CN114540663B - Cu-Ni-Si-Fe alloy and preparation method and application thereof - Google Patents
Cu-Ni-Si-Fe alloy and preparation method and application thereof Download PDFInfo
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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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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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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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Abstract
The invention provides a Cu-Ni-Si-Fe alloy and a preparation method and application thereof. The alloy is optimized in components, a base metal Fe element is adopted to replace part of Co elements or even all Co elements in the Cu-Ni-Co-Si alloy, and nanoscale FeSi phase particles with high hardness and high heat resistance are formed by means of strong atom bonding force between Fe and Si, so that the low-cost, high-strength and high-conductivity alloy is obtained. The invention also provides a preparation method and application of the alloy.
Description
Technical Field
The invention belongs to the technical field of copper alloy materials, and particularly relates to a Cu-Ni-Si-Fe alloy and a preparation method and application thereof.
Background
The Cu-Ni-Si alloy has high strength and elasticity and excellent electric conduction, heat conduction and processing forming performance, and has wide application prospect in the fields of aerospace, traffic tracks, electronic information and the like. With the development of electronic information and large-scale integrated circuit industries, higher requirements are put forward on high-performance Cu-Ni-Si alloys. The Cu-Ni-Co-Si series alloy with the brand numbers of C70250 and C70350 developed by Olin company is taken as a representative, and becomes a preferred material for manufacturing a second generation integrated circuit lead frame due to excellent stress relaxation resistance and punching performance, wherein the main component of the C70350 alloy is Ni:1.3wt% -1.8 wt%, si:0.4wt% -1.0 wt%, co:1.0 to 1.5wt%, the tensile strength of the alloy is 750 to 950MPa, the conductivity is 45% IACS to 50% IACS.
With the explosive development of the electronic information industry, the demand of the integrated circuit lead frame is continuously increasing. Meanwhile, due to the rapid arrival of the new energy automobile era and the growth of global electric automobiles, the demand of cobalt metal as a core raw material of a power battery is rapidly increased. Cobalt ore is widely applied to business, industry and military, relates to products such as smart phones, electric vehicles and airplane engines, and is a key strategic material. However, the cobalt resource reserves are scarce, the mining difficulty is high, the refining technology is complex, and the cost of cobalt metal rises year by year. In addition, in the large-scale semi-continuous casting process, the Co element is added, so that larger casting stress is easily generated in the large-scale Cu-Ni-Si alloy billet casting process, the hot cracking phenomenon is caused in the subsequent manufacturing and processing, and the yield is reduced. Therefore, it is important to develop low-cost, high-strength and high-conductivity low-Co or Co-free alloys.
Disclosure of Invention
The present invention is directed to solving at least one of the above problems in the prior art. Therefore, the invention provides a Cu-Ni-Si-Fe alloy, which is obtained by optimizing components, replacing part of Co elements even all Co elements in the Cu-Ni-Co-Si alloy with base metal Fe elements and forming nano FeSi phase particles with high hardness and high heat resistance by means of strong atom bonding force between Fe and Si.
The invention also provides a preparation method of the Cu-Ni-Si-Fe system alloy.
The invention also provides application of the Cu-Ni-Si-Fe system alloy.
The first aspect of the invention provides a Cu-Ni-Si-Fe system alloy, which comprises the following components in percentage by mass:
Ni：1.2wt％～5.0wt％，
Co：0wt％～0.8wt％，
Si：0.4wt％～2.0wt％，
Fe：0.1wt％～1.5wt％，
Mg：0.05wt％～0.15wt％，
the balance being copper.
The invention relates to a technical scheme of Cu-Ni-Si-Fe alloy, which at least has the following beneficial effects:
the Cu-Ni-Si-Fe alloy of the invention adopts base metal Fe element to replace part or even all Co element, and properly improves Ni and SiContent, obtaining high-hardness and high-heat-resistance nano FeSi phase and high-Ni content 3 Si phase, lamellar Ni 2 The discontinuous precipitated phase of Si solves the problem of low strength of the Cu-Ni-Si alloy with low Co or without Co, reduces the casting stress of the alloy and is beneficial to subsequent processing and forming.
The invention utilizes the strong binding energy of Fe and Si to form a Fe-Si phase with high hardness and high heat resistance; in addition, the precipitation capacity of the Fe-Si phase is stronger than that of the Fe phase, and the precipitation of Fe atoms in the matrix is promoted. Therefore, the addition of base metal Fe element and the combination of Si to form hard Fe-Si phase to replace Co-Si phase so as to reduce Co element content is significant in both raw material cost and relief of strategic scarce resources.
The precipitated phases which can be formed by Fe element and Si element comprise FeSi and beta-FeSi 2 、α-FeSi 2 、Fe 2 Si、Fe 5 Si 3 、Fe 11 Si 5 、Fe 3 And (3) Si. The FeSi phase has the largest shear modulus and Young modulus, which shows that the FeSi phase has the strongest deformation resistance, the largest hardness and the best strengthening effect. In addition, the FeSi phase has a smaller poisson's ratio than Fe, which is 0.21 (less than 0.25), indicating that FeSi phase is a hard brittle phase. The high brittleness enables the FeSi primary phase to be more easily broken in the cold processing process, and the FeSi primary phase is distributed in a matrix in the subsequent heat treatment process as fine dispersed particles, which is beneficial to improving the dispersion strengthening effect of the alloy. Therefore, the content and the proportion of Fe and Si are very important.
The conductivity of the copper alloy is mainly influenced by the effect of solute atoms in a matrix on electron scattering, so that the conductivity of the alloy is remarkably improved along with the precipitation of trace elements. In order to synergistically improve the strength and conductivity of the alloy, it is necessary to dissolve Ni, co, si and Fe elements in the matrix as much as possible in the form of Ni 2 Si、Ni 3 Si、Co 2 Si and FeSi phases are precipitated.
One of the key points of the Cu-Ni-Si-Fe alloy of the invention is to reasonably regulate the contents and the proportions of Ni, co, fe, si and other elements, properly improve the contents of Ni and Si, reduce the content of Co element or not add Co element, and precipitate phases such as (Ni,Co) 2 Si、Ni 3 the mass ratio of Si, feSi and the like, the upper and lower limits of the content of each element in the experimental alloy are reversely deduced, and the experimental alloy components are directionally designed by combining Ni-Co-Si and Fe-Si phase diagrams. According to the enthalpy of formation of Si atoms and Ni, co and Fe, the atomic affinity of Fe and Si is far stronger than that of Co and Si or Ni and Si, and Fe-Si, ni-Si and Co-Si phases are formed in the alloy in sequence.
If the Si content is too low, on the one hand, the Ni, co, fe elements cannot be made to FeSi, ni3Si, (Ni, co) 2 Si phase is fully precipitated, the strengthening effect is limited, and solute atoms remained in the matrix, particularly Co and Fe elements seriously harm the conductivity; if the Si content is too large, precipitation of the second phase is promoted as much as possible, but the excess Si remains in the copper matrix, which also results in a decrease in the conductivity of the alloy.
If the Fe content is too high, on one hand, most Si atoms are consumed to form a coarse brittle FeSi primary phase, so that a casting blank is easy to crack in the subsequent processing process and has low yield, and on the other hand, the remainder is combined with Ni and Co to form Ni 3 Si、(Ni，Co) 2 The Si content of the Si phase particles is insufficient, and the residual Ni and Co elements in the copper matrix are large, which lowers the conductivity. Therefore, the content of Si should be increased appropriately on the basis of sufficient consumption of Fe element.
If the contents of Ni and Co are too small, on the one hand, excessive Si atoms in the design composition cannot be precipitated, but remain dissolved in the Cu matrix in the form of solute atoms, deteriorating the conductivity, and Ni 3 Si、(Ni，Co) 2 The content of Si phase particles is too small, and the strengthening effect is low; if the Ni content and the Co content are too high, the cost of alloy raw materials is high, the casting stress of the alloy billet is large, heat cracks are generated, the subsequent processing is difficult, and the yield is reduced. Therefore, the Cu-Ni-Si-Fe alloy of the present invention can be prepared by comprehensively considering the contents and the proportions of the elements.
Taking the Fe in the Fe-Si binary phase: the two mass percentages of the lowest and the highest Si content ratios are used as the lower limit and the upper limit of the proportioning range, namely the weight percentage of Fe is more than or equal to 1.0 and less than or equal to 6.3.
When the mass ratio of (Ni + Co) to Si is 4.2-4.7: 1, the alloy shows good comprehensive performance. Therefore, it is required to satisfy 4.2. Ltoreq. Wt.% (Ni + Co) wt.%)/Si wt.% 4.7 or less.
According to some embodiments of the invention, the Cu-Ni-Si-Fe-based alloy comprises, in mass percent:
Ni：1.5wt％～4.8wt％，
Co：0wt％～0.6wt％，
Si：0.6wt％～1.8wt％，
Fe：0.3wt％～1.4wt％，
Mg：0.05wt％～0.15wt％，
the balance being copper.
According to some embodiments of the invention, the Cu-Ni-Si-Fe-based alloy comprises, in mass percent:
Ni：1.5wt％～4.8wt％，
Co：0.2wt％～0.6wt％，
Si：0.6wt％～1.8wt％，
Fe：0.3wt％～1.4wt％，
Mg：0.05wt％～0.15wt％，
the balance being copper.
The second aspect of the present invention provides a method for producing the above Cu-Ni-Si-Fe-based alloy, comprising the steps of:
s1: melting the raw materials according to a ratio, adding a covering agent and a refining agent for smelting, and casting and forming to obtain an ingot;
s2: homogenizing the cast ingot to obtain a billet;
s3: carrying out hot processing cogging treatment on the billet, and then carrying out first water cooling treatment to obtain a hot processing billet;
s4: and carrying out solid solution treatment and second water cooling treatment on the hot processing blank in a protective atmosphere, and then sequentially carrying out primary cold processing, primary aging, secondary cold processing, secondary aging, tertiary cold processing and tertiary aging.
The invention relates to a technical scheme of a preparation method of Cu-Ni-Si-Fe system alloy, which at least has the following beneficial effects:
the invention relates to a preparation method of Cu-Ni-Si-Fe alloy, which reasonably regulates and controls a processing-heat treatment process to ensure that elements such as Ni, co, si, fe and the like are respectively FeSi and Ni in a nano-scale manner 3 Si、(Ni，Co) 2 Si, lamellar Ni 2 The discontinuous precipitated phase of Si is fully dispersed and uniformly precipitated, the dislocation and the grain boundary motion are pinned, the comprehensive effects of multi-scale multi-morphology multi-phase synergetic dispersion strengthening, strain strengthening, subgrain strengthening, solid solution strengthening and the like are exerted, and the Cu-Ni-Si-Fe alloy with low cost, high strength, high conductivity and good heat resistance is obtained.
The invention relates to a preparation method of Cu-Ni-Si-Fe alloy, which provides a low-cost high-strength high-conductivity Cu-Ni-Si-Fe alloy through comprehensive regulation and control of multi-element alloying, processing and heat treatment processes of replacing Co with Fe, wherein the alloy has the hardness of 270-350 HV, the tensile strength of 890-1050 MPa, the yield strength of 860-1000 MPa, the secondary growth rate of 3-7%, the conductivity of 40-48 IACS and the heat-resisting temperature of more than or equal to 540 ℃, solves the problems of rare Co, high cost, low yield and the like of raw materials of the Cu-Ni-Co-Si alloy of a large-scale integrated circuit lead frame, and can meet the great requirements of rapid development of the modern electronic information industry on lead frames with high performance and low cost.
The invention also provides another key point of the Cu-Ni-Si-Fe alloy, which is to regulate and control the existing form and the spatial distribution state of elements such as Ni, si, fe, mg and the like in the alloy by designing a combined shape-changing thermal treatment technology for cooperative control of cold working and thermal treatment, play a role in multi-scale, multi-form and multi-phase cooperative reinforcement, improve the strength and the electric conductivity at the same time and obtain excellent comprehensive performance.
The method adopts 'large-deformation cold processing + high-temperature short-time aging treatment' to break and refine the FeSi primary phase and promote a part of Ni and Si in a matrix to form a fine lamellar discontinuous precipitated phase so as to increase the precipitation kinetics of redundant Ni elements in the alloy proportioning process and inhibit dynamic recrystallization. Subsequent thermomechanical treatment for further refining FeSi and Ni 3 Si、(Ni，Co) 2 Si、Ni 2 Si discontinuously precipitates phase particles and promotes residual Ni and CoSi and Fe atoms are nucleated and precipitated at the defects of dislocation, subgrain, twin crystal and the like introduced by cold working in the form of small-bean petal-shaped, disc-shaped and ellipsoidal nano-scale particles. However, the precipitation form of solute atoms is very sensitive to factors such as temperature, time and the like, so that the establishment of process parameters plays an important role in the existence form and the spatial distribution state of elements in the alloy.
If the cold working deformation is too small, ni cannot be provided 2 Nucleation energy storage of the discontinuous Si precipitated phase particles also influences precipitation of other atoms, and simultaneously, feSi primary phases formed in the solidification process of the alloy are not enough to be broken, so that the problems of poor subsequent processing performance and the like are caused; if the cold-working deformation is too large, on one hand, the alloy is seriously hardened, and is easy to generate defects such as cracks, and the like, so that the yield is reduced, and on the other hand, larger deformation energy storage is formed, and the recrystallization of the copper matrix in the subsequent aging process is easy to induce, so that the strength of the alloy is obviously reduced.
If the heat treatment temperature is too high, ni will be excessively promoted 2 The development of discontinuous Si precipitated phase particles, even abnormal growth of crystal grains, deteriorates the processing performance of the material; if the heat treatment temperature is too low, the diffusion rate of solute atoms is reduced, so that not only discontinuous precipitation cannot be realized, but also continuous precipitation phase Ni 3 Si、(Ni，Co) 2 Si and the like cannot be formed, the strengthening effect is reduced, and solute atoms remain in the matrix in short of diffusion, increasing the scattering of electrons, and being not favorable for improving the conductivity.
If the aging time is too long, precipitated phase particles with various shapes grow up and coarsen, and the strengthening effect is poor; if the aging time is too short, although a part of Ni can be formed 2 Although Si is not precipitated continuously, most of Ni, co, si, and Fe atoms are not precipitated in time and remain in the copper matrix, which deteriorates the strength and conductivity.
The Cu-Ni-Si-Fe alloy comprehensively considers the comprehensive action between component design and a processing-heat treatment system, optimizes the content and proportion of elements such as Ni, co, si, fe and the like, and adopts a Fe-Si phase to replace a Co-Si phase to obtain alloy components with low Co or no Co; on the other hand, ni is subjected to annealing by regulating and controlling a processing and heat treatment system,Co, si, fe and other elements are nano FeSi and Ni respectively 3 Si、(Ni，Co) 2 Si, lamellar Ni 2 The discontinuous precipitated phase form of Si is dispersed and uniformly distributed in the matrix, the dislocation and the grain boundary motion are pinned, and the comprehensive functions of multi-scale polymorphic multiphase synergetic dispersion strengthening, strain strengthening, sub-crystal strengthening, solid solution strengthening and the like are exerted, so that the Cu-Ni-Si-Fe system alloy is obtained.
According to some embodiments of the invention, the refining agent comprises a Cu-Ca alloy and a rare earth element Ce.
According to some embodiments of the invention, the temperature of the melting is from 1200 ℃ to 1400 ℃.
According to some embodiments of the invention, the casting temperature is 1100 ℃ to 1300 ℃.
In step S2, the homogenization treatment is performed in a protective atmosphere.
According to some embodiments of the invention, the protective atmosphere is 2%H 2 + balance N 2 。
According to some embodiments of the invention, the temperature of the homogenization treatment is 880 ℃ to 980 ℃.
According to some embodiments of the invention, the homogenization treatment is performed for a time period of 1h to 6h.
According to some embodiments of the invention, the hot working cogging temperature is from 900 ℃ to 980 ℃ and the deformation is from 60% to 90%.
In the hot working cogging, the hot working may be hot extrusion, hot rolling, hot forging, etc., and the cold working may be drawing, rolling, spinning, swaging, etc.
According to some embodiments of the invention, the temperature of the solution treatment is 900 ℃ to 980 ℃.
According to some embodiments of the invention, the time of the solution treatment is 1h to 4h.
In step S2, the solution treatment is performed in a protective atmosphere.
According to some embodiments of the invention, the protective atmosphere is 2%H 2 + balance N 2 。
According to some embodiments of the invention, the amount of deformation of the primary cold working is 60% to 80%.
According to some embodiments of the invention, the temperature of the primary aging is 450 ℃ to 550 ℃.
According to some embodiments of the invention, the time of the primary aging is 0.25h to 6h.
According to some embodiments of the invention, the secondary cold working has a deformation of 60% to 80%.
According to some embodiments of the invention, the temperature of the secondary ageing is between 400 ℃ and 500 ℃.
According to some embodiments of the invention, the time of the secondary aging is 0.25h to 6h.
According to some embodiments of the invention, the deformation of the third cold working is 20% to 40%.
According to some embodiments of the invention, the temperature of the tertiary aging is 300 ℃ to 400 ℃.
According to some embodiments of the invention, the time for the tertiary aging is between 0.25h and 6h.
The third aspect of the present invention provides the use of the above-mentioned Cu-Ni-Si-Fe-based alloy for producing electronic components.
According to some embodiments of the invention, the electronic component comprises: the electronic device comprises a resistor, a capacitor, an inductor, a potentiometer, an electronic tube, a radiator, an electromechanical element, a connector, a semiconductor discrete device, an electroacoustic device, a laser device, an electronic display device, a photoelectric device, a sensor, a power supply, a switch, a micro-special motor, an electronic transformer, a relay, a printed circuit board, an integrated circuit, various circuits, piezoelectricity, a crystal, quartz, a ceramic magnetic material, a substrate for a printed circuit, an electronic function process special material, an electronic adhesive (tape) product, an electronic chemical material, a component and the like.
The invention adopts microalloying technology, introduces a plurality of heat-resistant strengthening phases into the copper alloy, combines the regulation and control of processing-heat treatment process, leads alloy elements in a copper matrix to be dispersed and distributed in the form of a plurality of nano strengthening phases, and forms a submicron-grade heat-resistant strengthening phase with discontinuously distributed crystal boundaries, thereby not only greatly improving the strength, high-temperature softening resistance and stress relaxation resistance of the alloy, but also purifying the copper matrix to improve the conductivity of the alloy, and developing the high-strength high-conductivity heat-resistant copper alloy and the preparation method thereof, which are important ways for solving the problems and are also important development directions of high-performance alloys.
Aiming at the problems of scarce Co, high cost, low yield and the like of a raw material of a Cu-Ni-Co-Si alloy of a large-scale integrated circuit lead frame and urgent requirements for independently developing a next generation of very large-scale integrated circuits, the invention provides the Cu-Ni-Si-Fe system alloy, which adopts a base metal Fe element to replace part or even all Co elements in the Cu-Ni-Co-Si alloy, designs the content and proportion of elements such as Ni, co, fe, si and the like through component optimization, properly improves the content of Ni and Si, and forms nano FeSi phase particles with high hardness and high heat resistance by means of strong atom bonding force between Fe and Si. The addition of trace Mg can effectively reduce Ni 2 The interlayer spacing of the Si photo promotes the FeSi phase particles to be separated out and refines the crystal grains of the copper matrix, and the Cu-Ni-Si-Fe alloy with low cost, high strength and high strength is prepared.
In the preparation method, the invention promotes the Ni, co and Si atoms in the copper matrix to be fully precipitated through the heat treatment process to form the nano-scale (Ni, co) 2 Si、Ni 3 Si phase, lamellar Ni 2 The discontinuous precipitation of Si is equal, and the multi-scale, multi-form and multi-phase synergistic strengthening effect is realized.
Drawings
FIG. 1 is a schematic diagram of a process for preparing a Cu-Ni-Si-Fe system alloy according to the present invention.
FIG. 2 is the metallographic structure of the ingot prepared in example 4.
Fig. 3 is an SEM picture of the ingot prepared in example 4.
FIG. 4 shows the metallographic structure of example 4 after solution treatment at 940 ℃ for 1 hour.
FIG. 5 is an SEM picture of the Cu-Ni-Co-Si-Fe-Mg alloy prepared in example 4 after solution treatment.
FIG. 6 shows the metallographic structure of example 4 aged at 450 ℃ for 2 hours.
FIG. 7 is an SEM picture of a Cu-Ni-Co-Si-Fe alloy strip prepared in example 4.
Detailed Description
The following are specific examples of the present invention, and the technical solutions of the present invention will be further described with reference to the examples, but the present invention is not limited to the examples.
In some embodiments of the present invention, a Cu-Ni-Si-Fe system alloy is provided, comprising, in mass percent:
Ni：1.2wt％～5.0wt％，
Co：0wt％～0.8wt％.
Si：0.4wt％～2.0wt％，
Fe：0.1wt％～1.5wt％，
Mg：0.05wt％～0.15wt％，
the balance being copper.
As a preferred embodiment, the Cu-Ni-Si-Fe system alloy comprises the following components in percentage by mass:
Ni：1.5wt％～4.8wt％，
Co：0wt％～0.6wt％，
Si：0.6wt％～1.8wt％，
Fe：0.3wt％～1.4wt％，
Mg：0.05wt％～0.15wt％，
the balance being copper.
In some embodiments of the present invention, there is provided a method of preparing the above Cu-Ni-Si-Fe-based alloy, including the steps of:
s1: melting the raw materials according to a ratio, adding a covering agent and a refining agent for smelting, and casting and forming to obtain an ingot;
s2: homogenizing the cast ingot to obtain a billet;
s3: carrying out hot processing cogging treatment on the billet, and carrying out first water cooling treatment to obtain a hot processing billet;
s4: and (3) carrying out solid solution treatment and second water cooling treatment on the hot-worked blank in a protective atmosphere, and then sequentially carrying out primary cold working, primary aging, secondary cold working, secondary aging, tertiary cold working and tertiary aging.
The preparation method comprises the following steps of referring to the flow chart of figure 1.
Wherein, the refining agent comprises Cu-Ca alloy and rare earth element Ce.
In some embodiments of the invention, the temperature of the melting is 1200 ℃ to 1400 ℃.
In some embodiments of the invention, the casting temperature is 1100 ℃ to 1300 ℃.
In some embodiments of the invention, the homogenization treatment is carried out at a temperature of 880 ℃ to 980 ℃. The time of the homogenization treatment is 1-6 h.
In some embodiments of the invention, the hot working cogging temperature is 900 ℃ to 980 ℃ and the deformation is 60% to 90%.
In some embodiments of the invention, the solution treatment temperature is 900 ℃ to 980 ℃.
In some embodiments of the invention, the time for the solution treatment is 1h to 4h.
In some embodiments of the invention, the amount of deformation in a single cold working is 60% to 80%.
In some embodiments of the invention, the temperature of the primary aging is 450 ℃ to 550 ℃.
In some embodiments of the invention, the time for the primary aging is 0.25h to 6h.
In some embodiments of the invention, the secondary cold working has a deformation of 60% to 80%.
In some embodiments of the invention, the temperature of the secondary aging is 400 ℃ to 500 ℃.
In some embodiments of the invention, the time for the secondary aging is 0.25h to 6h.
In some embodiments of the invention, the amount of deformation from three cold working passes is 20% to 40%.
In some embodiments of the invention, the temperature of the tertiary aging is 300 ℃ to 400 ℃.
In some embodiments of the invention, the time for the third aging is 0.25h to 6h.
In some embodiments of the invention, the application of the Cu-Ni-Si-Fe system alloy in preparing electronic components is provided.
In the embodiment of the invention, the refining agent is Cu-Ca alloy and rare earth element Ce, wherein in the refining agent, ca accounts for 0.03wt% of the total mass of the alloy, and Ce accounts for 0.02wt% of the total mass of the alloy.
Example 1
The embodiment prepares a Cu-Ni-Si-Fe alloy, which specifically comprises the following steps:
the components are Ni:4.5wt%, co:0.2wt%, si:1.2wt%, fe:0.6wt%, mg:0.1wt% and the balance of Cu.
Preparing materials according to the weight percentage of the elements, firstly adding a copper source into a smelting furnace for melting, sequentially adding a copper-silicon intermediate alloy, a nickel source, a cobalt source and an iron source, finally adding a copper-magnesium intermediate alloy, and adding a covering agent and a refining agent when the raw materials begin to melt.
The covering agent charcoal is baked to red heat at 500 ℃.
Smelting in the atmosphere at 1300 ℃, casting and molding in an iron mold at 1200 ℃, and milling by a lathe after cooling to remove surface defects.
Cooling and then protecting in the protective atmosphere 2%H 2 + balance N 2 The homogenization treatment is carried out, the homogenization annealing temperature is 950 ℃, and the annealing time is 4 hours.
Subsequently, hot rolling cogging was performed at a reduction of 80%. After water cooling, the hot rolled plate is subjected to solid solution under the conditions of protective atmosphere and 980 ℃ for 1 hour, and then the solid solution plate is obtained by water cooling, wherein the water temperature is 20-25 ℃.
The plate after solid solution is firstly subjected to primary cold rolling at room temperature, the deformation is 80 percent, primary aging and quenching are carried out for 0.5 hour in a box-type resistance furnace at the temperature of 500 ℃, and the quenching mode is water cooling.
Then, secondary cold rolling was performed at room temperature with a strain of 60%, and secondary aging and quenching were performed in a box-type resistance furnace at 450 ℃ for 2 hours in a manner of water cooling.
And finally, carrying out three times of cold rolling at room temperature, wherein the deformation is 25%, carrying out three times of aging and quenching for 4 hours in a box-type resistance furnace at the temperature of 400 ℃, and carrying out water cooling in the quenching mode to obtain the high-strength high-conductivity heat-resistant copper alloy sample.
Example 2
The embodiment prepares a Cu-Ni-Si-Fe alloy, which specifically comprises the following steps:
the components are Ni:4.5wt%, co:0.2wt%, si:1.6wt%, fe:1.0wt%, mg:0.1wt% and the balance of Cu.
Preparing materials according to the weight percentage of the elements, firstly adding a copper source into a smelting furnace for melting, sequentially adding a copper-silicon intermediate alloy, a nickel source, a cobalt source and an iron source, finally adding a copper-magnesium intermediate alloy, adding a covering agent and a refining agent when the raw materials begin to melt, and drying covering agent charcoal to red heat at 500 ℃.
Smelting in the atmosphere at 1300 ℃, casting and molding in an iron mold at 1200 ℃, and milling by a lathe after cooling to remove surface defects.
Cooling in protective atmosphere 2%H 2 + balance N 2 And a homogenizing annealing at 950 ℃ for 4 hours, followed by hot rolling cogging at a reduction of 80%. After water cooling, the hot rolled plate is subjected to solid solution under the conditions of protective atmosphere and 980 ℃ for 1 hour, and then the solid solution plate is obtained by water cooling, wherein the water temperature is 20-25 ℃.
The plate after solid solution is firstly subjected to primary cold rolling at room temperature, the deformation is 80 percent, primary aging and quenching are carried out for 0.5 hour in a box-type resistance furnace at the temperature of 500 ℃, and the quenching mode is water cooling.
Then, secondary cold rolling was performed at room temperature with a strain of 60%, and secondary aging and quenching were performed in a box-type resistance furnace at 450 ℃ for 2 hours in a manner of water cooling.
And finally, carrying out cold rolling for three times at room temperature, wherein the deformation is 25%, carrying out aging and quenching for three times for 4 hours in a box-type resistance furnace at the temperature of 400 ℃, and carrying out water cooling on the quenching way to obtain the high-strength high-conductivity heat-resistant copper alloy sample.
Example 3
The embodiment prepares a Cu-Ni-Si-Fe alloy, which specifically comprises the following steps:
the components are Ni:1.7wt%, si:1.6wt%, fe:1.0wt%, mg:0.1wt% and the balance of Cu.
After adding sufficient covering agent and refining agent, smelting at 1300 ℃ in the atmosphere, fully stirring and slagging off to obtain a melt with uniform components and no macrosegregation. And casting the melt into an iron mold at 1200 ℃, cooling, and milling by a lathe to remove surface defects.
Ingot casting in protective atmosphere 2%H 2 + balance N 2 And a homogenizing annealing at 950 ℃ for 4 hours, followed by hot rolling cogging with a reduction of 80%. After water cooling, the hot rolled plate is subjected to solid solution under the conditions of protective atmosphere and 980 ℃ for 1 hour, and then the solid solution plate is obtained by water cooling, wherein the water temperature is 20-25 ℃.
The plate after solid solution is firstly subjected to primary cold rolling at room temperature, the deformation is 80 percent, primary aging and quenching are carried out for 0.5 hour in a box-type resistance furnace at the temperature of 500 ℃, and the quenching mode is water cooling.
Then, secondary cold rolling was performed at room temperature with a strain of 60%, and secondary aging and quenching were performed in a box-type resistance furnace at 450 ℃ for 2 hours in a manner of water cooling.
And finally, carrying out cold rolling for three times at room temperature, wherein the deformation is 25%, carrying out stress relief annealing and quenching for 4 hours in a box-type resistance furnace at the temperature of 400 ℃, and carrying out water cooling on the quenching mode to obtain the high-strength high-conductivity heat-resistant copper alloy sample.
Example 4
The embodiment prepares a Cu-Ni-Si-Fe alloy, which specifically comprises the following steps:
the components are Ni:1.7wt%, co:0.6wt%, si:0.7wt%, fe:0.4wt%, mg:0.1wt% of Cu and the balance of Cu are mixed, sufficient covering agent and refining agent are added, then the mixture is smelted in the atmosphere and at the temperature of 1300 ℃, melt with uniform components and no macrosegregation is obtained after full stirring and slag skimming, the melt is cast and molded in an iron mold at the temperature of 1200 ℃, and the surface defects are removed by milling through a lathe after cooling.
Ingot casting in protective atmosphere 2%H 2 + balance N 2 And a homogenizing annealing at 950 ℃ for 4 hours, followed by hot rolling cogging with a reduction of 80%. After water cooling, the hot rolled plate is cooled in protective atmosphere and at 980 DEG CCarrying out solid solution for 1 hour under the condition, and then carrying out water cooling to obtain a solid solution plate with the water temperature of 20-25 ℃.
The plate after solid solution is firstly subjected to primary cold rolling at room temperature, the deformation is 80%, primary aging and quenching are carried out for 0.5 hour in a box-type resistance furnace at the temperature of 500 ℃, and the quenching mode is water cooling.
Then, secondary cold rolling was performed at room temperature with a strain of 60%, and secondary aging and quenching were performed in a box-type resistance furnace at 450 ℃ for 2 hours in a manner of water cooling.
And finally, carrying out three times of cold rolling at room temperature, wherein the deformation is 25%, carrying out three times of aging and quenching for 4 hours in a box-type resistance furnace at the temperature of 400 ℃, and carrying out water cooling in the quenching mode to obtain the high-strength high-conductivity heat-resistant copper alloy sample.
Example 5
The embodiment prepares a Cu-Ni-Si-Fe alloy, which specifically comprises the following steps:
the components are Ni:4.5wt%, si:1.6wt%, fe:1.2wt%, mg:0.1wt% and the balance of Cu, adding sufficient covering agent and refining agent, smelting at 1300 ℃ in the atmosphere, fully stirring and slagging off to obtain a melt with uniform components and no macrosegregation. And casting the melt into an iron mold at 1200 ℃, cooling, and milling by a lathe to remove surface defects.
Ingot casting in protective atmosphere 2%H 2 + balance N 2 And a homogenizing annealing at 950 ℃ for 4 hours, followed by hot rolling cogging with a reduction of 80%. After water cooling, the hot rolled plate is subjected to solid solution under the conditions of protective atmosphere and 980 ℃ for 1 hour, and then the solid solution plate is obtained by water cooling, wherein the water temperature is 20-25 ℃.
The plate after solid solution is firstly subjected to primary cold rolling at room temperature, the deformation is 80 percent, primary aging and quenching are carried out for 0.5 hour in a box-type resistance furnace at the temperature of 500 ℃, and the quenching mode is water cooling.
Then, secondary cold rolling was performed at room temperature with a strain of 60%, and secondary aging and quenching were performed in a box-type resistance furnace at 450 ℃ for 2 hours in a manner of water cooling.
And finally, carrying out cold rolling for three times at room temperature, wherein the deformation is 25%, carrying out stress relief annealing and quenching for 4 hours in a box-type resistance furnace at the temperature of 400 ℃, and carrying out water cooling on the quenching mode to obtain the high-strength high-conductivity heat-resistant copper alloy sample.
Comparative example 1
The comparative example differs from example 1 only in that no Fe is added. Other components and contents and preparation method are the same as example 1.
Comparative example 2
The present comparative example is different from example 1 in that only the primary cold rolling with a deformation amount of 60% and the primary aging at 450 c/2 hours were performed during the manufacturing process without the subsequent secondary cold rolling, secondary aging, tertiary cold rolling and low temperature annealing, and the raw material composition and content were the same as example 1.
Test example 1
The copper alloys prepared in examples 1 to 5 were examined for hardness, electric conductivity, yield strength, tensile strength, elongation, and heat-resistant temperature. Wherein:
the standard of the hardness test is GB/T4340.1-2009.
The conductivity test is based on the standard GB/T32791-2016.
The standard of the yield strength, tensile strength and elongation rate test basis is GB/T34505-2017.
The heat-resisting temperature test is based on the standard GB/T33370-2016.
The test results are shown in table 1.
TABLE 1
| Test items | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| Hardness of | 308HV | 332HV | 296HV | 283HV | 329HV |
| Electrical conductivity of | 45.9％IACS | 44.56％IACS | 43.8％IACS | 42.5％IACS | 47.3％IACS |
| Yield strength | 960MPa | 983MPa | 905MPa | 866MPa | 975MPa |
| Tensile strength | 985MPa | 1062MPa | 937MPa | 891MPa | 1011MPa |
| Elongation percentage | 6.7％ | 4.8％ | 5.2％ | 3.4％ | 3.1％ |
| Heat resistance temperature | ≥560℃ | ≥580℃ | ≥545℃ | ≥550℃ | ≥560℃ |
Test example 2
The copper alloys prepared in comparative examples 1 and 2 were tested for hardness, electric conductivity, yield strength, tensile strength, elongation, heat-resistant temperature, and compared with example 1. Wherein:
the standard of the hardness test is GB/T4340.1-2009.
The conductivity test is based on the standard GB/T32791-2016.
The standard of the yield strength, tensile strength and elongation rate test basis is GB/T34505-2017.
The heat-resisting temperature test is based on the standard GB/T33370-2016.
The test results are shown in table 2.
TABLE 2
| Test items | Example 1 | Comparative example 1 | Comparative example 2 |
| Hardness of | 308HV | 281HV | 275HV |
| Electrical conductivity of | 45.9％IACS | 48.0％IACS | 45.2％IACS |
| Yield strength | 960MPa | 895MPa | 861MPa |
| Tensile strength | 985MPa | 924MPa | 903MPa |
| Elongation percentage | 6.7％ | 6.2％ | 9.8％ |
| Heat resistance temperature | ≥560℃ | ≥550℃ | ≥535℃ |
Test example 3
The microstructure morphology of the Cu-Ni-Si-Fe system alloy prepared in example 4 was observed. Wherein:
FIG. 2 shows the metallurgical structure of the ingot, and it can be seen from FIG. 2 that the alloy has no obvious dendritic structure, which indicates that the alloy elements are diffused more uniformly in the solidification process. The alloy crystal grains are relatively coarse, and black and fine specks, namely Fe-Si primary phase particles, appear in the crystal grains.
FIG. 3 is a SEM image of a secondary electron of an ingot, and it can be seen from FIG. 3 that although a small amount of particles of an alloying element that are not completely dissolved in a matrix are present in an as-cast structure of an alloy, the entire structure is uniform and fine, and defects of the ingot are few.
FIG. 4 is a metallographic structure of the alloy after being subjected to solution treatment at 940 ℃ for 1 hour, and it can be seen from FIG. 4 that the microstructure of the alloy after being subjected to solution treatment is a remarkable equiaxed annealed twin crystal, and nonequilibrium solidified phase particles are basically dissolved in a matrix to form a supersaturated solid solution. The alloy is recrystallized during solid solution, the recrystallized grains are fine, the average grain size is 20-80 mu m, and the conditions of coarse grains and uneven size distribution after hot working are effectively improved.
FIG. 5 is a SEM picture of the secondary electrons after the alloy is subjected to solution treatment, and it can be seen from FIG. 5 that the alloy elements are uniformly dispersed in the matrix, and the size distribution of the formed primary second phase is uniform and about 80-100nm.
FIG. 6 shows the metallographic structure of the alloy after aging at 450 ℃ for 2 hours, and it can be seen from FIG. 6 that the alloy has a distinct deformed structure, grains are elongated in the rolling direction, and a plurality of nanoscale black second-phase particles are distributed along the grain boundaries.
FIG. 7 is a secondary electron SEM picture of the Cu-Ni-Si-Fe system alloy strip prepared in example 4. From FIG. 7, it can be seen that many nano-sized precipitated phase particles and submicron particles are formed in the copper matrix structure, and the submicron particles are in both spherical and rod-like forms.
Aiming at the problems of scarce Co raw material, high cost, low yield and the like of the Cu-Ni-Co-Si alloy of the lead frame of the large-scale integrated circuit and the urgent need of independently developing the next generation of very large-scale integrated circuit, the invention provides the Cu-Ni-Si-Fe system alloy, which adopts base metal Fe element to replace part of the Cu-Ni-Co-Si alloyAnd (2) separating even all Co elements, designing the content and proportion of Ni, co, fe, si and other elements through component optimization, properly increasing the content of Ni and Si, and forming the nano FeSi phase particles with high hardness and high heat resistance by means of strong atom bonding force between Fe and Si. The addition of trace Mg can effectively reduce Ni 2 The interlayer spacing of the Si photo promotes the FeSi phase particles to be separated out and refines the crystal grains of the copper matrix, and the Cu-Ni-Si-Fe alloy with low cost, high strength and high strength is prepared.
In the preparation method, the invention promotes the Ni, co and Si atoms in the copper matrix to be fully precipitated through the heat treatment process to form the nano-scale (Ni, co) 2 Si、Ni 3 Si phase, lamellar Ni 2 The discontinuous precipitation of Si is equal, and the multi-scale, multi-form and multi-phase synergistic strengthening effect is realized.
The present invention has been described in detail with reference to the embodiments, but the present invention is not limited to the embodiments described above, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention.
Claims (4)
1. The Cu-Ni-Si-Fe system alloy is characterized by comprising the following components in percentage by mass:
Ni：1.2wt%~5.0wt%，
Si：0.4wt%~2.0wt%，
Fe：0.1wt%~1.5wt%，
Mg：0.05wt%~0.15wt%，
the balance being copper;
the method for preparing the Cu-Ni-Si-Fe system alloy comprises the following steps:
s1: melting the raw materials according to a ratio, adding a covering agent and a refining agent for smelting, and casting and forming to obtain an ingot;
s2: homogenizing the cast ingot to obtain a billet;
s3: carrying out hot processing cogging treatment on the billet, and then carrying out first water cooling treatment to obtain a hot processing billet;
s4: carrying out solid solution treatment and second water cooling treatment on the hot processing blank in a protective atmosphere, and then sequentially carrying out primary cold processing, primary aging, secondary cold processing, secondary aging, tertiary cold processing and tertiary aging;
the smelting temperature is 1200-1400 ℃; the casting temperature is 1100-1300 ℃; the temperature of the homogenization treatment is 880-980 ℃; the homogenization treatment time is 1h to 6h; the temperature of the hot working cogging treatment is 900-980 ℃, and the deformation is 60-90%; the temperature of the solid solution treatment is 900-980 ℃; the time of the solid solution treatment is 1h to 4h; the deformation amount of the primary cold machining is 60% -80%; the temperature of the primary aging is 450-550 ℃; the time of the primary aging is 0.25h to 6h; the deformation of the secondary cold machining is 60-80%; the temperature of the secondary aging is 400-500 ℃; the time of the secondary aging is 0.25h to 6h; the deformation of the third cold working is 20-40%; the temperature of the third aging is 300-400 ℃; the time of the third aging is 0.25h to 6h.
2. The Cu-Ni-Si-Fe-based alloy according to claim 1, wherein the Cu-Ni-Si-Fe-based alloy comprises the following components in mass percent:
Ni：1.5wt%~4.8wt%，
Si：0.6wt%~1.8wt%，
Fe：0.3wt%~1.4wt%，
Mg：0.05wt%~0.15wt%，
the balance being copper.
3. The Cu-Ni-Si-Fe-based alloy according to claim 1, wherein the refining agent comprises a Cu-Ca alloy and a rare earth element Ce.
4. Use of the Cu-Ni-Si-Fe-based alloy of any one of claims 1~3 in the manufacture of electronic components.
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