Etching-resistant phosphor bronze alloy and preparation method thereof

Abstract

The invention provides an etching-resistant phosphor bronze alloy and a preparation method thereof, and belongs to the field of phosphor bronze alloy preparation. According to the method, the alloy cast ingot is prepared in a horizontal continuous casting mode, the copper alloy melt can obtain a proper cooling rate, so that a uniform and fine cast ingot structure is obtained, and casting defects such as shrinkage porosity and shrinkage cavities are reduced; the size of the phosphor bronze alloy is continuously reduced through rolling and heat treatment, the grain size in the phosphor bronze alloy is continuously refined in the process, and element segregation is eliminated, so that the mechanical property of the phosphor bronze alloy is improved; by controlling the speed in the finished product continuous annealing process, the finished product continuous annealing process and the rotating speeds of upper and lower fans, on one hand, the hardness of the phosphor bronze alloy can be reduced, the toughness and plasticity of the phosphor bronze alloy can be improved, and on the other hand, the cooling rate of the phosphor bronze alloy can be controlled, so that the flatness and etching resistance of the phosphor bronze alloy are improved; therefore, the finished phosphor bronze strip foil can be used as a heat dissipation material of the vapor chamber after being half-etched.

Description

Technical Field

[0001] The present invention relates to the field of phosphor bronze alloy preparation, in particular to an etching-resistant phosphor bronze alloy and a preparation method thereof. Background Art

[0002] In recent years, with the rapid development of electronic technology, the applications and usage of various electronic and electrical equipment components have become increasingly widespread. Connectors, such as terminal connectors, relays, contactors, and contacts, serve as a bridge between electronic and electrical components, a role that is irreplaceable by any other electronic component. As the core component of electrical connectors, connectors are the cornerstone of this bridge. Currently, over 90% of connectors are made of copper alloy strip, making the development of electrical connectors inseparable from the development and innovation of copper alloy strip. The most widely used copper alloys for electrical connectors are beryllium copper, copper-nickel-silicon, and tin-phosphor bronze. Among these, tin-phosphor bronze is widely used due to its low price.

[0003] However, the phosphor bronze alloy strips currently available on the market warp after semi-etching, with warpage exceeding 1mm. This makes it impossible to weld the etched copper alloy strips together to form a closed cavity, severely limiting the application of phosphor bronze alloys. Therefore, reducing the warpage of phosphor bronze alloys has become a pressing technical problem in this field. Summary of the Invention

[0004] The object of the present invention is to provide an etching-resistant phosphor bronze alloy and a preparation method thereof. The preparation method provided by the present invention can significantly improve the etching resistance of the phosphor bronze alloy, while having excellent mechanical properties and low warping, and can be used as a heat dissipation material for a heat spreader after half etching.

[0005] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0006] The present invention provides a method for preparing an etching-resistant phosphor bronze alloy, comprising the following steps:

[0007] (1) melting the alloy raw materials and performing horizontal continuous casting to obtain alloy ingots;

[0008] (2) performing preliminary rolling and homogenization annealing on the alloy ingot obtained in step (1) to obtain a first annealed ingot;

[0009] (3) performing initial rolling and bell-type annealing on the first annealed ingot obtained in step (2) to obtain a second annealed ingot;

[0010] (4) subjecting the second annealed ingot obtained in step (3) to pre-finished product rolling, pre-finished product continuous annealing, unwinding and straightening in sequence to obtain a third annealed ingot;

[0011] (5) The third annealed ingot obtained in step (4) is subjected to finished product rolling and finished product continuous annealing in sequence to obtain an etching-resistant phosphor bronze alloy; the finished product continuous annealing temperature is 350 to 450° C., the finished product continuous annealing speed is 12 to 35 m / min, and the finished product continuous annealing furnace tension is 50 to 150 N; the upper and lower fan speeds during the finished product continuous annealing are 200 to 400 rpm.

[0012] Preferably, the casting temperature of the horizontal continuous casting in step (1) is 1200-1300° C.; the casting speed of the horizontal continuous casting is 110-180 mm / min.

[0013] Preferably, the total processing rate of the pre-rolling in step (2) is 50-60%; the processing rate of a single pass of the pre-rolling is 9-30%.

[0014] Preferably, the temperature of the homogenization annealing in step (2) is 600-700° C.; and the time of the homogenization annealing is 10-20 hours.

[0015] Preferably, the total processing rate of the initial rolling in step (3) is 60-85%; the processing rate of a single pass of the initial rolling is 9-30%.

[0016] Preferably, the temperature of the bell-shaped annealing in step (3) is 500-600° C.; and the time of the bell-shaped annealing is 5-15 hours.

[0017] Preferably, the total processing rate of the pre-finished product rolling in the step (4) is 55-65%; the single-pass processing rate of the pre-finished product rolling is 15-30%.

[0018] Preferably, the temperature of the pre-product continuous annealing in step (4) is 600-700° C.; the speed of the pre-product continuous annealing is 15-50 m / min.

[0019] Preferably, the total processing rate of the finished product rolling in step (5) is 10-28%; the number of processing passes of the finished product rolling is 1-2 times.

[0020] The present invention provides an etching-resistant phosphor bronze alloy prepared by the preparation method described in the above technical solution.

[0021] The invention provides a preparation method of an etching-resistant phosphor bronze alloy, comprising the following steps: (1) melting an alloy raw material and then performing horizontal continuous casting to obtain an alloy ingot; (2) sequentially performing pre-rolling and homogenization annealing on the alloy ingot obtained in the step (1) to obtain a first annealed ingot; (3) sequentially performing pre-rolling and ring bell annealing on the first annealed ingot obtained in the step (2) to obtain a second annealed ingot; (4) sequentially performing pre-finished product rolling, pre-finished product continuous annealing, unwinding and straightening on the second annealed ingot obtained in the step (3) to obtain a third annealed ingot; (5) sequentially performing finished product rolling and finished product continuous annealing on the third annealed ingot obtained in the step (4) to obtain an etching-resistant phosphor bronze alloy; the finished product continuous annealing temperature is 350-450°C, the finished product continuous annealing speed is 12-35 m / min, and the finished product continuous annealing furnace tension is 50-150 N; and the upper and lower fan speeds during the finished product continuous annealing are 200-400 rpm. The preparation method provided by the present invention adopts the horizontal continuous casting method to prepare alloy ingots, which can enable the copper alloy melt to obtain a suitable cooling rate, thereby obtaining a uniform and fine ingot structure and reducing casting defects such as shrinkage and shrinkage cavities; the size of the phosphor bronze alloy is continuously reduced by initial rolling, ring bell annealing, pre-finished product rolling, pre-finished product continuous annealing, finished product rolling and finished product continuous annealing, and in this process, the grain size in the phosphor bronze alloy is continuously refined, and element segregation is eliminated, thereby improving the mechanical properties of the phosphor bronze alloy; by controlling the speed during the finished product continuous annealing process, the finished product continuous annealing and the upper and lower fan speeds, on the one hand, the hardness of the phosphor bronze alloy can be reduced and its toughness and plasticity can be improved, and on the other hand, its cooling rate can be controlled, thereby improving the flatness and etching resistance of the phosphor bronze alloy, so that the phosphor bronze finished strip foil can be used as a heat dissipation material for a heat spreader after half etching. The results of the embodiment show that the etching-resistant phosphor bronze alloy provided by the present invention has a tensile strength greater than 530MPa, a yield strength greater than 480MPa, and an elongation A 50 ≥30%, hardness>170HV, warpage ≤0.3mm. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 This is a physical picture of the etching-resistant phosphor bronze alloy prepared in Examples 1 to 4;

[0023] Figure 2 for Figure 1 Actual picture of the medium-etching-resistant phosphor bronze alloy after turning over;

[0024] Figure 3 Detailed photos of phosphor bronze alloys prepared in Example 4 and Comparative Example 2;

[0025] Figure 4 This is a physical picture of the phosphor bronze alloy prepared in Example 5 and Comparative Example 3. DETAILED DESCRIPTION

[0026] The present invention provides a method for preparing an etching-resistant phosphor bronze alloy, comprising the following steps:

[0027] (1) melting the alloy raw materials and performing horizontal continuous casting to obtain alloy ingots;

[0028] (2) performing preliminary rolling and homogenization annealing on the alloy ingot obtained in step (1) to obtain a first annealed ingot;

[0029] (3) performing initial rolling and bell-type annealing on the first annealed ingot obtained in step (2) to obtain a second annealed ingot;

[0030] (4) subjecting the second annealed ingot obtained in step (3) to pre-finished product rolling, pre-finished product continuous annealing, unwinding and straightening in sequence to obtain a third annealed ingot;

[0031] (5) The third annealed ingot obtained in step (4) is subjected to finished product rolling and finished product continuous annealing in sequence to obtain an etching-resistant phosphor bronze alloy; the finished product continuous annealing temperature is 350 to 450° C., the finished product continuous annealing speed is 12 to 35 m / min, and the finished product continuous annealing furnace tension is 50 to 150 N; the upper and lower fan speeds during the finished product continuous annealing are 200 to 400 rpm.

[0032] The invention melts alloy raw materials and then performs horizontal continuous casting to obtain alloy ingots.

[0033] The present invention has no particular limitation on the specific type of the alloy raw material, as long as an etching-resistant phosphor bronze alloy with chemical composition meeting the requirements can be obtained.

[0034] The present invention does not specifically limit the temperature and time of the smelting. It can be determined according to the technical common sense of those skilled in the art, as long as the alloy raw materials can be completely melted and evenly mixed. As an embodiment of the present invention, the holding temperature of the smelting can be 1200-1300°C, or 1210°C, 1220°C, 1230°C, 1240°C, 1250°C, 1260°C, 1270°C, 1280°C, or 1290°C; the holding time of the smelting can be 15-30 minutes, or 18 minutes, 20 minutes, 22 minutes, 25 minutes, or 28 minutes. By controlling the holding temperature and holding time of the smelting, the present invention can effectively improve the uniformity of the copper alloy melt and reduce the segregation of the ingot.

[0035] In the present invention, the casting temperature of the horizontal continuous casting is preferably 1200-1300°C; the pulling speed of the horizontal continuous casting is preferably 110-180 mm / min. As an embodiment of the present invention, the casting temperature of the horizontal continuous casting can be 1210°C, 1220°C, 1230°C, 1240°C, 1250°C, 1260°C, 1270°C, 1280°C, or 1290°C; the pulling speed of the horizontal continuous casting can be 120 mm / min, 130 mm / min, 140 mm / min, 150 mm / min, 160 mm / min, or 170 mm / min. By controlling the casting temperature and pulling speed of the horizontal continuous casting, the present invention can achieve an appropriate cooling rate for the copper alloy melt, thereby obtaining a uniform and fine ingot structure and reducing casting defects such as shrinkage and shrinkage cavities.

[0036] After obtaining the alloy ingot, the present invention sequentially performs preliminary rolling and homogenization annealing on the alloy ingot to obtain a first annealed ingot.

[0037] In the present invention, the total processing rate of the pre-rough rolling is preferably 50-60%; the processing rate of a single pass of the pre-rough rolling is preferably 9-30%; and the pre-rough rolling is preferably cold rolling. As an embodiment of the present invention, the total processing rate of the pre-rough rolling can be 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58% or 59%; the processing rate of a single pass of the pre-rough rolling can be 10%, 12%, 15%, 18%, 20%, 22%, 25% or 28%. The present invention can reduce the size of the alloy ingot through pre-rough rolling. At the same time, during the pre-rough rolling process, the coarse grains inside the alloy ingot will be broken by external force to form fine grains, thereby improving the performance of the alloy ingot.

[0038] In the present invention, the homogenization annealing temperature is preferably 600-700°C; the homogenization annealing time is preferably 10-20 hours. As an embodiment of the present invention, the homogenization annealing temperature can be 610°C, 620°C, 630°C, 640°C, 650°C, 660°C, 670°C, 680°C, or 690°C; the homogenization annealing time can be 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, or 19 hours. The present invention can eliminate element segregation within the alloy through homogenization annealing.

[0039] The present invention preferably further comprises milling the upper and lower surfaces of the homogenized annealed product. In the present invention, the thickness of the milled surface is preferably 0.5 to 1 mm, more preferably 0.6 to 0.8 mm. The present invention can remove the surface oxide layer of the alloy ingot by milling.

[0040] After obtaining the first annealed ingot, the present invention sequentially performs initial rolling and ring bell annealing on the first annealed ingot to obtain the second annealed ingot.

[0041] In the present invention, the total processing rate of the initial rolling is preferably 60-85%; the processing rate of a single pass of the initial rolling is preferably 9-30%; and the initial rolling is preferably cold rolling. As one embodiment of the present invention, the total processing rate of the initial rolling can be 62%, 65%, 68%, 70%, 72%, 75%, 78%, 80%, or 82%; and the processing rate of a single pass of the initial rolling can be 10%, 12%, 15%, 18%, 20%, 22%, 25%, or 28%. The present invention can significantly reduce the size of the alloy ingot through initial rolling, and the large-scale plastic deformation is more conducive to grain refinement.

[0042] The present invention preferably performs trimming on the initially rolled product. The present invention has no particular limitation on the specific operation and size of the trimming, which can be determined according to the common sense of those skilled in the art, as long as the product can be cut into a standard width of 630 mm.

[0043] In the present invention, the temperature of the ring bell annealing is preferably 500-600°C; the time of the ring bell annealing is preferably 5-15h. As an embodiment of the present invention, the temperature of the ring bell annealing can be 510°C, 520°C, 530°C, 540°C, 550°C, 560°C, 570°C, 580°C or 590°C; the time of the ring bell annealing can be 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h or 14h. The present invention can eliminate the internal stress generated during the initial rolling process, reduce the hardness of the secondary annealing ingot, improve its toughness and plasticity, and facilitate subsequent rolling through the ring bell annealing. On the other hand, it can further eliminate the element segregation generated during the rolling process.

[0044] The present invention preferably further comprises brushing the second annealed ingot. The present invention does not particularly limit the specific operation of the brushing, as long as the surface of the second annealed ingot can be brushed clean. As an embodiment of the present invention, the brushing can be performed sequentially using a PC brush and a needle brush.

[0045] In the present invention, the thickness of the second annealing ingot is preferably 1.2 to 2.0 mm. By controlling the thickness of the second annealing ingot, the present invention facilitates subsequent processing to obtain a final product with a thickness that meets the requirements.

[0046] After obtaining the second annealing ingot, the present invention sequentially performs pre-finished product rolling, pre-finished product continuous annealing, unwinding and straightening on the second annealing ingot to obtain a tertiary annealing ingot.

[0047] In the present invention, the total processing rate of the pre-finished product rolling is preferably 55-65%; the processing rate of a single pass of the pre-finished product rolling is preferably 15-30%; and the pre-finished product rolling is preferably cold-rolled. As one embodiment of the present invention, the total processing rate of the pre-finished product rolling can be 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, or 64%; and the processing rate of a single pass of the pre-finished product rolling can be 18%, 20%, 22%, 25%, or 28%. The present invention, through pre-finished product rolling, can significantly reduce the size of the annealed ingot on the one hand, and further break up the grains in the alloy, thereby refining the grains and further improving the mechanical properties of the alloy ingot on the other hand.

[0048] In the present invention, the temperature for continuous annealing of the pre-finished product is preferably 600-700°C; the speed for continuous annealing of the pre-finished product is preferably 15-50 m / min. As one embodiment of the present invention, the temperature for continuous annealing of the pre-finished product may be 610°C, 620°C, 630°C, 640°C, 650°C, 660°C, 670°C, 680°C, or 690°C; the speed for continuous annealing of the pre-finished product may be 20 m / min, 25 m / min, 30 m / min, 35 m / min, 40 m / min, or 45 m / min. Through continuous annealing of the pre-finished product, the present invention ensures that the grain size of the ingot is between 0.003 and 0.005 mm, the grains are uniform, and the properties are uniform.

[0049] The present invention has no special limitation on the specific operation of unwinding. It is sufficient to use unwinding operations well known to those skilled in the art to clean the rolls.

[0050] The present invention has no particular limitation on the specific operation of the tension-leveling, and any tension-leveling operation well known to those skilled in the art can be used. The present invention can control the shape of the plate before rolling by tension-leveling.

[0051] In the present invention, the thickness of the third annealing ingot is preferably 0.25 to 0.3 mm. By controlling the thickness of the third annealing ingot, the present invention can facilitate subsequent rolling to obtain an etching-resistant phosphor bronze alloy with a size that meets the requirements.

[0052] After obtaining the third annealing ingot, the present invention sequentially performs finished product rolling and finished product continuous annealing on the third annealing ingot to obtain an etching-resistant phosphor bronze alloy.

[0053] In the present invention, the total processing rate of the finished product rolling is preferably 10-28%; the number of processing passes of the finished product rolling is preferably 1-2; and the effective rolling surface during the finished product rolling is preferably ≥640 mm, more preferably ≥650 mm. As one embodiment of the present invention, the total processing rate of the finished product rolling can be 12%, 14%, 16%, 18%, 20%, 22%, 24%, or 26%. The present invention ensures that the effective rolling surface is ≥640 mm through finished product rolling, thereby ensuring an effective rolling surface and controlling the plate shape, thereby obtaining an etching-resistant phosphor bronze alloy that meets the requirements.

[0054] In the present invention, the temperature of the finished product continuous annealing is 350-450°C; the speed of the finished product continuous annealing is 12-35 m / min; and the tension in the furnace during the finished product continuous annealing is 50-150 N. In the present invention, the speed of the upper and lower fans during the finished product continuous annealing is 200-400 rpm; the fans include fans in the heating zone and the cooling zone. As one embodiment of the present invention, the temperature of the finished product continuous annealing can be 360°C, 370°C, 380°C, 390°C, 400°C, 410°C, 420°C, 430°C, or 440°C; the speed of the finished product continuous annealing can be 15 m / min, 18 m / min, 20 m / min, 22 m / min, 25 m / min, 28 m / min, 30 m / min, or 32 m / min; and the tension in the furnace during the finished product continuous annealing can be 60 N, 70 N, 80 N, 90 N, 100 N, 110 N, 120 N, 130 N, or 140 N. As an embodiment of the present invention, the speed of the upper and lower fans of the finished product continuous annealing can be 220rpm, 250rpm, 280rpm, 300rpm, 320rpm, 350rpm or 380rpm. The present invention does not have any special limitation on the number of the fans, as long as it can ensure the uniform atmosphere in the furnace. The present invention can eliminate the internal stress generated during the rolling process of the finished product through the continuous annealing of the finished product, thereby improving the toughness and plasticity of the copper alloy; by controlling the tension in the furnace and the speed of the upper and lower fans during the continuous annealing of the finished product, the atmosphere in the furnace can be made uniform, further improving the flatness and etching resistance uniformity of the phosphor bronze alloy, so that the phosphor bronze finished strip foil can be used as a heat dissipation material for a heat spreader after half etching.

[0055] In the present invention, the chemical composition of the etching-resistant phosphor bronze alloy preferably includes, by mass percentage, Sn: 5.0-9.0%, P: 0.01-0.2%, Ni: 0.001-0.1%, and the balance Cu. As an embodiment of the present invention, the mass percentage of Sn in the etching-resistant phosphor bronze alloy may be 5.5%, 6.0%, 6.5%, 7.0%, 7.5%, 8.0%, or 8.5%; the mass percentage of P in the etching-resistant phosphor bronze alloy may be 0.02%, 0.05%, 0.08%, 0.1%, 0.12%, 0.15%, or 0.18%; and the mass percentage of Ni in the etching-resistant phosphor bronze alloy may be 0.002%, 0.005%, 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, or 0.09%. The present invention can make the material meet the requirements of phosphor bronze alloy by controlling its chemical composition.

[0056] The preparation method provided by the present invention adopts a horizontal continuous casting method to prepare alloy ingots, which can enable the copper alloy melt to obtain a suitable cooling rate, thereby obtaining a uniform and fine ingot structure and reducing casting defects such as shrinkage and shrinkage cavities; the size of the phosphor bronze alloy is continuously reduced through initial rolling, ring bell annealing, pre-finished product rolling, pre-finished product continuous annealing, finished product rolling and finished product continuous annealing, and in this process, the grain size in the phosphor bronze alloy is continuously refined, and element segregation is eliminated, thereby improving the mechanical properties of the phosphor bronze alloy; by controlling the speed during the finished product continuous annealing process, the finished product continuous annealing and the upper and lower fan speeds, on the one hand, the hardness of the phosphor bronze alloy can be reduced and its toughness and plasticity can be improved; on the other hand, its cooling rate can be controlled, thereby improving the flatness and etching resistance of the phosphor bronze alloy, so that the finished phosphor bronze foil can be used as a heat dissipation material for a heat spreader after half etching.

[0057] The present invention also provides an etching-resistant phosphor bronze alloy prepared by the preparation method described in the above technical solution.

[0058] In the present invention, the chemical composition of the etching-resistant phosphor bronze alloy preferably includes, by mass percentage, Sn: 5.0-9.0%, P: 0.01-0.2%, Ni: 0.001-0.1%, and the balance Cu. As an embodiment of the present invention, the mass percentage of Sn in the etching-resistant phosphor bronze alloy may be 5.5%, 6.0%, 6.5%, 7.0%, 7.5%, 8.0%, or 8.5%; the mass percentage of P in the etching-resistant phosphor bronze alloy may be 0.02%, 0.05%, 0.08%, 0.1%, 0.12%, 0.15%, or 0.18%; and the mass percentage of Ni in the etching-resistant phosphor bronze alloy may be 0.002%, 0.005%, 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, or 0.09%. The etching-resistant phosphor bronze alloy provided by the present invention has good etching resistance. After etching, the warpage is ≤0.3 mm, and the mechanical properties are excellent.

[0059] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions of the present invention. Obviously, the embodiments described are only some of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0060] Example 1

[0061] A method for preparing an etching-resistant phosphor bronze alloy comprises the following steps:

[0062] (1) After melting the alloy raw materials, horizontal continuous casting is performed to obtain an alloy ingot; the holding temperature of the melting is 1250° C., and the holding time of the melting is 25 minutes; the casting temperature of the horizontal continuous casting is 1230-1300° C., and the casting speed of the horizontal continuous casting is 150 mm / min;

[0063] (2) The alloy ingot obtained in step (1) is subjected to pre-rolling and homogenization annealing in sequence, and finally the upper and lower surfaces are milled by 0.8 mm to obtain a first annealed ingot; the total processing rate of the pre-rolling is 54%, the single-pass processing rate is 9%, and the pre-rolling is cold rolling; the temperature of the homogenization annealing is 680° C., and the homogenization annealing time is 15 hours;

[0064] (3) The first annealed ingot obtained in step (2) is subjected to initial rolling, trimming (cutting into products with a standard width of 630 mm) and ring bell annealing in sequence to obtain a second annealed ingot, and then the surface of the second annealed ingot is brushed clean with a PC brush + a needle brush; the total processing rate of the initial rolling is 72%, the single pass processing rate is 9%, and the initial rolling is cold rolling; the temperature of the ring bell annealing is 550°C, and the time of the ring bell annealing is 8 hours;

[0065] (4) the second annealed ingot obtained in step (3) is subjected to pre-finished product rolling and pre-finished product continuous annealing in sequence, and then subjected to unwinding and straightening in sequence to obtain a third annealed ingot; the total processing rate of the pre-finished product rolling is 60%, the single-pass processing rate is 15%, and the pre-finished product rolling is cold rolling; the temperature of the pre-finished product continuous annealing is 650° C., the speed of the pre-finished product continuous annealing is 30 m / min, and the grain size is ensured to be 0.003 to 0.005 mm; the thickness of the three-times annealed ingot is 0.32 mm;

[0066] (5) The third annealed ingot obtained in step (4) is subjected to finished product rolling and finished product continuous annealing in sequence to obtain an etching-resistant phosphor bronze alloy with a thickness of 0.25 mm; the finished product rolling process is performed in two passes, with a total processing rate of 28%, and the roll shifting amount of the rolling mill is adjusted to ensure that the effective rolling plane is 650 mm; the finished product continuous annealing temperature is 380° C., the finished product continuous annealing speed is 18 m / min, and the finished product continuous annealing furnace tension is 70 N; the upper and lower fan speeds during the finished product continuous annealing are 380 rpm.

[0067] The chemical composition of the etching-resistant phosphor bronze alloy prepared in Example 1 is as follows, by mass percentage: Sn: 6.0%, P: 0.7%, Ni: 0.06% and the balance copper.

[0068] Example 2

[0069] A method for preparing an etching-resistant phosphor bronze alloy comprises the following steps:

[0070] (1) After melting the alloy raw materials, horizontal continuous casting is performed to obtain an alloy ingot; the holding temperature of the melting is 1250° C., and the holding time of the melting is 25 minutes; the casting temperature of the horizontal continuous casting is 1230-1300° C., and the casting speed of the horizontal continuous casting is 150 mm / min;

[0071] (2) The alloy ingot obtained in step (1) is subjected to pre-rolling and homogenization annealing in sequence, and finally the upper and lower surfaces are milled by 0.8 mm to obtain a first annealed ingot; the total processing rate of the pre-rolling is 54%, the single-pass processing rate is 9%, and the pre-rolling is cold rolling; the temperature of the homogenization annealing is 680° C., and the homogenization annealing time is 15 hours;

[0072] (3) The first annealed ingot obtained in step (2) is subjected to initial rolling, trimming (cutting into products with a standard width of 630 mm) and ring bell annealing in sequence to obtain a second annealed ingot, and then the surface of the second annealed ingot is brushed clean with a PC brush + a needle brush; the total processing rate of the initial rolling is 72%, the single pass processing rate is 9%, and the initial rolling is cold rolling; the temperature of the ring bell annealing is 550°C, and the time of the ring bell annealing is 8 hours;

[0073] (4) the second annealed ingot obtained in step (3) is subjected to pre-finished product rolling and pre-finished product continuous annealing in sequence, and then subjected to unwinding and straightening in sequence to obtain a third annealed ingot; the total processing rate of the pre-finished product rolling is 60%, the single-pass processing rate is 15%, and the pre-finished product rolling is cold rolling; the temperature of the pre-finished product continuous annealing is 650° C., the speed of the pre-finished product continuous annealing is 30 m / min, and the grain size is ensured to be 0.003 to 0.005 mm; the thickness of the third annealed ingot is 0.32 mm;

[0074] (5) The third annealed ingot obtained in step (4) is subjected to finished product rolling and finished product continuous annealing in sequence to obtain an etching-resistant phosphor bronze alloy with a thickness of 0.25 mm; the finished product rolling process is performed in two passes, with a total processing rate of 28%, and the roll shifting amount of the rolling mill is adjusted to ensure that the effective rolling plane is 650 mm; the finished product continuous annealing temperature is 400° C., the finished product continuous annealing speed is 20 m / min, and the finished product continuous annealing furnace tension is 90 N; the upper and lower fan speeds during the finished product continuous annealing are 350 rpm.

[0075] The chemical composition of the etching-resistant phosphor bronze alloy prepared in Example 2 is as follows, by mass percentage: Sn: 7.5%, P: 0.1%, Ni: 0.08% and the balance copper.

[0076] Example 3

[0077] A method for preparing an etching-resistant phosphor bronze alloy comprises the following steps:

[0078] (1) After melting the alloy raw materials, horizontal continuous casting is performed to obtain an alloy ingot; the holding temperature of the melting is 1250° C., and the holding time of the melting is 25 minutes; the casting temperature of the horizontal continuous casting is 1230-1300° C., and the casting speed of the horizontal continuous casting is 150 mm / min;

[0079] (2) The alloy ingot obtained in step (1) is subjected to pre-rolling and homogenization annealing in sequence, and finally the upper and lower surfaces are milled by 0.8 mm to obtain a first annealed ingot; the total processing rate of the pre-rolling is 54%, the single-pass processing rate is 9%, and the pre-rolling is cold rolling; the temperature of the homogenization annealing is 680° C., and the homogenization annealing time is 15 hours;

[0080] (3) The first annealed ingot obtained in step (2) is subjected to initial rolling, trimming (cutting into products with a standard width of 630 mm) and ring bell annealing in sequence to obtain a second annealed ingot, and then the surface of the second annealed ingot is brushed clean with a PC brush + a needle brush; the total processing rate of the initial rolling is 72%, the single pass processing rate is 9%, and the initial rolling is cold rolling; the temperature of the ring bell annealing is 550°C, and the time of the ring bell annealing is 8 hours;

[0081] (4) the second annealed ingot obtained in step (3) is subjected to pre-finished product rolling and pre-finished product continuous annealing in sequence, and then subjected to unwinding and straightening in sequence to obtain a third annealed ingot; the total processing rate of the pre-finished product rolling is 60%, the single-pass processing rate is 15%, and the pre-finished product rolling is cold rolling; the temperature of the pre-finished product continuous annealing is 650° C., the speed of the pre-finished product continuous annealing is 30 m / min, and the grain size is ensured to be 0.003 to 0.005 mm; the thickness of the third annealed ingot is 0.32 mm;

[0082] (5) The third annealed ingot obtained in step (4) is subjected to finished product rolling and finished product continuous annealing in sequence to obtain an etching-resistant phosphor bronze alloy with a thickness of 0.25 mm; the finished product rolling process is performed in two passes, with a total processing rate of 28%, and the roll shifting amount of the rolling mill is adjusted to ensure that the effective rolling plane is 650 mm; the finished product continuous annealing temperature is 420° C., the finished product continuous annealing speed is 25 m / min, and the finished product continuous annealing furnace tension is 100 N; the upper and lower fan speeds during the finished product continuous annealing are 300 rpm.

[0083] The chemical composition of the etching-resistant phosphor bronze alloy prepared in Example 3 is as follows, by mass percentage: Sn: 8.6%, P: 0.14%, Ni: 0.05% and the balance copper.

[0084] Example 4

[0085] A method for preparing an etching-resistant phosphor bronze alloy comprises the following steps:

[0086] (1) After melting the alloy raw materials, horizontal continuous casting is performed to obtain an alloy ingot; the holding temperature of the melting is 1250° C., and the holding time of the melting is 25 minutes; the casting temperature of the horizontal continuous casting is 1230-1300° C., and the casting speed of the horizontal continuous casting is 150 mm / min;

[0087] (2) The alloy ingot obtained in step (1) is subjected to pre-rolling and homogenization annealing in sequence, and finally the upper and lower surfaces are milled by 0.8 mm to obtain a first annealed ingot; the total processing rate of the pre-rolling is 54%, the single-pass processing rate is 9%, and the pre-rolling is cold rolling; the temperature of the homogenization annealing is 680° C., and the homogenization annealing time is 15 hours;

[0088] (3) The first annealed ingot obtained in step (2) is subjected to initial rolling, trimming (cutting into products with a standard width of 630 mm) and ring bell annealing in sequence to obtain a second annealed ingot, and then the surface of the second annealed ingot is brushed clean with a PC brush + a needle brush; the total processing rate of the initial rolling is 72%, the single pass processing rate is 9%, and the initial rolling is cold rolling; the temperature of the ring bell annealing is 550°C, and the time of the ring bell annealing is 8 hours;

[0089] (4) the second annealed ingot obtained in step (3) is subjected to pre-finished product rolling and pre-finished product continuous annealing in sequence, and then subjected to unwinding and straightening in sequence to obtain a third annealed ingot; the total processing rate of the pre-finished product rolling is 60%, the single-pass processing rate is 15%, and the pre-finished product rolling is cold rolling; the temperature of the pre-finished product continuous annealing is 650° C., the speed of the pre-finished product continuous annealing is 30 m / min, and the grain size is ensured to be 0.003 to 0.005 mm; the thickness of the third annealed ingot is 0.32 mm;

[0090] (5) The third annealed ingot obtained in step (4) is subjected to finished product rolling and finished product continuous annealing in sequence to obtain an etching-resistant phosphor bronze alloy with a thickness of 0.25 mm; the finished product rolling process is performed in two passes, with a total processing rate of 28%, and the roll shifting amount of the rolling mill is adjusted to ensure that the effective rolling plane is 650 mm; the finished product continuous annealing temperature is 410° C., the finished product continuous annealing speed is 28 m / min, and the finished product continuous annealing furnace tension is 80 N; the upper and lower fan speeds during the finished product continuous annealing are 340 rpm.

[0091] The chemical composition of the etching-resistant phosphor bronze alloy prepared in Example 4 is as follows, by mass percentage: Sn: 6.3%, P: 0.08%, Ni: 0.009% and the balance copper.

[0092] Example 5

[0093] A method for preparing an etching-resistant phosphor bronze alloy comprises the following steps:

[0094] (1) After melting the alloy raw materials, horizontal continuous casting is performed to obtain an alloy ingot; the holding temperature of the melting is 1250° C., and the holding time of the melting is 25 minutes; the casting temperature of the horizontal continuous casting is 1230-1300° C., and the casting speed of the horizontal continuous casting is 150 mm / min;

[0095] (2) The alloy ingot obtained in step (1) is subjected to pre-rolling and homogenization annealing in sequence, and finally the upper and lower surfaces are milled by 0.8 mm to obtain a first annealed ingot; the total processing rate of the pre-rolling is 54%, the single-pass processing rate is 9%, and the pre-rolling is cold rolling; the temperature of the homogenization annealing is 680° C., and the homogenization annealing time is 15 hours;

[0096] (3) The first annealed ingot obtained in step (2) is subjected to initial rolling, trimming (cutting into products with a standard width of 630 mm) and ring bell annealing in sequence to obtain a second annealed ingot, and then the surface of the second annealed ingot is brushed clean with a PC brush + a needle brush; the total processing rate of the initial rolling is 72%, the single pass processing rate is 9%, and the initial rolling is cold rolling; the temperature of the ring bell annealing is 550°C, and the time of the ring bell annealing is 8 hours;

[0097] (4) the second annealed ingot obtained in step (3) is subjected to pre-finished product rolling and pre-finished product continuous annealing in sequence, and then subjected to unwinding and straightening in sequence to obtain a third annealed ingot; the total processing rate of the pre-finished product rolling is 60%, the single-pass processing rate is 15%, and the pre-finished product rolling is cold rolling; the temperature of the pre-finished product continuous annealing is 650° C., the speed of the pre-finished product continuous annealing is 30 m / min, and the grain size is ensured to be 0.003 to 0.005 mm; the thickness of the third annealed ingot is 0.24 mm;

[0098] (5) The third annealed ingot obtained in step (4) is subjected to finished product rolling and finished product continuous annealing in sequence to obtain an etching-resistant phosphor bronze alloy with a thickness of 0.2 mm; the finished product rolling process is performed in two passes, with a total processing rate of 16.7%, and the roll shifting amount of the rolling mill is adjusted to ensure that the effective rolling plane is 650 mm; the finished product continuous annealing temperature is 400° C., the finished product continuous annealing speed is 26 m / min, and the finished product continuous annealing furnace tension is 100 N; the upper and lower fan speeds during the finished product continuous annealing are 400 rpm.

[0099] The chemical composition of the etching-resistant phosphor bronze alloy prepared in Example 5 is as follows, by mass percentage: Sn: 7.8%, P: 0.12%, Ni: 0.024% and the balance copper.

[0100] Comparative Example 1

[0101] A method for preparing a phosphor bronze alloy comprises the following steps:

[0102] (1) After melting the alloy raw materials, horizontal continuous casting is performed to obtain an alloy ingot; the holding temperature of the melting is 1250° C., and the holding time of the melting is 25 minutes; the casting temperature of the horizontal continuous casting is 1230-1300° C., and the casting speed of the horizontal continuous casting is 150 mm / min;

[0103] (2) The alloy ingot obtained in step (1) is subjected to pre-rolling and homogenization annealing in sequence, and finally the upper and lower surfaces are milled by 0.8 mm to obtain a first annealed ingot; the total processing rate of the pre-rolling is 54%, the single-pass processing rate is 9%, and the pre-rolling is cold rolling; the temperature of the homogenization annealing is 680° C., and the homogenization annealing time is 15 hours;

[0104] (3) The first annealed ingot obtained in step (2) is subjected to initial rolling, trimming (cutting into products with a standard width of 630 mm) and ring bell annealing in sequence to obtain a second annealed ingot, and then the surface of the second annealed ingot is brushed clean using a PC brush and a needle brush in sequence; the total processing rate of the initial rolling is 72%, the single-pass processing rate is 9%, and the initial rolling is cold rolling; the temperature of the ring bell annealing is 550° C., and the time of the ring bell annealing is 8 hours;

[0105] (4) the second annealed ingot obtained in step (3) is subjected to pre-finished product rolling and pre-finished product continuous annealing in sequence, and then unwinding is performed to obtain a third annealed ingot; the total processing rate of the pre-finished product rolling is 60%, the single-pass processing rate is 15%, and the pre-finished product rolling is cold rolling; the temperature of the pre-finished product continuous annealing is 650° C., the speed of the pre-finished product continuous annealing is 30 m / min, and the grain size is ensured to be 0.003 to 0.005 mm; the thickness of the third annealed ingot is 0.24 mm;

[0106] (5) The third annealed ingot obtained in step (4) is subjected to finished product rolling to obtain a phosphor bronze alloy with a thickness of 0.2 mm; the finished product rolling process is performed in two passes, with a total processing rate of 16.7%, and the roll shifting amount of the rolling mill is adjusted to ensure that the effective rolling plane is 650 mm.

[0107] The chemical composition of the phosphor bronze alloy prepared in Comparative Example 1 is as follows, by mass percentage: Sn: 7.2%, P: 0.6%, Ni: 0.07% and the balance copper.

[0108] Comparative Example 2

[0109] A method for preparing a phosphor bronze alloy comprises the following steps:

[0110] (1) After melting the alloy raw materials, horizontal continuous casting is performed to obtain an alloy ingot; the holding temperature of the melting is 1250° C., and the holding time of the melting is 25 minutes; the casting temperature of the horizontal continuous casting is 1230-1300° C., and the casting speed of the horizontal continuous casting is 150 mm / min;

[0111] (2) The alloy ingot obtained in step (1) is subjected to pre-rolling and homogenization annealing in sequence, and finally the upper and lower surfaces are milled by 0.8 mm to obtain a first annealed ingot; the total processing rate of the pre-rolling is 54%, the single-pass processing rate is 9%, and the pre-rolling is cold rolling; the temperature of the homogenization annealing is 680° C., and the homogenization annealing time is 15 hours;

[0112] (3) The first annealed ingot obtained in step (2) is subjected to initial rolling, trimming (cutting into products with a standard width of 630 mm) and ring bell annealing in sequence to obtain a second annealed ingot, and then the surface of the second annealed ingot is brushed clean using a PC brush and a needle brush in sequence; the total processing rate of the initial rolling is 72%, the single-pass processing rate is 9%, and the initial rolling is cold rolling; the temperature of the ring bell annealing is 550° C., and the time of the ring bell annealing is 8 hours;

[0113] (4) the second annealed ingot obtained in step (3) is subjected to pre-finished product rolling and pre-finished product continuous annealing in sequence, and then unwinding is performed to obtain a third annealed ingot; the total processing rate of the pre-finished product rolling is 60%, the single-pass processing rate is 15%, and the pre-finished product rolling is cold rolling; the temperature of the pre-finished product continuous annealing is 650° C., the speed of the pre-finished product continuous annealing is 30 m / min, and the grain size is ensured to be 0.003 to 0.005 mm; the thickness of the third annealed ingot is 0.24 mm;

[0114] (5) The third annealed ingot obtained in step (4) is subjected to finished product rolling and finished product continuous annealing in sequence to obtain a phosphor bronze alloy with a thickness of 0.2 mm; the finished product rolling process is performed in two passes, with a total processing rate of 16.7%, and the roll shifting amount of the rolling mill is adjusted to ensure that the effective rolling plane is 650 mm; the finished product continuous annealing temperature is 380° C., the finished product continuous annealing speed is 18 m / min, and the finished product continuous annealing furnace tension is 70 N; the upper and lower fan speeds during the finished product continuous annealing are 380 rpm.

[0115] The chemical composition of the phosphor bronze alloy prepared in Comparative Example 2 is as follows, by mass percentage: Sn: 7.8%, P: 0.2%, Ni: 0.03% and the balance copper.

[0116] Comparative Example 3

[0117] A method for preparing a phosphor bronze alloy comprises the following steps:

[0118] (1) After melting the alloy raw materials, horizontal continuous casting is performed to obtain an alloy ingot; the holding temperature of the melting is 1250° C., and the holding time of the melting is 25 minutes; the casting temperature of the horizontal continuous casting is 1230-1300° C., and the casting speed of the horizontal continuous casting is 150 mm / min;

[0119] (2) The alloy ingot obtained in step (1) is subjected to pre-rolling and homogenization annealing in sequence, and finally the upper and lower surfaces are milled by 0.8 mm to obtain a first annealed ingot; the total processing rate of the pre-rolling is 54%, the single-pass processing rate is 9%, and the pre-rolling is cold rolling; the temperature of the homogenization annealing is 680° C., and the homogenization annealing time is 15 hours;

[0120] (3) The first annealed ingot obtained in step (2) is subjected to initial rolling, trimming (cutting into products with a standard width of 630 mm) and ring bell annealing in sequence to obtain a second annealed ingot, and then the surface of the second annealed ingot is brushed clean using a PC brush and a needle brush in sequence; the total processing rate of the initial rolling is 72%, the single-pass processing rate is 9%, and the initial rolling is cold rolling; the temperature of the ring bell annealing is 550° C., and the time of the ring bell annealing is 8 hours;

[0121] (4) the second annealed ingot obtained in step (3) is subjected to pre-finished product rolling and pre-finished product continuous annealing in sequence, and then subjected to unwinding and straightening in sequence to obtain a third annealed ingot; the total processing rate of the pre-finished product rolling is 60%, the single-pass processing rate is 15%, and the pre-finished product rolling is cold rolling; the temperature of the pre-finished product continuous annealing is 650° C., the speed of the pre-finished product continuous annealing is 30 m / min, and the grain size is ensured to be 0.003 to 0.005 mm; the thickness of the third annealed ingot is 0.24 mm;

[0122] (5) The third annealed ingot obtained in step (4) is subjected to finished product rolling to obtain a phosphor bronze alloy with a thickness of 0.2 mm; the finished product rolling process is performed twice, with a total processing rate of 16.7%, and the roll shifting amount of the rolling mill is adjusted to ensure that the effective rolling plane is 650 mm.

[0123] The chemical composition of the phosphor bronze alloy prepared in Comparative Example 3 is as follows, by mass percentage: Sn: 6.1%, P: 0.72%, Ni: 0.06% and the balance copper.

[0124] The properties of the phosphor bronze alloys prepared in Examples 1 to 5 and Comparative Examples 1 to 3 were tested, and the results are shown in Table 1:

[0125] Table 1 Properties of phosphor bronze alloys prepared in Examples 1 to 5 and Comparative Examples 1 to 3

[0126]

[0127]

[0128] Among them, the test methods for tensile strength and yield strength are: GB / T 34505-2017 Room temperature tensile test method;

[0129] The test method for elongation is: GB / T 34505-2017 Room temperature tensile test method;

[0130] The test method for hardness is: GB / T 4340.1 Metallic materials Vickers hardness test Part 1: Test method;

[0131] The test method for warpage is: YS / T 1678-2023 Copper and copper alloy plates, strips and foils residual stress test method etching strip method.

[0132] As can be seen from Table 1, the phosphor bronze alloy obtained by the preparation method provided by the present invention not only has high tensile strength, yield strength and hardness, but also has high hardness and a warpage of 0.3 mm or less. In Comparative Examples 1 and 3, after omitting the continuous annealing of the finished product, although the tensile strength, yield strength and hardness are greatly improved, on the one hand, the elongation is greatly reduced, and the toughness and plasticity cannot meet the technical requirements, and on the other hand, the warpage is greatly increased, which cannot solve the technical problem of the present invention. In Comparative Examples 1 and 2, after omitting the tensile leveling, the warpage of the phosphor bronze alloy is greatly improved.

[0133] The physical pictures of the etching-resistant phosphor bronze alloys prepared in Examples 1 to 4 (Examples 1 to 4 from left to right) are as follows: Figure 1 As shown; Figure 1 The etching-resistant phosphor bronze alloy in the embodiment 1 to 4 is turned over (from left to right). Figure 2 As shown. Figure 1 and Figure 2 It can be seen that the warping of the etching-resistant phosphor bronze alloy prepared by the present invention is very small, and the warping is almost invisible.

[0134] The physical pictures of the phosphor bronze alloys prepared in Example 4 (right) and Comparative Example 2 (left) are as follows: Figure 3 As shown. Figure 3 It can be seen that the warping of the etching-resistant phosphor bronze alloy prepared in the present invention is very small, and almost no warping is visible, while the phosphor bronze alloy prepared in Comparative Example 2 has obvious warping.

[0135] The physical pictures of the phosphor bronze alloys prepared in Example 5 (right) and Comparative Example 3 (left) are as follows: Figure 4 As shown. Figure 4 It can be seen that the warping of the etching-resistant phosphor bronze alloy prepared in the present invention is very small, and almost no warping is visible, while the phosphor bronze alloy prepared in Comparative Example 3 has obvious warping.

[0136] From the above analysis, it can be seen that the preparation method provided by the present invention can significantly reduce the warpage of the etching-resistant phosphor bronze alloy. Compared with the comparative example, the warpage is greatly reduced.

[0137] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A method for preparing an etching-resistant phosphor bronze alloy, characterized in that: The following steps are involved: (1) melting the alloy raw materials and performing horizontal continuous casting to obtain alloy ingots; (2) performing preliminary rolling and homogenization annealing on the alloy ingot obtained in step (1) to obtain a first annealed ingot; (3) performing initial rolling and bell-type annealing on the first annealed ingot obtained in step (2) to obtain a second annealed ingot; (4) subjecting the second annealed ingot obtained in step (3) to pre-finished product rolling, pre-finished product continuous annealing, unwinding and straightening in sequence to obtain a third annealed ingot; (5) The third annealed ingot obtained in step (4) is subjected to finished product rolling and finished product continuous annealing in sequence to obtain an etching-resistant phosphor bronze alloy; the finished product continuous annealing temperature is 350 to 450° C., the finished product continuous annealing speed is 12 to 35 m / min, and the finished product continuous annealing furnace tension is 50 to 150 N; the upper and lower fan speeds during the finished product continuous annealing are 200 to 400 rpm.

2. The preparation method according to claim 1, characterized in that The casting temperature of the horizontal continuous casting in the step (1) is 1200-1300° C.; the casting speed of the horizontal continuous casting is 110-180 mm / min.

3. The preparation method according to claim 1, characterized in that The total processing rate of the pre-rolling in step (2) is 50-60%; the processing rate of a single pass of the pre-rolling is 9-30%.

4. The preparation method according to claim 1, characterized in that The temperature of the homogenization annealing in the step (2) is 600-700° C.; the time of the homogenization annealing is 10-20 hours.

5. The preparation method according to claim 1, characterized in that The total processing rate of the initial rolling in the step (3) is 60-85%; the processing rate of a single pass of the initial rolling is 9-30%.

6. The preparation method according to claim 1, characterized in that The temperature of the bell-shaped annealing in step (3) is 500-600° C.; the time of the bell-shaped annealing is 5-15 hours.

7. The preparation method according to claim 1, characterized in that The total processing rate of the pre-finished product rolling in the step (4) is 55-65%; the single-pass processing rate of the pre-finished product rolling is 15-30%.

8. The preparation method according to claim 1, characterized in that The temperature of the pre-product continuous annealing in step (4) is 600-700° C.; the speed of the pre-product continuous annealing is 15-50 m / min.

9. The preparation method according to claim 1, characterized in that The total processing rate of the finished product rolling in the step (5) is 10-28%; the number of processing passes of the finished product rolling is 1-2 times.

10. The etching-resistant phosphor bronze alloy prepared by the preparation method according to any one of claims 1 to 9.

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