WO2024108719A1 - Low-nickel zinc-cupronickel alloy and preparation method therefor - Google Patents

Low-nickel zinc-cupronickel alloy and preparation method therefor Download PDF

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WO2024108719A1
WO2024108719A1 PCT/CN2022/141737 CN2022141737W WO2024108719A1 WO 2024108719 A1 WO2024108719 A1 WO 2024108719A1 CN 2022141737 W CN2022141737 W CN 2022141737W WO 2024108719 A1 WO2024108719 A1 WO 2024108719A1
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zinc
nickel
low
alloy
copper alloy
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PCT/CN2022/141737
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French (fr)
Chinese (zh)
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熊承义
邵海洋
王林伟
宋玉波
刘庆
陈嘉兴
谢全文
张桂飞
张轩瑞
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宁波博威合金材料股份有限公司
宁波博威新材料有限公司
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Publication of WO2024108719A1 publication Critical patent/WO2024108719A1/en

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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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C22C30/06—Alloys containing less than 50% by weight of each constituent containing zinc
    • 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
    • C22C9/04—Alloys based on copper with zinc as the next major constituent
    • 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
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
    • 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
    • C22C9/08—Alloys based on copper with lead 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
    • C22F1/08—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

Definitions

  • the invention belongs to the field of copper alloys, and in particular relates to a low-nickel-zinc white copper alloy and a preparation method thereof.
  • Nickel silver has a beautiful luster similar to that of silver, as well as good thermal processing performance and excellent corrosion resistance. It is a commonly used material in the industries of instruments, meters, coinage, arts and crafts, glasses, etc. However, with the rapid development of industry, the service life of traditional nickel silver alloy products can no longer meet the demand, especially for products with high frequency of use such as keys and pen tips. The extension of service life has put forward higher requirements on its performance, such as corrosion resistance, strength, processing performance, etc.
  • zinc-nickel-copper alloys in order to improve the strength and corrosion resistance of zinc-nickel-copper alloys, a high content of nickel is often added to the copper base, and the nickel content is usually above 10%.
  • nickel is a scarce strategic material and is relatively expensive.
  • the cost of zinc-nickel-copper products with high nickel content is relatively high, which limits the application of the product.
  • zinc-nickel-copper alloys with high nickel content have poor processing plasticity, high hardening rate, low yield rate, and general surface accuracy, which makes it difficult to meet the market's high-speed and high-precision processing needs.
  • the alloy is required to have not only the excellent properties of high-nickel zinc white copper alloy, but also excellent processing performance, and achieve the purpose of "nickel saving" to reduce material production costs.
  • the technical problem to be solved by the present invention is to provide a low-nickel-zinc-white copper alloy having excellent cutting performance, good tensile strength and corrosion resistance and excellent processing performance and a preparation method thereof under the premise of reducing nickel content and reducing manufacturing cost.
  • a low-nickel zinc white copper alloy the mass percentage composition of the low-nickel zinc white copper alloy includes: Cu 47.0-55.0%, Pb 1.5-3.0%, Ni 5.5-7.5%, Mn 1.5-4.0%, X 0.0001-0.5%, and the balance is Zn and unavoidable impurities, wherein X is at least one element selected from Fe, Sn, and Si.
  • Zn as the main element, can be dissolved in a large amount in the copper matrix to form a wide single-phase ⁇ solid solution zone, which has a solid solution strengthening effect, improves the strength and hardness of the alloy, and in addition, the addition of the Zn element can improve the corrosion resistance of the alloy.
  • the alloy With the increase of the Zn content, the alloy changes into an ⁇ + ⁇ phase and enters a dual-phase structure. Since the ⁇ phase is easier to soften than the ⁇ phase at high temperature, the appearance of the ⁇ phase can improve the hot processing performance of the alloy, but the ⁇ phase is hard and brittle at room temperature, which increases the difficulty of cold processing of the alloy.
  • the ⁇ phase structure content is reduced or even does not exist.
  • the alloy is hot extruded at high temperature, cracking is likely to occur, the processing difficulty increases, and it is not conducive to the strengthening of strength, hardness and corrosion resistance; but if the Zn content is too high, the ⁇ phase content will increase and grow, reduce the plastic deformation ability of the alloy, and cannot meet the cold processing requirements. Therefore, the present invention reduces the Ni content appropriately and increases the Zn content, so that the alloy has an ⁇ + ⁇ dual-phase structure, and improves the strength, hardness, hot and cold processing and corrosion resistance of the alloy.
  • the Ni element in the zinc-white copper alloy of the present invention, can infinitely solid-dissolve with the Cu base to form a continuous solid solution, has a solid solution strengthening effect, and significantly improves the strength and hardness of the alloy.
  • Ni can form compounds such as Ni-Mn with elements including Mn, and the formation of the compound is conducive to further improving the strength and corrosion resistance of the alloy.
  • the low-melting-point Pb element in the alloy interacts with hydrogen during high-temperature hot extrusion of the alloy, causing the alloy to crack.
  • the present invention reduces production costs by adding a low-content Ni element, and increases the content of the Zn element, releases hydrogen through heat treatment, expands the ⁇ phase region of the alloy, improves plasticity when the alloy strength is slightly improved, improves the processing performance of the alloy, reduces the tendency of stress cracking, and improves corrosion resistance.
  • the Ni content in the zinc-white copper alloy of the present invention is 5.5-7.5%.
  • the Ni content is lower than 5.5%, the tensile strength, hardness and corrosion resistance of the alloy are reduced, and the elongation is increased, which cannot meet the product requirements; on the other hand, if the Ni content is higher than 7.5%, the plasticity index of the alloy begins to decrease, the amount of Zn added in the alloy will be reduced accordingly, the ⁇ phase content is reduced, the hot working performance of the alloy is deteriorated, cracks are easily generated during hot extrusion, and the alloy manufacturing cost is increased.
  • the alloy strength and processing performance can be further improved by adding an appropriate amount of Mn element.
  • the Mn element has a large solid solubility in the copper alloy, and improves the alloy strength through solid solution strengthening.
  • the Mn element has the effect of expanding the ⁇ phase region, further improving the alloy processing performance, especially the hot processing performance, and avoiding the linear cracking phenomenon after the alloy heat treatment.
  • the free enthalpy of the reaction between Mn and oxygen is greatly different from the free enthalpy of the reaction between nickel and oxygen, so it has a good deoxidation effect, can improve the quality of the alloy ingot, eliminate the adverse effects of excess oxygen in the zinc-white copper alloy, reduce the deformation resistance caused by the Ni element during the extrusion process, promote the formation of the ⁇ phase, and improve the processing performance of the alloy.
  • the Mn content in the alloy of the present invention is controlled at 1.5-4.0%. When the Mn content is lower than 1.5%, the improvement effect on the strength and processing properties of the alloy is reduced.
  • the present invention adds a certain amount of Pb element to the zinc-nickel-copper alloy to form lead-zinc-nickel-copper.
  • the Pb element plays a role in improving the cutting performance of the alloy during the cutting process and improving the accuracy of the alloy cutting shape.
  • the solid solubility of the Pb element in the zinc-nickel-copper alloy is almost zero.
  • Pb is dispersed in the matrix in the form of particles.
  • Such Pb particles have both lubrication and chip breaking during cutting, thereby improving the cutting performance of the zinc-nickel-copper and obtaining a smooth surface. Therefore, the higher the Pb content, the more the Pb particles are continuously diffused and evenly distributed through subsequent processing, and the better the cutting performance.
  • the melting point of Pb is relatively low.
  • the heat generated by the alloy during high-speed turning can make the Pb near the processing part melt quickly and form a fusible eutectic with copper, cut off the continuity of the material processing, and avoid the problem of long chip entanglement during the processing process.
  • the Pb element content of the alloy of the present invention is controlled at 1.5-3.0%. Compared with the cutting performance of C3604 with the same Pb content, the cutting performance reaches more than 80%.
  • X is selected from at least one element of Fe, Sn, and Si. These elements mainly play a role of solid solution strengthening by solid solution in copper, thereby improving the mechanical properties, processing properties and corrosion resistance of the zinc-white copper alloy of the present invention.
  • Fe has the function of refining alloy grains, mainly exists in the form of single substance Fe, improves the mechanical properties of the alloy, and when the alloy contains excessive single substance Fe particles, the corrosion resistance of the alloy is weakened; trace amounts of Sn can improve the mechanical properties and corrosion resistance of the alloy, but excessive Sn will increase the tendency of alloy annealing cracking; Si element has the function of expanding the ⁇ phase region of the alloy of the present invention, improving the processing properties of the alloy, in addition, Si and Ni generate NiSi compounds, which can improve the strength of the alloy, but excessive NiSi compounds will increase the wear of the cutting tool during operation.
  • the content of the above elements is too low, the effect is not obvious; if the content is too high, it will affect the comprehensive performance of the zinc-white copper alloy of the present invention, and will also have an adverse effect on the surface flatness. Therefore, the content of X in the zinc-white copper alloy of the present invention is controlled at 0.0001-0.5%.
  • the mass percentage composition of the low nickel zinc white copper alloy also includes a total amount of less than 0.5% M, where M is at least one element selected from P, Al, Cr, Mg, Ti, Sb, Bi, and Zr.
  • M is at least one element selected from P, Al, Cr, Mg, Ti, Sb, Bi, and Zr.
  • P, Al, Cr, Mg, Ti, Sb, Bi, and Zr will not have a significant negative impact on the processing performance of the alloy while improving the strength, cutting performance and corrosion resistance of the alloy.
  • Adding trace amounts of P, Ti or Zr elements to the zinc white copper alloy of the present invention can further refine the grains and improve the strength of the alloy, but if the content is too high, the alloy will increase its cracking tendency during high temperature extrusion.
  • the P, Mg, Zr or Sb elements added to the alloy of the present invention can form intermetallic compounds with Cu, and the intermetallic compounds help break chips during the turning process, thereby improving the cutting performance of the alloy, but too high a content will increase the wear of the cutting tool.
  • the Al element in the alloy of the present invention can form a NiAl compound with Ni to improve the strength of the alloy.
  • Al can form a dense Al 2 O 3 protective film on the surface of the alloy, which has the effect of improving the corrosion resistance of the alloy.
  • the Cr element can improve the corrosion resistance of the alloy, and can form a single Cr phase in the zinc white copper to improve the strength and cutting performance.
  • the addition of Bi element improves the cutting and drilling performance of the alloy.
  • the present invention also achieves the improvement of the cutting performance of the zinc-white copper alloy with low nickel content as well as the comprehensive performance including strength, corrosion resistance and hot and cold processing performance by optimizing the microstructure of the alloy such as the phase composition and phase ratio.
  • the microstructure of the zinc-nickel white copper alloy of the present invention mainly includes ⁇ phase, ⁇ phase and Pb particles, and the microstructure on the cross section of the low-nickel zinc-nickel white copper alloy is controlled, the area ratio of the ⁇ phase is 67-93%, the area ratio of the ⁇ phase is 5-30%, and the ⁇ phase, ⁇ phase and Pb particles are evenly distributed, so that the alloy has excellent cold and hot processing performance, and the alloy strength, corrosion resistance and cutting performance are enhanced.
  • the ⁇ phase is hard, and the excessive ⁇ phase in the alloy leads to poor hot processing performance and difficulty in extrusion.
  • the surface cracks increase, it is easy to break, the tensile strength and hardness values are low, and the extrusion process is difficult to complete, mainly because in the extrusion process, the large friction force of the hard ⁇ phase leads to a sharp temperature rise, and after the alloy partially exceeds the melting point and melts, radial cracks are generated on the surface of the extruded wire billet; while the ⁇ phase is soft at high temperature, the appearance of the ⁇ phase makes hot extrusion easy to achieve, after high-temperature extrusion, the surface of the wire billet is smooth, crack-free, tensile strength and hardness values increase, corrosion resistance is improved, elongation is reduced, and hot processing performance is good.
  • the present invention controls the area ratios of ⁇ and ⁇ phases in the alloy to 67-93% and 5-30% respectively, achieving excellent comprehensive performance of the alloy.
  • the present invention controls the ratio of the number of ⁇ phases with an area less than 10 ⁇ m 2 to the total number of ⁇ phases in the unit area of 10000 ⁇ m 2 on the cross section of the zinc-white copper alloy to ⁇ 30%.
  • the size and distribution of the ⁇ phase affect the strength, corrosion resistance, processing characteristics and application performance of the alloy. When the grain size is small and dispersed, the alloy has better compactness and stronger resistance to neutral salt spray corrosion, thus having better corrosion resistance.
  • the ⁇ phase itself belongs to a hard and brittle phase with high hardness. When it is dispersed in the alloy with a small grain size, it can play a role in fine grain enhancement.
  • the ⁇ phase is evenly distributed in the alloy, which can improve the rheological uniformity of the alloy during pressure processing and reduce the tendency of processing cracking caused by inconsistent tissue rheology.
  • the uniform distribution of fine ⁇ phases can also reduce the microhardness fluctuation caused by the different hardness of ⁇ phase and ⁇ phase in the microscopic scale range, improve the force uniformity of the cutting tool during processing, and improve the cutting performance of the alloy product.
  • the present invention controls the average area of the Pb particles in the microstructure on the cross section of the zinc-white copper alloy to be no more than 20 ⁇ m 2 , and the ratio of the number of Pb particles with an area less than 5 ⁇ m 2 to the total number of Pb particles is ⁇ 30%.
  • the fine Pb particles can be evenly distributed in the copper matrix, further improving the cutting uniformity of the alloy; on the other hand, during the hot working process, the fine Pb particles are partially dissolved in the ⁇ phase, and at the same time, some Pb particles enter the crystal during the ⁇ and ⁇ phase transformation.
  • the fine Pb particles distributed at the grain boundary can reduce the penetration of Cl- ions between the Pb particles and the grains, thereby improving the corrosion resistance of the alloy.
  • the interface area between the Pb particles and the grain boundary will be increased, accelerating the penetration of Cl- ions and reducing the corrosion resistance of the alloy.
  • the low nickel zinc white copper alloy has a tensile strength of ⁇ 550MPa, a yield strength of ⁇ 500MPa, an elongation of ⁇ 2%, a microhardness HV value of ⁇ 120, no corrosion occurs in a neutral salt spray with a pH value of 7 for 24 hours, and a cutting performance of more than 80% of that of the C3604 alloy.
  • the present invention also provides a method for preparing the low-nickel zinc white copper alloy, comprising the following steps: melting and casting ⁇ hot extrusion ⁇ primary annealing ⁇ primary stretching ⁇ secondary annealing ⁇ secondary stretching, specifically as follows:
  • the continuous casting temperature is controlled in the range of 1000-1110°C to obtain an ingot with a smooth surface and fine and uniform grains.
  • the present invention controls the casting speed of the melt casting to be 20-40 mm/min. If the casting speed is too low, the melt solidifies too quickly, the solid-liquid area of the alloy is close to the furnace mouth, the friction contact area between the ingot and the graphite crystal increases, the casting force increases, and the ingot may not be pulled properly. In addition, the production efficiency of the alloy ingot is reduced. If the casting speed is too fast, the solid-liquid area of the alloy is close to the crystallizer mouth, which is not conducive to the gas discharge of the melt. The solid-liquid area of the alloy is too close to the crystallizer outlet. If the temperature of the holding furnace fluctuates at this time, leakage is very likely to occur.
  • Hot extrusion The extrusion temperature of hot extrusion is 700-800°C, and the deformation is ⁇ 90%.
  • the lower limit temperature during extrusion should be higher than 700°C.
  • too high a temperature will have an adverse effect on the surface quality.
  • the plasticity of the alloy decreases and the deformation unevenness increases.
  • the surface layer alloy of the extruded product recrystallizes into coarse grains, forming a coarse grain ring, which reduces the plasticity index of cold working.
  • the upper limit temperature is controlled at 800°C.
  • the extrusion speed of the zinc-white copper alloy of the present invention is controlled in the range of 2-8mm/s. If the extrusion speed is too fast, the alloy will produce non-contact deformation in the mold, and the mold hole will not be filled and waste will appear; if the extrusion speed is too slow, the efficiency will be too low.
  • the annealing temperature is 600-700°C, and the holding time is 2-4h. If the temperature is lower than 600°C or the holding time is less than 2h, it is difficult to fully eliminate the deformed structure after processing, which is not conducive to the subsequent processing of the alloy; if the annealing temperature is higher than 700°C or the holding time exceeds 4h, it will lead to excessively large grains and uneven distribution of ⁇ and ⁇ phases.
  • Stretching is performed at a stretching processing rate of 15 to 25%, which is beneficial to the redistribution of grains and the improvement of the uniformity of grain size.
  • Secondary annealing The annealing temperature of the secondary annealing is 600-670°C and the annealing time is 2-4 hours to obtain a uniform grain structure.
  • the stretching processing rate is 15-35% to obtain a smooth material surface, specific microstructure and properties.
  • the samples after secondary stretching can be annealed and stretched multiple times.
  • the present invention has the following advantages:
  • the present invention reduces the nickel content in the zinc-nickel alloy and adds Mn and Pb elements so that the alloy microstructure contains ⁇ phase, ⁇ phase and Pb particles, thereby obtaining a zinc-nickel alloy with excellent cutting performance, good tensile strength and corrosion resistance, excellent processing performance and low manufacturing cost.
  • the present invention controls the proportion and size of the ⁇ phase and the proportion of the ⁇ phase in the alloy to ensure that in the microstructure on the cross section of the alloy, the area ratio of the ⁇ phase is 67-93%, and the area ratio of the ⁇ phase is 5-30%; within a unit area of 10000 ⁇ m2 on the cross section of the alloy, the ratio of the number of ⁇ phases with an area less than 10 ⁇ m2 to the total number of ⁇ phases in the unit area is ⁇ 30%, thereby achieving good tensile strength, corrosion resistance and processing performance of the alloy.
  • the present invention controls the size and number of Pb particles to ensure that in the microstructure on the cross section of the alloy, the average area of the Pb particles does not exceed 20 ⁇ m 2 and the number of Pb particles with an area less than 5 ⁇ m 2 accounts for ⁇ 30% of the total number of Pb particles, thereby achieving excellent cutting performance and processing performance of the alloy.
  • the zinc white copper with low nickel content of the present invention has excellent comprehensive performance and can effectively reduce the production cost of alloy products and increase the service life of products.
  • FIG1 is a metallographic microstructure photograph of the distribution of Pb particles on a cross section of a low-nickel zinc-nickel white copper alloy of Example 7;
  • FIG. 2 is a metallographic microstructure photograph of the distribution of ⁇ phase and ⁇ phase on the cross section of the low nickel zinc white copper alloy of Example 7.
  • the raw materials were weighed and mixed according to the proportions, smelted at 1050-1150° C., and after melting, continuously casted at a continuous casting temperature of 1000-1110° C. and a casting speed of 20-40 mm/min to form an ingot, and the ingot was subjected to a turning surface treatment, and then hot extruded at an extrusion temperature of 700-800° C., an extrusion speed of 2-8 mm/s, an extrusion rate of ⁇ 90%, and an extrusion pressure of 60-100 bar. Then, the product was subjected to a hot extrusion process.
  • the sample is pickled and planed to remove surface impurities, and then the extruded billet is stretched and annealed twice: one annealing is performed at 600-700°C for 2-4 hours, and after annealing, the sample surface is pickled to remove surface impurities, and then a stretching is performed at a stretching processing rate of 15-25%; finally, a secondary annealing and secondary stretching are performed: the sample is annealed at 600-670°C for 2-4 hours, the sample after the secondary annealing is pickled to remove surface impurities, and then a secondary stretching is performed at a stretching processing rate of 15-35% to obtain a sample of the required specifications.
  • the room temperature tensile test is carried out in accordance with GB/T 228.1-2010 Tensile test of metallic materials Part 1: Room temperature test method, and the tensile strength and elongation are tested on an electronic universal mechanical properties testing machine.
  • microhardness HV value is tested on a digital Vickers hardness tester in accordance with GB-T 4340.1-2009 Metallic Materials Vickers Hardness Test Part 1: Test Method.
  • the corrosion resistance performance is tested in accordance with the NSS test of GB/T 10125-2021 "Artificial atmosphere corrosion test salt spray test" and is carried out for 24 hours in neutral salt spray with a pH value of 7.
  • Figure 1 is a metallographic microstructure photo of the distribution of Pb particles on the cross section of the low-nickel zinc-white copper alloy of Example 7
  • Figure 2 is a metallographic microstructure photo of the distribution of ⁇ phase and ⁇ phase on the cross section of the low-nickel zinc-white copper alloy of Example 7.
  • the average area of the Pb particles is 12.3 ⁇ m 2 , and the number of Pb particles with an area of less than 5 ⁇ m 2 accounts for 45% of the total number of Pb particles; the area ratio of the ⁇ phase is 88.82%, the area ratio of the ⁇ phase is 9.38%, and within a unit area of 10000 ⁇ m 2 , the number of ⁇ phases with an area of less than 10 ⁇ m 2 accounts for 48% of the total number of ⁇ phases within the unit area.
  • a value the ratio of the number of ⁇ phases with an area less than 10 ⁇ m 2 to the total number of ⁇ phases in a unit area of 10000 ⁇ m 2 on the cross section of the low nickel-zinc white copper alloy;
  • B value The ratio of the number of Pb particles with an area less than 5 ⁇ m2 to the total number of Pb particles in the microstructure of the cross section of the low-nickel-zinc white copper alloy.

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Abstract

A low-nickel zinc-cupronickel alloy, which comprises the following components in percentages by mass: 47.0-55.0% of Cu, 1.5-3.0% of Pb, 5.5-7.5% of Ni, 1.5-4.0% of Mn, 0.0001-0.5% of X and the balance of Zn and inevitable impurities, wherein X is at least one element selected from Fe, Sn and Si. By adding Mn and Pb into the low-nickel zinc-cupronickel alloy, it is guaranteed that in a microstructure on the cross section of the alloy, the area ratio of an α phase is 67-93%, the area ratio of a β phase is 5-30%, the average area of Pb particles does not exceed 20 μm2, and the ratio of the number of the Pb particles with an area smaller than 5 μm2 to the total number of the Pb particles is more than or equal to 30%; and finally a zinc-cupronickel alloy with good cutting performance, good tensile strength and corrosion resistance, good processability and low manufacturing cost is obtained.

Description

一种低镍锌白铜合金及其制备方法A low-nickel zinc white copper alloy and preparation method thereof 技术领域Technical Field
本发明属于铜合金领域，具体涉及一种低镍锌白铜合金及其制备方法。The invention belongs to the field of copper alloys, and in particular relates to a low-nickel-zinc white copper alloy and a preparation method thereof.
背景技术Background technique
锌白铜具有近似白银般的美丽光泽，以及良好的热加工性能、优良的耐腐蚀性能，是仪器、仪表、造币、工艺美术品、眼镜等行业常用的材料。但随着工业的快速发展，传统锌白铜合金的产品使用寿命已无法满足需求，尤其像钥匙、笔头等使用频率高的产品，使用寿命的延长对其性能提出了更高的要求，如耐腐蚀性能、强度、加工性能等。Nickel silver has a beautiful luster similar to that of silver, as well as good thermal processing performance and excellent corrosion resistance. It is a commonly used material in the industries of instruments, meters, coinage, arts and crafts, glasses, etc. However, with the rapid development of industry, the service life of traditional nickel silver alloy products can no longer meet the demand, especially for products with high frequency of use such as keys and pen tips. The extension of service life has put forward higher requirements on its performance, such as corrosion resistance, strength, processing performance, etc.
目前对锌白铜合金所进行的研发和开发中，为提高锌白铜合金的强度和耐腐蚀性，常在铜基中加入高含量的镍元素，镍含量通常在10％以上，但镍元素属于稀缺的战略物资，价格比较昂贵，高镍含量的锌白铜产品成本偏高，限制了产品的应用；此外，高镍含量的锌白铜合金加工塑性差，硬化率高，成材率低，表面精度一般，难以满足市场高速高精度的加工需求。In the current research and development of zinc-nickel-copper alloys, in order to improve the strength and corrosion resistance of zinc-nickel-copper alloys, a high content of nickel is often added to the copper base, and the nickel content is usually above 10%. However, nickel is a scarce strategic material and is relatively expensive. The cost of zinc-nickel-copper products with high nickel content is relatively high, which limits the application of the product. In addition, zinc-nickel-copper alloys with high nickel content have poor processing plasticity, high hardening rate, low yield rate, and general surface accuracy, which makes it difficult to meet the market's high-speed and high-precision processing needs.
随着市场竞争日益激烈，企业进入薄利化时代，迫切需求降低各方面成本来提高盈利水平，同时为满足企业对锌白铜日益增长的性能需求，需继续研制出低镍锌白铜，要求该合金不仅具有高镍锌白铜合金的优异性能，而且加工性能优异，并达到“节镍”目的，降低材料生产成本。As market competition becomes increasingly fierce, enterprises have entered an era of thin profits and are in urgent need of reducing costs in all aspects to improve profitability. At the same time, in order to meet the growing performance requirements of enterprises for zinc white copper, it is necessary to continue to develop low-nickel zinc white copper. The alloy is required to have not only the excellent properties of high-nickel zinc white copper alloy, but also excellent processing performance, and achieve the purpose of "nickel saving" to reduce material production costs.
发明内容Summary of the invention
本发明所要解决的技术问题是，在降低镍含量并减少制造成本的前提下，提供一种具有优异的切削性能、良好的抗拉强度和耐腐蚀性能，且加工性能优异的低镍锌白铜合金及其制备方法。The technical problem to be solved by the present invention is to provide a low-nickel-zinc-white copper alloy having excellent cutting performance, good tensile strength and corrosion resistance and excellent processing performance and a preparation method thereof under the premise of reducing nickel content and reducing manufacturing cost.
本发明解决上述技术问题所采用的技术方案为：一种低镍锌白铜合金，该低镍锌白铜合金的质量百分比组成包括：Cu 47.0～55.0％、Pb 1.5～3.0％、Ni 5.5～7.5％、Mn 1.5～4.0％、X 0.0001～0.5％，余量为Zn和不可避免的杂质，其中X为选自Fe、Sn、Si中的至少一种元素。The technical solution adopted by the present invention to solve the above technical problems is: a low-nickel zinc white copper alloy, the mass percentage composition of the low-nickel zinc white copper alloy includes: Cu 47.0-55.0%, Pb 1.5-3.0%, Ni 5.5-7.5%, Mn 1.5-4.0%, X 0.0001-0.5%, and the balance is Zn and unavoidable impurities, wherein X is at least one element selected from Fe, Sn, and Si.
本发明锌白铜合金中，Zn作为主要元素，能大量溶于铜基体中，形成一个广泛的单相α固溶体区，具有固溶强化作用，提高合金的强度和硬度，此外，Zn元素的加入可以提升合金的耐腐蚀性。随着Zn含量的升高，合金变为α+β相进入双相组织。由于β相在高温下比α相更易软化，β相的出现可提高合金热加工性能，但β相在室温下硬而脆，使合金冷加工难 度增加。而Zn含量过低的锌白铜合金中，β相组织含量降低甚至不存在，合金在高温下进行热挤压时，容易出现开裂现象，加工难度增大，且不利于强度、硬度和耐腐蚀性能的强化；但若Zn含量过高，会导致β相含量增加和长大，降低合金的塑性变形能力，无法满足冷加工需求。因此，本发明通过适量降低Ni含量，提高Zn含量，使合金具有α+β双相组织，提高合金的强度、硬度、冷热加工性和耐腐蚀性能。In the zinc-white copper alloy of the present invention, Zn, as the main element, can be dissolved in a large amount in the copper matrix to form a wide single-phase α solid solution zone, which has a solid solution strengthening effect, improves the strength and hardness of the alloy, and in addition, the addition of the Zn element can improve the corrosion resistance of the alloy. With the increase of the Zn content, the alloy changes into an α+β phase and enters a dual-phase structure. Since the β phase is easier to soften than the α phase at high temperature, the appearance of the β phase can improve the hot processing performance of the alloy, but the β phase is hard and brittle at room temperature, which increases the difficulty of cold processing of the alloy. In the zinc-white copper alloy with too low Zn content, the β phase structure content is reduced or even does not exist. When the alloy is hot extruded at high temperature, cracking is likely to occur, the processing difficulty increases, and it is not conducive to the strengthening of strength, hardness and corrosion resistance; but if the Zn content is too high, the β phase content will increase and grow, reduce the plastic deformation ability of the alloy, and cannot meet the cold processing requirements. Therefore, the present invention reduces the Ni content appropriately and increases the Zn content, so that the alloy has an α+β dual-phase structure, and improves the strength, hardness, hot and cold processing and corrosion resistance of the alloy.
本发明锌白铜合金中，Ni元素作为主要添加元素，能与Cu基无限固溶，形成连续固溶体，具有固溶强化作用，显著提高合金强度、硬度。其次，Ni可以与包括Mn在内的元素形成Ni-Mn等化合物，化合物的形成有利于进一步提高合金强度和耐腐蚀性能。但Ni元素由于资源的限制和价格昂贵，而且合金加工过程中Ni元素易吸氢，导致合金在高温热挤压时，合金中的低熔点Pb元素与氢相互作用，使合金出现开裂现象。因此，本发明通过加入低含量的Ni元素，降低生产成本，并提高Zn元素的含量，经过热处理将氢释放，扩大合金的β相区，使合金强度稍有提高的情况下提高塑性，以及改善合金的加工性能和减轻应力破裂的倾向，提高耐腐蚀性能。本发明锌白铜合金中Ni含量为5.5～7.5％，一方面若Ni含量低于5.5％，合金的抗拉强度、硬度和耐腐蚀性能降低，延伸率增大，无法满足产品需求；另一方面，若Ni含量高于7.5％，合金的塑性指标开始下降，合金中Zn的添加量会相应的减少，β相含量降低，合金的热加工性能变差，热挤压时容易产生裂纹，且合金制造成本增加。In the zinc-white copper alloy of the present invention, the Ni element, as the main additive element, can infinitely solid-dissolve with the Cu base to form a continuous solid solution, has a solid solution strengthening effect, and significantly improves the strength and hardness of the alloy. Secondly, Ni can form compounds such as Ni-Mn with elements including Mn, and the formation of the compound is conducive to further improving the strength and corrosion resistance of the alloy. However, due to the limitation of resources and the high price of the Ni element, and the Ni element is easy to absorb hydrogen during the alloy processing, the low-melting-point Pb element in the alloy interacts with hydrogen during high-temperature hot extrusion of the alloy, causing the alloy to crack. Therefore, the present invention reduces production costs by adding a low-content Ni element, and increases the content of the Zn element, releases hydrogen through heat treatment, expands the β phase region of the alloy, improves plasticity when the alloy strength is slightly improved, improves the processing performance of the alloy, reduces the tendency of stress cracking, and improves corrosion resistance. The Ni content in the zinc-white copper alloy of the present invention is 5.5-7.5%. On the one hand, if the Ni content is lower than 5.5%, the tensile strength, hardness and corrosion resistance of the alloy are reduced, and the elongation is increased, which cannot meet the product requirements; on the other hand, if the Ni content is higher than 7.5%, the plasticity index of the alloy begins to decrease, the amount of Zn added in the alloy will be reduced accordingly, the β phase content is reduced, the hot working performance of the alloy is deteriorated, cracks are easily generated during hot extrusion, and the alloy manufacturing cost is increased.
本发明锌白铜合金中，通过加入适量的Mn元素能进一步提高合金强度和加工性能。Mn元素在铜合金中固溶度较大，通过固溶强化改善合金强度，同时Mn元素具有扩大β相区的作用，进一步改善合金加工性能，特别是热加工性能，避免合金热处理之后的直线开裂现象。除此之外，在高温时Mn与氧反应的自由焓和镍与氧反应的自由焓相差较大，故具有较好的脱氧效果，可改善合金铸锭的质量，消除锌白铜合金中过剩氧的不良影响，降低挤压过程中Ni元素带来的变形抗力，促进形成β相，改善合金的加工性能。本发明合金中的Mn元素含量控制在1.5～4.0％，Mn含量低于1.5％时，对合金强度加工性能的改善效果降低；Mn含量高于4.0％时，一方面过量的Mn元素会使合金中形成大量的Ni-Mn化合物，导致合金过硬，不利于塑性加工，另一方面过量的Mn含量会使β相含量过高，β相与α相相比易腐蚀，含量过高会影响合金的耐蚀性能，且降低合金冷加工性能。In the zinc-white copper alloy of the present invention, the alloy strength and processing performance can be further improved by adding an appropriate amount of Mn element. The Mn element has a large solid solubility in the copper alloy, and improves the alloy strength through solid solution strengthening. At the same time, the Mn element has the effect of expanding the β phase region, further improving the alloy processing performance, especially the hot processing performance, and avoiding the linear cracking phenomenon after the alloy heat treatment. In addition, at high temperatures, the free enthalpy of the reaction between Mn and oxygen is greatly different from the free enthalpy of the reaction between nickel and oxygen, so it has a good deoxidation effect, can improve the quality of the alloy ingot, eliminate the adverse effects of excess oxygen in the zinc-white copper alloy, reduce the deformation resistance caused by the Ni element during the extrusion process, promote the formation of the β phase, and improve the processing performance of the alloy. The Mn content in the alloy of the present invention is controlled at 1.5-4.0%. When the Mn content is lower than 1.5%, the improvement effect on the strength and processing properties of the alloy is reduced. When the Mn content is higher than 4.0%, on the one hand, excessive Mn elements will form a large amount of Ni-Mn compounds in the alloy, resulting in the alloy being too hard and not conducive to plastic processing. On the other hand, excessive Mn content will make the β phase content too high. Compared with the α phase, the β phase is more susceptible to corrosion. Too high a content will affect the corrosion resistance of the alloy and reduce the cold processing performance of the alloy.
为改善切削性能，本发明在锌白铜合金中加入一定量的Pb元素，形成铅锌白铜。Pb元素在切削加工过程中起改善合金切削加工性能的作用，提高合金切削形状的精准度。Pb元素在锌白铜合金中的固溶度几乎为零，Pb是以颗粒的形态分散于基体中，这种Pb颗粒既有润滑的作用，也可使切削时断屑，从而改善锌白铜的切削性能，且可获得光洁的表面，因而含 Pb量越高，通过后续加工，使Pb颗粒不断扩散并均匀分布，切削性能也越好。除此之外，Pb的熔点较低，合金在高速车削过程中产生的热量，可使加工部位附近的Pb快速融化并与铜形成易熔共晶，切断材料加工时的连续性，避免加工过程的较长车屑缠刀问题。本发明合金的Pb元素含量控制在1.5～3.0％，与相同Pb含量的C3604切削性能相比，切削性能达到80％以上。当Pb含量低于1.5％时，合金切削性能降低，无法满足产品需求；当Pb含量高于3.0％时，Pb颗粒容易聚集，会导致合金热加工性能变差，强度、延伸率降低，严重的可能发生热脆和应力开裂。In order to improve the cutting performance, the present invention adds a certain amount of Pb element to the zinc-nickel-copper alloy to form lead-zinc-nickel-copper. The Pb element plays a role in improving the cutting performance of the alloy during the cutting process and improving the accuracy of the alloy cutting shape. The solid solubility of the Pb element in the zinc-nickel-copper alloy is almost zero. Pb is dispersed in the matrix in the form of particles. Such Pb particles have both lubrication and chip breaking during cutting, thereby improving the cutting performance of the zinc-nickel-copper and obtaining a smooth surface. Therefore, the higher the Pb content, the more the Pb particles are continuously diffused and evenly distributed through subsequent processing, and the better the cutting performance. In addition, the melting point of Pb is relatively low. The heat generated by the alloy during high-speed turning can make the Pb near the processing part melt quickly and form a fusible eutectic with copper, cut off the continuity of the material processing, and avoid the problem of long chip entanglement during the processing process. The Pb element content of the alloy of the present invention is controlled at 1.5-3.0%. Compared with the cutting performance of C3604 with the same Pb content, the cutting performance reaches more than 80%. When the Pb content is lower than 1.5%, the cutting performance of the alloy is reduced and cannot meet product requirements; when the Pb content is higher than 3.0%, Pb particles are prone to aggregate, which will cause the alloy's hot processing performance to deteriorate, and the strength and elongation to decrease. In severe cases, hot brittleness and stress cracking may occur.
本发明锌白铜合金中，X选自Fe、Sn、Si中的至少一种元素，这些元素主要是通过固溶于铜中，起固溶强化的作用，从而有利于提高本发明锌白铜合金的机械性能、加工性能和耐腐蚀性能。其中Fe具有细化合金晶粒的作用，主要以单质Fe的形式存在，提升合金的机械性能，当合金中含有过量的单质Fe颗粒时，合金的耐腐蚀性能减弱；微量的Sn可提高合金的机械性能和耐腐蚀性能，但过量的Sn会增加合金退火开裂的倾向；Si元素有扩大本发明合金的β相区的作用，提高合金的加工性能，此外，Si与Ni生成NiSi化合物，可提升合金强度，但过量的NiSi化合物会增加切削刀具工作时的磨损。上述元素的含量若过低则效果不明显；若含量过高，则会影响本发明锌白铜合金的综合性能，对表面平整度也会产生不利的影响。因此，本发明锌白铜合金中的X的含量控制在0.0001～0.5％。In the zinc-white copper alloy of the present invention, X is selected from at least one element of Fe, Sn, and Si. These elements mainly play a role of solid solution strengthening by solid solution in copper, thereby improving the mechanical properties, processing properties and corrosion resistance of the zinc-white copper alloy of the present invention. Among them, Fe has the function of refining alloy grains, mainly exists in the form of single substance Fe, improves the mechanical properties of the alloy, and when the alloy contains excessive single substance Fe particles, the corrosion resistance of the alloy is weakened; trace amounts of Sn can improve the mechanical properties and corrosion resistance of the alloy, but excessive Sn will increase the tendency of alloy annealing cracking; Si element has the function of expanding the β phase region of the alloy of the present invention, improving the processing properties of the alloy, in addition, Si and Ni generate NiSi compounds, which can improve the strength of the alloy, but excessive NiSi compounds will increase the wear of the cutting tool during operation. If the content of the above elements is too low, the effect is not obvious; if the content is too high, it will affect the comprehensive performance of the zinc-white copper alloy of the present invention, and will also have an adverse effect on the surface flatness. Therefore, the content of X in the zinc-white copper alloy of the present invention is controlled at 0.0001-0.5%.
作为优选，该低镍锌白铜合金的质量百分比组成中还包括总量0.5％以下的M，M为选自P、Al、Cr、Mg、Ti、Sb、Bi、Zr中的至少一种元素。这些元素在改善合金强度、切削性和耐腐蚀性能的同时，对合金的加工性能不会造成显著的负面影响。本发明锌白铜合金中添加微量P、Ti或Zr元素，能够进一步细化晶粒，提升合金的强度，但若含量过高，合金在高温挤压时开裂倾向增大。除此之外，本发明合金添加的P、Mg、Zr或Sb元素可与Cu形成金属间化合物，金属间化合物有助于车削过程的断屑，从而改善合金的切削性能，但含量过高会增加切削刀具的磨损。本发明合金中Al元素可与Ni形成NiAl化合物，提升合金强度，此外，Al可在合金表面形成一层致密的Al 2O 3保护膜，具有提高合金耐腐蚀性能的作用。Cr元素可提升合金的耐腐蚀性能，在锌白铜中可形成单质Cr相，提升强度和切削性能。Bi元素的添加对合金的切削和钻削性能具有改善作用。 Preferably, the mass percentage composition of the low nickel zinc white copper alloy also includes a total amount of less than 0.5% M, where M is at least one element selected from P, Al, Cr, Mg, Ti, Sb, Bi, and Zr. These elements will not have a significant negative impact on the processing performance of the alloy while improving the strength, cutting performance and corrosion resistance of the alloy. Adding trace amounts of P, Ti or Zr elements to the zinc white copper alloy of the present invention can further refine the grains and improve the strength of the alloy, but if the content is too high, the alloy will increase its cracking tendency during high temperature extrusion. In addition, the P, Mg, Zr or Sb elements added to the alloy of the present invention can form intermetallic compounds with Cu, and the intermetallic compounds help break chips during the turning process, thereby improving the cutting performance of the alloy, but too high a content will increase the wear of the cutting tool. The Al element in the alloy of the present invention can form a NiAl compound with Ni to improve the strength of the alloy. In addition, Al can form a dense Al 2 O 3 protective film on the surface of the alloy, which has the effect of improving the corrosion resistance of the alloy. The Cr element can improve the corrosion resistance of the alloy, and can form a single Cr phase in the zinc white copper to improve the strength and cutting performance. The addition of Bi element improves the cutting and drilling performance of the alloy.
除了控制添加的元素及其含量外，本发明还通过优化合金的相组成、相占比等微观组织结构，实现低镍含量的锌白铜合金的切削性能以及包括强度、耐腐蚀性和冷热加工性能在内的综合性能的提升。In addition to controlling the added elements and their contents, the present invention also achieves the improvement of the cutting performance of the zinc-white copper alloy with low nickel content as well as the comprehensive performance including strength, corrosion resistance and hot and cold processing performance by optimizing the microstructure of the alloy such as the phase composition and phase ratio.
本发明锌白铜合金的微观组织主要包括α相、β相和Pb颗粒，并控制该低镍锌白铜合金 横截面上的微观组织中，α相的面积率为67～93％，β相的面积率为5～30％，且α相、β相和Pb颗粒均匀分布，使合金在具有优异冷热加工性能的前提下，合金强度、耐腐蚀性和切削性能得到增强。高温下α相呈硬态，合金中过量的α相导致热加工性能差，挤压困难，高温挤压后，表面裂纹增多，易脆断，抗拉强度和硬度值较低，挤压工艺难以完成，主要是因为在挤压工序中，硬态α相的较大摩擦力导致升温剧烈，合金局部超过熔点而熔化后，挤压线坯表面产生径向裂纹；而高温下β相呈软态，β相的出现导致热挤压容易实现，在高温挤压后，线坯表面光滑，无裂纹，抗拉强度和硬度值增大，耐腐蚀性能提高，伸长率降低，热加工性能好。但低温下β相是硬态，过量的β相有助于合金热挤压工艺，而使冷加工难度增大。因此，本发明将合金中的α、β相的面积率分别控制在67～93％和5～30％范围，实现合金优异的综合性能。The microstructure of the zinc-nickel white copper alloy of the present invention mainly includes α phase, β phase and Pb particles, and the microstructure on the cross section of the low-nickel zinc-nickel white copper alloy is controlled, the area ratio of the α phase is 67-93%, the area ratio of the β phase is 5-30%, and the α phase, β phase and Pb particles are evenly distributed, so that the alloy has excellent cold and hot processing performance, and the alloy strength, corrosion resistance and cutting performance are enhanced. At high temperature, the α phase is hard, and the excessive α phase in the alloy leads to poor hot processing performance and difficulty in extrusion. After high-temperature extrusion, the surface cracks increase, it is easy to break, the tensile strength and hardness values are low, and the extrusion process is difficult to complete, mainly because in the extrusion process, the large friction force of the hard α phase leads to a sharp temperature rise, and after the alloy partially exceeds the melting point and melts, radial cracks are generated on the surface of the extruded wire billet; while the β phase is soft at high temperature, the appearance of the β phase makes hot extrusion easy to achieve, after high-temperature extrusion, the surface of the wire billet is smooth, crack-free, tensile strength and hardness values increase, corrosion resistance is improved, elongation is reduced, and hot processing performance is good. However, the β phase is hard at low temperatures, and excessive β phase helps the alloy hot extrusion process, but makes cold processing more difficult. Therefore, the present invention controls the area ratios of α and β phases in the alloy to 67-93% and 5-30% respectively, achieving excellent comprehensive performance of the alloy.
另外，本发明控制锌白铜合金横截面上的10000μm 2的单位面积内，面积小于10μm 2的β相的数量占该单位面积内β相的总数量的比值≥30％。β相的大小和分布影响合金的强度、耐腐蚀性、加工特性和应用性能，其晶粒尺寸小且弥散分布的情况下，合金致密性较好，抗中性盐雾腐蚀性更强，从而具有更优秀的耐蚀性能。β相本身属于硬脆相，其硬度较高，当以小晶粒尺寸弥散分布在合金中时，可以起到细晶增强的作用。另外，β相均匀分布于合金中，可以提高合金在压力加工过程中的流变均匀性，降低因组织流变不一致导致的加工开裂倾向。细小的β相均匀分布还可以降低在微观尺度范围内因α相和β相硬度不同导致的显微硬度波动，提高切削刀具在加工过程中的受力均匀性，并提升合金产品的切削性能。 In addition, the present invention controls the ratio of the number of β phases with an area less than 10 μm 2 to the total number of β phases in the unit area of 10000 μm 2 on the cross section of the zinc-white copper alloy to ≥30%. The size and distribution of the β phase affect the strength, corrosion resistance, processing characteristics and application performance of the alloy. When the grain size is small and dispersed, the alloy has better compactness and stronger resistance to neutral salt spray corrosion, thus having better corrosion resistance. The β phase itself belongs to a hard and brittle phase with high hardness. When it is dispersed in the alloy with a small grain size, it can play a role in fine grain enhancement. In addition, the β phase is evenly distributed in the alloy, which can improve the rheological uniformity of the alloy during pressure processing and reduce the tendency of processing cracking caused by inconsistent tissue rheology. The uniform distribution of fine β phases can also reduce the microhardness fluctuation caused by the different hardness of α phase and β phase in the microscopic scale range, improve the force uniformity of the cutting tool during processing, and improve the cutting performance of the alloy product.
本发明控制锌白铜合金横截面上的微观组织中，Pb颗粒的平均面积不超过20μm 2，且面积小于5μm 2的Pb颗粒的数量占Pb颗粒的总数量的比值≥30％。细小的Pb颗粒一方面能够均匀分布于铜基体中，进一步提高合金的的切削均匀性；另一方面，在热加工过程中，细小的Pb颗粒部分溶于β相中，同时也有部分Pb颗粒在α与β相变中进入晶内，分布于晶界处的细小Pb颗粒能够减少Cl -离子在Pb颗粒与晶粒之间的渗透，使合金耐腐蚀性提高。当Pb颗粒尺寸过大时，将增大Pb颗粒和晶界之间的界面面积，加速Cl -离子的渗透，降低合金的耐腐蚀性。 The present invention controls the average area of the Pb particles in the microstructure on the cross section of the zinc-white copper alloy to be no more than 20 μm 2 , and the ratio of the number of Pb particles with an area less than 5 μm 2 to the total number of Pb particles is ≥30%. On the one hand, the fine Pb particles can be evenly distributed in the copper matrix, further improving the cutting uniformity of the alloy; on the other hand, during the hot working process, the fine Pb particles are partially dissolved in the β phase, and at the same time, some Pb particles enter the crystal during the α and β phase transformation. The fine Pb particles distributed at the grain boundary can reduce the penetration of Cl- ions between the Pb particles and the grains, thereby improving the corrosion resistance of the alloy. When the size of the Pb particles is too large, the interface area between the Pb particles and the grain boundary will be increased, accelerating the penetration of Cl- ions and reducing the corrosion resistance of the alloy.
作为优选，该低镍锌白铜合金的拉伸强度≥550MPa，屈服强度≥500MPa，延伸率≥2％，显微硬度HV值≥120，在pH值＝7的中性盐雾下24h不发生腐蚀，切削性能为C3604合金切削性能的80％以上。Preferably, the low nickel zinc white copper alloy has a tensile strength of ≥550MPa, a yield strength of ≥500MPa, an elongation of ≥2%, a microhardness HV value of ≥120, no corrosion occurs in a neutral salt spray with a pH value of 7 for 24 hours, and a cutting performance of more than 80% of that of the C3604 alloy.
本发明还提供了上述低镍锌白铜合金的制备方法，包括如下步骤：熔铸→热挤压→一次退火→一次拉伸→二次退火→二次拉伸，具体如下：The present invention also provides a method for preparing the low-nickel zinc white copper alloy, comprising the following steps: melting and casting → hot extrusion → primary annealing → primary stretching → secondary annealing → secondary stretching, specifically as follows:
1)熔铸：按成分要求配好的炉料放入熔炼炉中进行连续铸造，得到铸锭，其中熔炼温度为1050～1150℃，连铸温度为1000～1110℃。当连铸温度偏低时，晶粒组织较细，有利于提高引锭速度，但是铸锭容易产生冷隔和表面出现裂纹，甚至在结晶器内断裂。反之，温度过高，铸锭表面会较光滑，但冷却强度低时容易拉漏，晶粒粗大。综合考虑各种因素的影响，连铸温度控制在1000～1110℃范围，得到表面光滑且晶粒细小均匀的铸锭。本发明控制熔铸的拉铸速度为20～40mm/min，若拉铸速度过低，熔体凝固过快，合金的固液区靠近炉口，铸坯与石墨结晶的摩擦接触区增加，拉铸力增大，严重可能出现拉不动现象，另外，合金铸坯的生产效率降低；若拉铸速度过快，则合金的固液区向结晶器口靠近，不利于熔体的气体排出，且合金的固液区过于靠近结晶器出口，如果此时保温炉存在炉温波动，那么极有可能出现拉漏现象。1) Melting and casting: The charge prepared according to the composition requirements is placed in a smelting furnace for continuous casting to obtain an ingot, wherein the smelting temperature is 1050-1150°C and the continuous casting temperature is 1000-1110°C. When the continuous casting temperature is low, the grain structure is finer, which is conducive to increasing the ingot drawing speed, but the ingot is prone to cold shut and surface cracks, and even breaks in the crystallizer. On the contrary, if the temperature is too high, the surface of the ingot will be smoother, but it is easy to leak when the cooling intensity is low, and the grains are coarse. Taking into account the influence of various factors, the continuous casting temperature is controlled in the range of 1000-1110°C to obtain an ingot with a smooth surface and fine and uniform grains. The present invention controls the casting speed of the melt casting to be 20-40 mm/min. If the casting speed is too low, the melt solidifies too quickly, the solid-liquid area of the alloy is close to the furnace mouth, the friction contact area between the ingot and the graphite crystal increases, the casting force increases, and the ingot may not be pulled properly. In addition, the production efficiency of the alloy ingot is reduced. If the casting speed is too fast, the solid-liquid area of the alloy is close to the crystallizer mouth, which is not conducive to the gas discharge of the melt. The solid-liquid area of the alloy is too close to the crystallizer outlet. If the temperature of the holding furnace fluctuates at this time, leakage is very likely to occur.
2)热挤压：热挤压的挤压温度为700～800℃，变形量≥90％。当挤压温度偏低时，α相和β相之间变形不均匀，产生负拉力，导致合金在冷拉时易出现裂纹，因而挤压时下限温度应高于700℃。但温度过高，对表面质量产生不利影响，因挤压温度升高后，合金的塑性降低，变形不均匀性增加，其结果是挤压制品的表面层合金再结晶为粗大晶粒，形成粗晶环，降低冷加工的塑性指标，因此热挤压过程中，上限温度控制在800℃。本发明锌白铜合金的挤压速度控制在2～8mm/s范围，若挤压速度过快，会导致合金在模具中产生非接触变形，填充不满模孔而出现废品；若挤压速度过慢，则效率过低。2) Hot extrusion: The extrusion temperature of hot extrusion is 700-800℃, and the deformation is ≥90%. When the extrusion temperature is low, the deformation between the α phase and the β phase is uneven, resulting in negative tension, which makes the alloy prone to cracks during cold drawing. Therefore, the lower limit temperature during extrusion should be higher than 700℃. However, too high a temperature will have an adverse effect on the surface quality. After the extrusion temperature increases, the plasticity of the alloy decreases and the deformation unevenness increases. As a result, the surface layer alloy of the extruded product recrystallizes into coarse grains, forming a coarse grain ring, which reduces the plasticity index of cold working. Therefore, during the hot extrusion process, the upper limit temperature is controlled at 800℃. The extrusion speed of the zinc-white copper alloy of the present invention is controlled in the range of 2-8mm/s. If the extrusion speed is too fast, the alloy will produce non-contact deformation in the mold, and the mold hole will not be filled and waste will appear; if the extrusion speed is too slow, the efficiency will be too low.
3)一次退火：退火温度为600～700℃，保温时间为2～4h。若温度低于600℃或保温时间少于2h时，难以充分消除加工后的变形组织，不利于合金的后续加工；若退火温度高于700℃或保温时间超过4h，则会导致晶粒过大、α和β相分布不均匀。3) Primary annealing: The annealing temperature is 600-700℃, and the holding time is 2-4h. If the temperature is lower than 600℃ or the holding time is less than 2h, it is difficult to fully eliminate the deformed structure after processing, which is not conducive to the subsequent processing of the alloy; if the annealing temperature is higher than 700℃ or the holding time exceeds 4h, it will lead to excessively large grains and uneven distribution of α and β phases.
4)一次拉伸：在15～25％的拉伸加工率下进行拉伸，该加工率有利于晶粒的重新分布及晶粒尺寸均匀性的提高。4) Primary stretching: Stretching is performed at a stretching processing rate of 15 to 25%, which is beneficial to the redistribution of grains and the improvement of the uniformity of grain size.
5)二次退火：二次退火的退火温度为600～670℃，退火时间为2～4h，以获得均匀的晶粒组织。5) Secondary annealing: The annealing temperature of the secondary annealing is 600-670°C and the annealing time is 2-4 hours to obtain a uniform grain structure.
6)二次拉伸：拉伸加工率为15～35％，以获得光洁的材料表面、特定的微观组织及性能。6) Secondary stretching: The stretching processing rate is 15-35% to obtain a smooth material surface, specific microstructure and properties.
为满足所需规格的样品的制备，可对二次拉伸后的样品进行多次退火、拉伸。In order to prepare samples that meet the required specifications, the samples after secondary stretching can be annealed and stretched multiple times.
与现有技术相比，本发明具有如下优点：Compared with the prior art, the present invention has the following advantages:
(1)本发明通过降低锌白铜合金中的镍含量，并添加Mn和Pb元素，使合金微观组织含有α相、β相和Pb颗粒，获得具有优异的切削性能，良好的抗拉强度和耐腐蚀性能，且加工性能优异、制造成本低的锌白铜合金。(1) The present invention reduces the nickel content in the zinc-nickel alloy and adds Mn and Pb elements so that the alloy microstructure contains α phase, β phase and Pb particles, thereby obtaining a zinc-nickel alloy with excellent cutting performance, good tensile strength and corrosion resistance, excellent processing performance and low manufacturing cost.
(2)本发明通过对合金中的β相占比和大小、以及α相占比进行控制，保证合金的横截面上的微观组织中，α相的面积率为67～93％，β相的面积率为5～30％；合金横截面上的10000μm 2的单位面积内，面积小于10μm 2的β相的数量占该单位面积内β相的总数量的比值≥30％，实现了合金良好的抗拉强度、耐腐蚀性能和加工性能。 (2) The present invention controls the proportion and size of the β phase and the proportion of the α phase in the alloy to ensure that in the microstructure on the cross section of the alloy, the area ratio of the α phase is 67-93%, and the area ratio of the β phase is 5-30%; within a unit area of 10000μm2 on the cross section of the alloy, the ratio of the number of β phases with an area less than 10μm2 to the total number of β phases in the unit area is ≥30%, thereby achieving good tensile strength, corrosion resistance and processing performance of the alloy.
(3)本发明通过对Pb颗粒尺寸和数量进行控制，保证合金横截面上的微观组织中，Pb颗粒的平均面积不超过20μm 2，且面积小于5μm 2的Pb颗粒的数量占Pb颗粒的总数量的比值≥30％，实现了合金优异切削性能和加工性能。 (3) The present invention controls the size and number of Pb particles to ensure that in the microstructure on the cross section of the alloy, the average area of the Pb particles does not exceed 20 μm 2 and the number of Pb particles with an area less than 5 μm 2 accounts for ≥30% of the total number of Pb particles, thereby achieving excellent cutting performance and processing performance of the alloy.
(4)本发明可以实现拉伸强度≥550MPa，屈服强度≥500MPa，延伸率≥2％，显微硬度HV值≥120，在pH值＝7的中性盐雾下24h不发生腐蚀，切削性能为C3604切削性能的80％以上，本发明低镍含量的锌白铜具有优异的综合性能可有效降低合金产品的生产成本和提高产品使用寿命。(4) The present invention can achieve tensile strength ≥550MPa, yield strength ≥500MPa, elongation ≥2%, microhardness HV value ≥120, no corrosion occurs for 24 hours under neutral salt spray with pH value = 7, and the cutting performance is more than 80% of the cutting performance of C3604. The zinc white copper with low nickel content of the present invention has excellent comprehensive performance and can effectively reduce the production cost of alloy products and increase the service life of products.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为实施例7的低镍锌白铜合金横截面上Pb颗粒分布的金相显微组织照片；FIG1 is a metallographic microstructure photograph of the distribution of Pb particles on a cross section of a low-nickel zinc-nickel white copper alloy of Example 7;
图2为实施例7的低镍锌白铜合金横截面上α相和β相分布的金相显微组织照片。FIG. 2 is a metallographic microstructure photograph of the distribution of α phase and β phase on the cross section of the low nickel zinc white copper alloy of Example 7.
具体实施方式Detailed ways
以下结合附图实施例对本发明作进一步详细描述。The present invention is further described in detail below with reference to the accompanying drawings.
按照表1中20个实施例合金和1个对比例合金的成分，分别按配比称取各原料并配料，在1050～1150℃温度下熔炼，熔化后在1000～1110℃的连铸温度和20～40mm/min的拉铸速度下进行连续铸造形成铸锭，并将铸锭进行车削表面处理，然后再进行热挤压，挤压温度为700～800℃，挤压速度为2～8mm/s，挤压率≥90％，挤压力控制在60～100bar，接着对产品进行酸洗和刨皮除去表面杂质，然后对挤压坯进行2次拉伸和2次退火：在600～700℃温度下一次退火2～4h，退火后对样品表面进行酸洗除去表面杂质，随后在15～25％的拉伸加工率下进行一次拉伸；最后进行二次退火和二次拉伸：样品在600～670℃温度下退火2～4h，二次退火后的样品进行酸洗去除表面杂质后，在15～35％的拉伸加工率下进行二次拉伸，获得所需规格的样品。According to the compositions of the 20 example alloys and 1 comparative example alloy in Table 1, the raw materials were weighed and mixed according to the proportions, smelted at 1050-1150° C., and after melting, continuously casted at a continuous casting temperature of 1000-1110° C. and a casting speed of 20-40 mm/min to form an ingot, and the ingot was subjected to a turning surface treatment, and then hot extruded at an extrusion temperature of 700-800° C., an extrusion speed of 2-8 mm/s, an extrusion rate of ≥90%, and an extrusion pressure of 60-100 bar. Then, the product was subjected to a hot extrusion process. The sample is pickled and planed to remove surface impurities, and then the extruded billet is stretched and annealed twice: one annealing is performed at 600-700°C for 2-4 hours, and after annealing, the sample surface is pickled to remove surface impurities, and then a stretching is performed at a stretching processing rate of 15-25%; finally, a secondary annealing and secondary stretching are performed: the sample is annealed at 600-670°C for 2-4 hours, the sample after the secondary annealing is pickled to remove surface impurities, and then a secondary stretching is performed at a stretching processing rate of 15-35% to obtain a sample of the required specifications.
对于所得到的各实施例和对比例合金样品，在以下条件下进行特性评价，测试结果如表2和表3所示。The properties of the obtained alloy samples of the embodiments and comparative examples were evaluated under the following conditions. The test results are shown in Tables 2 and 3.
室温拉伸试验按照《GB/T 228.1-2010金属材料拉伸试验第1部分：室温试验方法》在电子万能力学性能试验机上测试抗拉强度和延伸率。The room temperature tensile test is carried out in accordance with GB/T 228.1-2010 Tensile test of metallic materials Part 1: Room temperature test method, and the tensile strength and elongation are tested on an electronic universal mechanical properties testing machine.
显微硬度HV值按照《GB-T 4340.1-2009金属材料维氏硬度试验第1部分：试验方法》在数显维氏硬度计进行测试。The microhardness HV value is tested on a digital Vickers hardness tester in accordance with GB-T 4340.1-2009 Metallic Materials Vickers Hardness Test Part 1: Test Method.
耐腐蚀性能按照GB/T 10125-2021《人造气氛腐蚀试验盐雾试验》NSS实验，在pH值＝7的中性盐雾中进行24h试验。The corrosion resistance performance is tested in accordance with the NSS test of GB/T 10125-2021 "Artificial atmosphere corrosion test salt spray test" and is carried out for 24 hours in neutral salt spray with a pH value of 7.
在相同的机械加工条件下，采用切削力实验仪测得各实施例和对比例合金样品的切削力，并由此计算出各合金样品相对于黄铜C3604的切削性指数，假设C3604的切削性能是100％。Under the same machining conditions, the cutting force of each embodiment and comparative alloy sample was measured by a cutting force tester, and the machinability index of each alloy sample relative to brass C3604 was calculated based on this, assuming that the cutting performance of C3604 is 100%.
各实施例合金样品的α相、β相和Pb颗粒尺寸和数量测试采用金相显微镜对样品组织进行观察，并根据结果计算相的面积率和占比等。图1为实施例7的低镍锌白铜合金横截面上Pb颗粒分布的金相显微组织照片，图2为实施例7的低镍锌白铜合金横截面上α相和β相分布的金相显微组织照片。从图1和图2可见，在该锌白铜合金横截面中，Pb颗粒的平均面积为12.3μm 2，面积小于5μm 2的Pb颗粒的数量占Pb颗粒的总数量的比值为45％Pb；α相的面积率为88.82％，β相的面积率为9.38％，在10000μm 2的单位面积内，面积小于10μm 2的β相的数量占该单位面积内β相的总数量的比值为48％。 The size and quantity of α phase, β phase and Pb particles of the alloy samples of each embodiment were tested by using a metallographic microscope to observe the sample structure, and the area ratio and proportion of the phases were calculated based on the results. Figure 1 is a metallographic microstructure photo of the distribution of Pb particles on the cross section of the low-nickel zinc-white copper alloy of Example 7, and Figure 2 is a metallographic microstructure photo of the distribution of α phase and β phase on the cross section of the low-nickel zinc-white copper alloy of Example 7. It can be seen from Figures 1 and 2 that in the cross section of the zinc-white copper alloy, the average area of the Pb particles is 12.3μm 2 , and the number of Pb particles with an area of less than 5μm 2 accounts for 45% of the total number of Pb particles; the area ratio of the α phase is 88.82%, the area ratio of the β phase is 9.38%, and within a unit area of 10000μm 2 , the number of β phases with an area of less than 10μm 2 accounts for 48% of the total number of β phases within the unit area.
为了观察合金样品的表面质量，通过对合金样品表面进行肉眼观察，合金样品表面不产生裂纹的表示为“OK”，产生裂纹的表示为“NO”。In order to observe the surface quality of the alloy samples, the surfaces of the alloy samples were observed with the naked eye. The alloy samples with no cracks on the surface were marked as "OK", and those with cracks on the surface were marked as "NO".
表1实施例和对比例的成分Table 1 Composition of Examples and Comparative Examples
Figure PCTCN2022141737-appb-000001
Figure PCTCN2022141737-appb-000001
表2实施例和对比例的性能Table 2 Performance of Examples and Comparative Examples
Figure PCTCN2022141737-appb-000002
Figure PCTCN2022141737-appb-000002
表3实施例和对比例的微观组织Table 3 Microstructure of Examples and Comparative Examples
Figure PCTCN2022141737-appb-000003
Figure PCTCN2022141737-appb-000003
A值：在低镍锌白铜合金横截面上的10000μm 2的单位面积内，面积小于10μm 2的β相的数量占该单位面积内β相的总数量的比值； A value: the ratio of the number of β phases with an area less than 10 μm 2 to the total number of β phases in a unit area of 10000 μm 2 on the cross section of the low nickel-zinc white copper alloy;
B值：在低镍锌白铜合金横截面上的微观组织中，面积小于5μm 2的Pb颗粒的数量占Pb颗粒的总数量的比值。 B value: The ratio of the number of Pb particles with an area less than 5μm2 to the total number of Pb particles in the microstructure of the cross section of the low-nickel-zinc white copper alloy.

Claims (9)

  1. 一种低镍锌白铜合金，其特征在于，该低镍锌白铜合金的质量百分比组成包括：Cu 47.0～55.0％、Pb 1.5～3.0％、Ni 5.5～7.5％、Mn 1.5～4.0％、X 0.0001～0.5％，余量为Zn和不可避免的杂质，其中X为选自Fe、Sn、Si中的至少一种元素。A low-nickel zinc white copper alloy, characterized in that the mass percentage composition of the low-nickel zinc white copper alloy includes: Cu 47.0-55.0%, Pb 1.5-3.0%, Ni 5.5-7.5%, Mn 1.5-4.0%, X 0.0001-0.5%, and the balance is Zn and unavoidable impurities, wherein X is at least one element selected from Fe, Sn, and Si.
  2. 根据权利要求1所述的一种低镍锌白铜合金，其特征在于，该低镍锌白铜合金的质量百分比组成中还包括总量0.5％以下的M，M为选自P、Al、Cr、Mg、Ti、Sb、Bi、Zr中的至少一种元素。The low-nickel-zinc-white copper alloy according to claim 1 is characterized in that the mass percentage composition of the low-nickel-zinc-white copper alloy also includes M in a total amount of less than 0.5%, and M is at least one element selected from P, Al, Cr, Mg, Ti, Sb, Bi, and Zr.
  3. 根据权利要求1所述的一种低镍锌白铜合金，其特征在于，该低镍锌白铜合金的微观组织主要由α相、β相和Pb颗粒组成；在该低镍锌白铜合金横截面上的微观组织中，α相的面积率为67～93％，β相的面积率为5～30％。The low-nickel-zinc-white copper alloy according to claim 1 is characterized in that the microstructure of the low-nickel-zinc-white copper alloy is mainly composed of α phase, β phase and Pb particles; in the microstructure on the cross section of the low-nickel-zinc-white copper alloy, the area ratio of the α phase is 67-93%, and the area ratio of the β phase is 5-30%.
  4. 根据权利要求3所述的一种低镍锌白铜合金，其特征在于，在该低镍锌白铜合金横截面上的10000μm 2的单位面积内，面积小于10μm 2的β相的数量占该单位面积内β相的总数量的比值≥30％。 The low-nickel-zinc-white copper alloy according to claim 3 is characterized in that, within a unit area of 10000 μm 2 on a cross section of the low-nickel-zinc-white copper alloy, the ratio of the number of β phases with an area less than 10 μm 2 to the total number of β phases in the unit area is ≥30%.
  5. 根据权利要求3所述的一种低镍锌白铜合金，其特征在于，在该低镍锌白铜合金横截面上的微观组织中，Pb颗粒的平均面积不超过20μm 2，且面积小于5μm 2的Pb颗粒的数量占Pb颗粒的总数量的比值≥30％。 The low-nickel-zinc-white copper alloy according to claim 3 is characterized in that, in the microstructure on the cross section of the low-nickel-zinc-white copper alloy, the average area of the Pb particles does not exceed 20 μm 2 , and the number of Pb particles with an area less than 5 μm 2 accounts for ≥30% of the total number of Pb particles.
  6. 根据权利要求1所述的一种低镍锌白铜合金，其特征在于，该低镍锌白铜合金的拉伸强度≥550MPa，屈服强度≥500MPa，延伸率≥2％，显微硬度HV值≥120，在pH值＝7的中性盐雾下24h不发生腐蚀，切削性能为C3604合金切削性能的80％以上。The low-nickel-zinc-white copper alloy according to claim 1 is characterized in that the low-nickel-zinc-white copper alloy has a tensile strength of ≥550 MPa, a yield strength of ≥500 MPa, an elongation of ≥2%, a microhardness HV value of ≥120, no corrosion occurs for 24 hours under neutral salt spray with a pH value of 7, and a cutting performance of more than 80% of the cutting performance of the C3604 alloy.
  7. 一种权利要求1至6中任一项所述的低镍锌白铜合金的制备方法，其特征在于，包括如下步骤：熔铸→热挤压→一次退火→一次拉伸→二次退火→二次拉伸，其中，所述的熔铸的熔炼温度为1050～1150℃，连铸温度为1000～1110℃，拉铸速度为20～40mm/min。A method for preparing a low-nickel-zinc white copper alloy according to any one of claims 1 to 6, characterized in that it comprises the following steps: melting and casting → hot extrusion → primary annealing → primary stretching → secondary annealing → secondary stretching, wherein the melting temperature of the melting and casting is 1050-1150°C, the continuous casting temperature is 1000-1110°C, and the drawing speed is 20-40 mm/min.
  8. 根据权利要求7所述的低镍锌白铜合金的制备方法，其特征在于，所述的热挤压的挤压温度为700～800℃，挤压速度为2～8mm/s，变形量≥90％。The method for preparing a low-nickel-zinc-white copper alloy according to claim 7 is characterized in that the extrusion temperature of the hot extrusion is 700-800°C, the extrusion speed is 2-8 mm/s, and the deformation is ≥90%.
  9. 根据权利要求7所述的低镍锌白铜合金的制备方法，其特征在于，所述的一次退火的退火温度为600～700℃，退火时间为2～4h；所述的一次拉伸的拉伸加工率为15～25％；所述的二次退火的退火温度为600～670℃，退火时间为2～4h；所述的二次拉伸的拉伸加工率为15～35％。The method for preparing a low-nickel-zinc-white copper alloy according to claim 7 is characterized in that the annealing temperature of the primary annealing is 600-700°C, and the annealing time is 2-4 hours; the stretching processing rate of the primary stretching is 15-25%; the annealing temperature of the secondary annealing is 600-670°C, and the annealing time is 2-4 hours; the stretching processing rate of the secondary stretching is 15-35%.
PCT/CN2022/141737 2022-11-23 2022-12-25 Low-nickel zinc-cupronickel alloy and preparation method therefor WO2024108719A1 (en)

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