CN111363953A - High-strength medium-conductivity copper-iron-phosphorus-zinc-magnesium alloy foil and processing method thereof - Google Patents
High-strength medium-conductivity copper-iron-phosphorus-zinc-magnesium alloy foil and processing method thereof Download PDFInfo
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C21/00—Alloys based on aluminium
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- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
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- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
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- 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
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Abstract
The invention discloses a high-strength medium-conductivity copper-iron-phosphorus-zinc-magnesium alloy foil and a processing method thereof, wherein the alloy foil comprises the following components: 2.1 to 2.4 percent of iron, 0.015 to 0.05 percent of phosphorus, 0.05 to 0.1 percent of zinc, 0.03 to 0.08 percent of magnesium, and the balance of copper and a small amount of impurities; the processing method comprises the steps of smelting and casting, solid solution, surface milling, primary cold rolling, primary aging, secondary cold rolling, secondary aging, tertiary cold rolling, stress relief annealing and stretch bending straightening. According to the invention, trace Zn and Mg are added on the basis of Cu-Fe-P, and the high-strength high-conductivity copper-iron-phosphorus-zinc-magnesium alloy foil with the thickness of 0.04-0.15mm is obtained through casting, hot working, cold working and aging treatment, wherein the tensile strength of the product reaches 500MPa, the electric conductivity is not less than 70% IACS, the softening resistance temperature exceeds 450 ℃, and the ultrathin high-strength structural support for the industries of communication, mobile phones and the like can be met.
Description
Technical Field
The invention belongs to the technical field of copper alloy foil processing, and particularly relates to a high-strength medium-conductivity copper-iron-phosphorus-zinc-magnesium alloy foil and a processing method thereof.
Background
With the arrival of the 5G era, the trend of integration, miniaturization and arrangement densification of devices such as electric power and electronics is developed, the requirement of an internal electronic supporting piece is also developed towards the aspects of thinner, high-strength and excellent heat transfer, the requirement on the performance of copper alloy is higher and higher, and the production cost is lower and lower. This requires the development of copper alloy products for communication and mobile phone industries toward high performance foils.
The Integrated Circuit (IC) is composed of a chip, a lead frame and a plastic package. The lead frame has the main functions of providing a mechanical support carrier for the chip, serving as a conductive medium to be connected with an IC external circuit, transmitting an electric signal, and outwards dissipating heat generated during the operation of the chip together with a plastic package material to become a critical part in the IC. With the development of high density, miniaturization and multi-functionalization of integrated circuits, the requirements on lead frames and electronic packaging materials are higher and higher.
The current common copper alloy foil applied to the ultrathin high-strength structural support is mainly a high-strength low-conductivity phosphorus copper alloy foil, the main representative is copper tin phosphorus (Cu-Sn-P) alloy, the thickness of the copper alloy foil is between 0.1 and 0.2mm, the tensile strength reaches 600MPa, but the conductivity is less than 30 percent, and the softening resistance temperature is below 400 ℃, so that the requirements of the current ultrathin high-strength structural support on the performances of conductivity, heat dissipation, softening resistance and the like cannot be met. Therefore, the development of the ultrathin high-strength copper foil tape with good conductivity, heat dissipation and softening resistance conditions is of great significance.
Disclosure of Invention
Aiming at the problem that the copper alloy foil in the prior art is poor in electric conductivity, heat resistance and etching arching performance, the invention provides the high-strength intermediate-conductivity copper-iron-phosphorus-zinc-magnesium alloy foil and the processing method thereof by adding trace Zn and Mg on the basis of Cu-Fe-P, so that the copper alloy foil with better electric conductivity and etching performance is obtained, and the copper alloy foil can meet the requirements of ultrathin high-strength structural supporting pieces and connectors for the industries of communication, mobile phones and the like.
The invention is realized by the following technical scheme:
a high-strength medium-conductivity copper-iron-phosphorus-zinc-magnesium alloy foil comprises the following raw materials in percentage by weight: 2.1 to 2.4 percent of iron, 0.015 to 0.05 percent of phosphorus, 0.05 to 0.1 percent of zinc, 0.03 to 0.08 percent of magnesium and the balance of copper and impurities; the content of the impurities is less than 0.1 percent.
Preferably, the thickness of the copper-iron-phosphorus-zinc-magnesium alloy foil is 0.04-0.15mm, and the product has high strength and excellent conductivity.
The preparation method of the high-strength medium-conductivity copper-iron-phosphorus-zinc-magnesium alloy foil comprises the following steps of:
(1) smelting and casting: smelting and casting according to the chemical components of the alloy, wherein the smelting temperature is 1280-1320 ℃, the casting temperature is 1240-1280 ℃, and the casting speed is 70-110mm/min, so as to process the alloy into an ingot;
(2) solid solution: heating in a stepping type homogenization heating mode, wherein the temperature range is 800-1200 ℃, the speed is 10-14 m/min, then carrying out hot processing at the temperature of 930-;
(3) milling a surface: milling the surface for 1-3 times at a milling cutter rotation speed of 650 plus 850rpm and a train running speed of 3-6 m/min;
(4) primary cold rolling: low-temperature rolling is carried out at 80-120 ℃, the processing rate of the rolling process is 80-96%, the speed of the roller is 120-;
(5) primary aging: a step-type heating mode is adopted, the temperature is raised to 600-700 ℃ in the first stage, the temperature is kept for 4-6 hours, and then the temperature is lowered to 250-350 ℃; in the second stage, the temperature is raised to 450-550 ℃, the temperature is kept for 4-6 h, the second phase is completely separated out through double-stage aging, the electric conductivity of the second phase is over 70% IACS after aging, the crystal grain size is ensured to be over 35 mu m through long-time heating and heat preservation, and the phenomena of incomplete separation, fine separated crystal grains and re-dissolution of the crystal grains after rolling with large processing rate are avoided;
(6) secondary cold rolling: low-temperature rolling is carried out at 80-120 ℃, the processing rate of the rolling process is 30-80%, the speed of the roller is 200-300m/min, and the cooling capacity is 1.0-1.5 bar;
(7) secondary aging: a continuous annealing mode is adopted, the temperature is between 500 and 650 ℃, the alloy is rapidly cooled, and the secondary phase precipitation of FeP and FeMg in the alloy matrix is effectively controlled by secondary aging, so that the matrix strength is enhanced, and the strength and softening resistance are improved;
(8) and (3) cold rolling for three times: rolling at 80-120 deg.c at low temperature, rolling process rate of 20-50%, rolling speed of 200-300m/min and cooling amount of 1.0-1.5 bar;
(9) stress relief annealing: the temperature is 250 ℃ and 320 ℃, and the heat preservation time is 2-8 h;
(10) and (6) stretch bending and straightening.
Preferably, when the smelting temperature in the step (1) reaches 1300 ℃, power-off standing is needed for 15-30min, then casting is carried out, a crucible furnace is adopted for casting, the furnace has high power and fast smelting, the melting temperature can exceed 1300 ℃, power-off standing can be realized, complete fusion of copper and iron is ensured, the influence of ferromagnetism on components is eliminated, and the problems that iron is difficult to add and single ingots have uneven components are solved.
Preferably, the pass processing rate in the step (1) is 10-50%, the rolling speed is 200-300m/min, and the cooling amount is 1.0-1.5 bar.
Preferably, the step-by-step homogenizing heating mode in the step (2) is that a furnace is divided into ten cells, each cell independently controls the temperature, the first cell is 800 ℃, the tenth cell is 1200 ℃, other cells are ascended in a step-by-step mode at 45 ℃, and the step-by-step homogenizing heating mode is adopted and is characterized in that the step-by-step heating temperature distribution is carried out between 800 ℃ and 1200 ℃, so that the dendritic crystal segregation phenomenon generated by casting of the red ingot is completely eliminated.
Preferably, the copper-iron-phosphorus-zinc-magnesium alloy foil is rolled by a multi-roll mill, and a pair of strip holding rollers is assembled at a position 80mm outside a rolling area to ensure that the rolling area is stably rolled.
Preferably, in the step (10), the elongation of the high-strength medium-conductivity copper-iron-phosphorus-zinc-magnesium alloy foil is 0.5-1.2%, the tension is 10-25KN, and the uneven distribution of the internal stress of the alloy foil is further controlled.
The invention provides a process for smelting and casting a high-strength medium-conductivity Cu-Fe-P-Zn-Mg alloy, performing solution quenching, performing graded aging and the like, solves the problems of uneven iron, incomplete solution and low foil conductivity during smelting of the high-strength medium-conductivity Cu-Fe-P-Zn-Mg alloy, and can greatly improve the yield of alloy production and reduce the production cost. The alloy is subjected to casting, hot working, cold working and aging treatment to obtain the high-strength high-conductivity Cu-Fe-P-Zn-Mg alloy foil with the thickness of 0.04-0.15mm, the tensile strength of the product reaches 500MPa, the conductivity of the product is more than or equal to 70% IACS, the softening resistance temperature of the product exceeds 450 ℃, and the ultrathin high-strength structural support member for the industries of communication, mobile phones and the like can be met.
Advantageous effects
(1) The invention mainly solves the problems of uneven iron, incomplete solid solution and low foil conductivity during the smelting of the high-strength medium-conductivity Cu-Fe-P-Zn-Mg, can greatly improve the yield of alloy production and reduce the production cost;
(2) the alloy of the invention is subjected to casting, hot working, cold working and aging treatment to obtain the high-strength high-conductivity Cu-Fe-P-Zn-Mg alloy foil with the thickness of 0.04-0.15mm, the tensile strength of the product reaches 500MPa, the conductivity is more than or equal to 70% IACS, the softening resistance temperature exceeds 450 ℃, and the ultrathin high-strength structural support member for the industries of communication, mobile phones and the like can be met.
Drawings
FIG. 1 is a dendritic structure diagram of Cu-Fe-P-Zn-Mg alloy after hot working
FIG. 2 is a structural diagram of the Cu-Fe-P-Zn-Mg alloy after high temperature homogenization
FIG. 3 is a phase diagram of the grain structure of the Cu-Fe-P-Zn-Mg ribbon blank after primary aging
FIG. 4 is a gold phase diagram of a first-order aged small-grained structure.
Detailed Description
In order to make the technical solutions of the present invention better understood, the following description is provided clearly and completely, and other similar embodiments obtained by those skilled in the art without creative efforts shall fall within the protection scope of the present application based on the embodiments in the present application.
The raw materials in the embodiment of the invention are cathode copper, copper-iron alloy containing 10% of iron, zinc ingot and copper-magnesium alloy containing 20% of magnesium.
Example 1
A finished product of a 0.05mm high-strength medium-conductivity copper-iron-phosphorus-zinc-magnesium alloy foil (iron 2.31wt%, phosphorus 0.032 wt%, zinc 0.08 wt%, magnesium 0.061 wt%, and the balance of copper and impurities with a content of less than 0.1 wt%), which is a process flow for preparing the high-strength medium-conductivity copper-iron-phosphorus-zinc-magnesium alloy foil in this embodiment: smelting and casting, solid solution, surface milling, primary cold rolling, primary aging, secondary cold rolling, secondary aging, tertiary cold rolling, low-temperature stress relief annealing and stretch bending straightening, in the embodiment 1, a multi-roll mill is adopted for rolling, a pair of strip holding rollers are assembled at the position of 80mm outside a rolling area, and the stable rolling in the rolling area is ensured, and the method specifically comprises the following steps:
(1) smelting and casting: smelting and casting according to the chemical components of the alloy, wherein the smelting temperature is 1310 ℃, the casting temperature is 1275 ℃, the casting speed is 85mm/min, the smelting temperature is higher than 1300 ℃, and the casting is carried out after the power is cut off and the standing is carried out for 20 min;
(2) solution treatment, namely heating in a stepping homogenization heating mode at the temperature range of 800-1200 ℃ at the speed of 12 m/min, dividing a furnace into ten cells, independently controlling the temperature of each cell, namely 800 ℃ in the first cell and 1200 ℃ in the tenth cell, and ascending other cells in a step mode at 45 ℃, then carrying out hot working at the temperature of 950 ℃, controlling the pass processing rate to be 25%, the roller speed to be 250m/min, the cooling capacity to be 1.5bar, the total processing rate to be 92%, finally rolling a strip billet with the specification of 15mm × 650mm, controlling the final rolling temperature to be 720 ℃, carrying out high-temperature online quenching after the hot working, and rapidly cooling within 15s, wherein a dendritic tissue diagram of the copper-iron-phosphorus-magnesium alloy after the hot working is shown in figure 1, and a tissue diagram of the copper-iron-phosphorus-zinc-magnesium alloy after the high-temperature online quenching after the high-temperature homogenization is shown in figure 2;
(3) milling a surface: plating a layer of titanium powder with the thickness of 2mm on a milling cutter of hard alloy to avoid copper adhesion and pressing, milling for 2 times at the milling cutter rotating speed of 700rpm and the train running speed of 4m/min, wherein the thickness of a strip blank after milling is 13.5 mm;
(4) primary cold rolling: cold rolling the milled strip blank at 120 ℃, wherein the rolling speed is 180m/min, the cooling amount is 0.7bar, and the strip blank is rolled from the thickness of 13.5mm to 0.8 mm;
(5) primary aging: heating the strip after the first cold rolling to 640 ℃, preserving the heat for 5 hours, and then cooling to 320 ℃; in the second stage, the temperature is raised from 320 ℃ to 510 ℃, the temperature is kept for 5h, the temperature is cooled along with the furnace after aging, the texture phase diagram of the copper-iron-phosphorus-zinc-magnesium ribbon blank crystal grains after primary aging is shown in figure 3, and the grain size exceeds 35 mu m;
(6) secondary cold rolling: cold rolling the strip subjected to primary aging treatment at 120 ℃, wherein the rolling speed is 300m/min, the cooling capacity is 1.5bar, and the strip is rolled from the thickness of 0.8mm to 0.12 mm;
(7) secondary aging: heating the strip after the second cold rolling to 500 ℃, and rapidly cooling at the speed of 35 m/min;
(8) and (3) rolling for the third time: cold rolling the strip subjected to secondary aging treatment at 120 ℃, wherein the rolling speed is 300m/min, the cooling capacity is 1.5bar, and the strip is rolled from the thickness of 0.12mm to 0.05 mm;
(9) stress relief annealing: annealing the strip rolled for the third time in a bell jar type annealing furnace at the temperature of 280 ℃ for 5 hours;
(10) stretch bending and straightening: and (3) stretch bending and straightening the strip subjected to stress relief annealing, wherein the elongation is 0.5%, and the tension is 16 KN.
Example 2
The invention discloses a 0.1mm high-strength medium-conductivity copper-iron-phosphorus-zinc-magnesium alloy foil finished product (2.28 wt% of iron, 0.035 wt% of phosphorus, 0.06 wt% of zinc, 0.068 wt% of magnesium, and the balance of copper and impurities with the content lower than 0.1 wt%). Smelting and casting, solid solution, surface milling, primary cold rolling, primary aging, secondary cold rolling, secondary aging, tertiary cold rolling, low-temperature stress relief annealing and stretch bending straightening, in the embodiment 2, a multi-roll mill is adopted for rolling, a pair of strip holding rollers are assembled at the position of 80mm outside a rolling area, and the stable rolling in the rolling area is ensured, and the method specifically comprises the following steps:
(1) smelting and casting: smelting and casting according to the chemical components of the alloy, wherein the smelting temperature is 1320 ℃, the casting temperature is 1250 ℃, the casting speed is 75mm/min, and when the smelting temperature is higher than 1300 ℃, the casting is carried out after the power-off and standing for 15-30 min;
(2) solution treatment, namely heating in a stepping type homogenization heating mode at the temperature range of 800-1200 ℃ at the speed of 12 m/min, dividing a furnace into ten cells, independently controlling the temperature of each cell, namely 800 ℃ in the first cell and 1200 ℃ in the tenth cell, and ascending other cells in a step mode at 45 ℃, then carrying out hot working at the temperature of 965 ℃, controlling the pass processing rate to be 20%, the roller speed to be 200m/min, the cooling capacity to be 1.0bar, the total processing rate to be 92%, and finishing the strip billet with the finishing specification of 15mm × 650mm, controlling the finishing temperature to be above 700 ℃, carrying out high-temperature on-line quenching after the hot working, and rapidly cooling within 15 s;
(3) milling a surface: plating a layer of titanium powder with the thickness of 2mm on the milling cutter of the hard alloy by adopting a special milling cutter to avoid copper adhesion and pressing, and milling the surface for 2 times by adopting the rotation speed of the milling cutter of 800rpm and the running speed of a machine line of 6 m/min;
(4) primary cold rolling: cold rolling the milled plate at 100 ℃, wherein the rolling speed is 120m/min, the cooling capacity is 0.5bar, and the plate is rolled from the thickness of 13.5mm to 1.0 mm;
(5) primary aging: heating the strip after the first cold rolling to 600 ℃, preserving the heat for 6 hours, and then cooling to 350 ℃; in the second stage, the temperature is raised from 350 ℃ to 530 ℃, the temperature is kept for 4h, the furnace is cooled after aging, and the grain size exceeds 35 mu m;
(6) secondary cold rolling: cold rolling the strip subjected to primary aging treatment at 100 ℃, wherein the rolling speed is 200m/min, the cooling capacity is 1.0bar, and the strip is rolled from the thickness of 1.0mm to 0.2 mm;
(7) secondary aging: heating the strip after the second cold rolling to 500 ℃, and rapidly cooling at the speed of 30 m/min;
(8) and (3) rolling for the third time: cold rolling the strip subjected to secondary aging treatment at 100 ℃, wherein the rolling speed is 200m/min, the cooling capacity is 1.0bar, and the strip is rolled from the thickness of 0.2mm to 0.1 mm;
(9) stress relief annealing: annealing the strip rolled for the third time in a bell jar type annealing furnace at the temperature of 300 ℃ for 5 hours;
(10) stretch bending and straightening: and (3) stretch bending and straightening the strip subjected to stress relief annealing, wherein the elongation is 0.9%, and the tension is 21 KN.
Comparative example 1
The melting and casting temperature in the step (1) in the example 1 was changed, and the ingot casting was directly carried out without stopping the power supply and standing when the temperature reached 1300 ℃.
Comparative example 2
Heating was carried out by changing the stepwise homogenization heating method in the step (2) of example 1 to a conventional solid solution method at a solid solution temperature of 950 ℃ for 5 hours, and the rest of the steps were the same as those of example 1.
Comparative example 3
The conventional primary aging treatment mode is changed, the aging temperature is 530 ℃, the temperature is kept for 13 hours, and the grain structure gold phase diagram after primary aging is shown in figure 4.
Performance testing
Claims (8)
1. The high-strength medium-conductivity copper-iron-phosphorus-zinc-magnesium alloy foil is characterized by comprising the following raw materials in percentage by weight: 2.1 to 2.4 percent of iron, 0.015 to 0.05 percent of phosphorus, 0.05 to 0.1 percent of zinc, 0.03 to 0.08 percent of magnesium and the balance of copper and impurities; the content of the impurities is less than 0.1 percent.
2. A high-strength medium-conductivity copper-iron-phosphorus-zinc-magnesium alloy foil according to claim 1, wherein the thickness of the copper-iron-phosphorus-zinc-magnesium alloy foil is 0.04-0.15 mm.
3. A preparation method of the high-strength medium-conductivity copper-iron-phosphorus-zinc-magnesium alloy foil as recited in claim 1 or 2, characterized by comprising the following steps:
(1) smelting and casting: smelting and casting according to the chemical components of the alloy, wherein the smelting temperature is 1280-1320 ℃, the casting temperature is 1240-1280 ℃, and the casting speed is 70-110mm/min, so as to process the alloy into an ingot;
(2) solid solution: heating in a step-by-step homogenizing heating mode at a temperature range of 800-1200 ℃ and a speed of 10-14 m/min, then performing thermal processing at a temperature of 930-;
(3) milling a surface: milling the surface for 1-3 times at a milling cutter rotation speed of 650 plus 850rpm and a train running speed of 3-6 m/min;
(4) primary cold rolling: low-temperature rolling is carried out at 80-120 ℃, the processing rate of the rolling process is 80-96%, the speed of the roller is 120-;
(5) primary aging: a step-type heating mode is adopted, the temperature is raised to 600-700 ℃ in the first stage, the temperature is kept for 4-6 hours, and then the temperature is lowered to 250-350 ℃; in the second stage, heating to 450-550 ℃, and preserving heat for 4-6 h;
(6) secondary cold rolling: low-temperature rolling is carried out at the temperature of 80-120 ℃, the processing rate of the rolling process is 30-80%, the rolling speed is 200-300m/min, and the cooling capacity is 1.0-1.5 bar;
(7) secondary aging: rapidly cooling in a continuous annealing mode at the temperature of 500-650 ℃;
(8) and (3) cold rolling for three times: low-temperature rolling is carried out at the temperature of 80-120 ℃, the processing rate of the rolling process is 20-50%, the rolling speed is 200-300m/min, and the cooling capacity is 1.0-1.5 bar;
(9) stress relief annealing: the temperature is 250 ℃ and 320 ℃, and the heat preservation time is 2-8 h;
(10) and (6) stretch bending and straightening.
4. The preparation method according to claim 3, wherein the casting is carried out after the power-off standing for 15-30min when the smelting temperature in the step (1) reaches 1300 ℃.
5. The method as claimed in claim 3, wherein the pass reduction in step (1) is 10-50%, the roll speed is 200-300m/min, and the cooling amount is 1.0-1.5 bar.
6. The method according to claim 3, wherein the step-wise homogenizing heating in step (2) is performed by dividing the furnace into ten cells, wherein each cell is independently controlled in temperature, the first cell is 800 ℃, the tenth cell is 1200 ℃, and the other cells are raised in a stepwise manner at 45 ℃.
7. The production method according to claim 3, wherein the copper-iron-phosphorus-zinc-magnesium alloy foil is rolled by a multi-roll mill, and a pair of strip holding rolls is provided 80mm outside the rolling zone.
8. The preparation method according to claim 3, characterized in that, in the step (10), the elongation of the high-strength medium-conductivity copper-iron-phosphorus-zinc-magnesium alloy foil is 0.5-1.2%, and the tension is 10-25 KN.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112626371A (en) * | 2020-12-10 | 2021-04-09 | 中色奥博特铜铝业有限公司 | High-strength medium-conductivity copper-nickel-silicon-tin-magnesium alloy foil and processing method thereof |
| CN114990377A (en) * | 2022-06-09 | 2022-09-02 | 宁波兴敖达金属新材料有限公司 | High-strength high-conductivity iron bronze alloy for electric connector |
| CN115896538A (en) * | 2022-10-27 | 2023-04-04 | 中色奥博特铜铝业有限公司 | High-performance copper-nickel-silicon-chromium alloy plate and processing method and application thereof |
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| CN115896538B (en) * | 2022-10-27 | 2024-04-26 | 中色正锐(山东)铜业有限公司 | High-performance copper-nickel-silicon-chromium alloy plate and processing method and application thereof |
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