein the processing rate is controlled to be 10-35%; after the stretching is finished, peeling treatment is carried out, and the peeling amount is 0.2-1 mm;
5) Intermediate high-temperature annealing: annealing the stretched blank, wherein the annealing temperature range is as follows: keeping the temperature at 520-600 ℃ for 2-5 h;
6) And (3) second stretching: stretching the blank after intermediate high-temperature annealing, wherein the second-pass stretching processing rate is controlled to be 30-60%;
7) Intermediate low-temperature annealing: annealing the stretched blank, wherein the annealing temperature range is as follows: keeping the temperature at 350-450 ℃ for 3-10 h;
8) And (3) finished product stretching: and (3) stretching the blank subjected to intermediate low-temperature annealing, wherein the finished product stretching is carried out in 2-4 passes, and the processing rate of each pass is controlled as follows: 10 to 30 percent, and the total stretching processing rate is 40 to 70 percent;
9) Stress relief annealing: and (3) performing stress relief annealing on the finished bar, and performing atmosphere protection, wherein the heating speed is controlled to be 5-10 ℃/min, the heat preservation temperature is controlled to be 150-200 ℃, and the heat preservation time is 4-12 h.
3. A tin-phosphor bronze alloy according to claim 2, characterized in that: in the step 2), the area ratio of the radial columnar crystal of the obtained blank is controlled to be below 50%.
4. A tin-phosphor bronze alloy according to claim 2, characterized in that: in the step 3), the Sn content deviation of the center and the edge of the annealed blank is controlled within 0.3%, the In-delta phase is granular, and the elongation of the blank reaches more than 70%.
5. A tin-phosphor bronze alloy according to claim 2, characterized in that: in the step 5), the area proportion of the longitudinal strip-shaped processing structure in the annealed blank is reduced to be within 10 percent, the average grain size of the structure is below 30 mu m, and the elongation rate is above 60 percent.
6. A tin-phosphor bronze alloy according to claim 2, characterized in that: in the step 7), the average grain size of the structure after annealing is less than 5 μm, and the elongation can reach more than 50%.
7. A tin-phosphor bronze alloy as claimed in claim 2, wherein: in the step 8), the axial and radial residual stress values of the stretched bar are controlled within 200 MPa.
8. A tin-phosphor bronze alloy according to claim 2, characterized in that: in the step 9), the axial and radial residual stress values of the annealed bar are controlled within 80 MPa.
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