CN108456797A - A kind of Cu-Ag-Fe-C systems alloy and preparation method thereof - Google Patents

A kind of Cu-Ag-Fe-C systems alloy and preparation method thereof Download PDF

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Publication number
CN108456797A
CN108456797A CN201810259998.5A CN201810259998A CN108456797A CN 108456797 A CN108456797 A CN 108456797A CN 201810259998 A CN201810259998 A CN 201810259998A CN 108456797 A CN108456797 A CN 108456797A
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alloy
preparation
melting
prealloys
systems
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CN108456797B (en
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许磊
王有超
邓小玲
孙丽虹
历长云
陈鹏飞
米国发
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Henan University of Technology
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C9/00Alloys based on copper
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/02Making non-ferrous alloys by melting
    • C22C1/03Making non-ferrous alloys by melting using master alloys

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
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  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Conductive Materials (AREA)

Abstract

The invention discloses a kind of Cu Ag Fe C systems alloy and preparation method thereof, which is grouped as by following group by mass percentage:Ag, 0.5 3%;Fe C prealloys, 10 15%, surplus Cu.Preparation method includes:The melting step of Cu and Ag, the addition step of Fe C prealloys, quick coagulation step, to obtain the Cu Ag Fe C systems alloy that Fe C prealloy particles are uniformly distributed in Cu Ag matrixes.The method of the present invention can improve the conductivity and tensile strength of Cu Fe systems alloy, and the tensile strength of obtained cast alloy is 420 500MPa, and conductivity is 40 55%IACS.

Description

A kind of Cu-Ag-Fe-C systems alloy and preparation method thereof
Technical field
The present invention relates to the preparation methods of an Albatra metal, more particularly it relates to which a kind of Cu-Ag-Fe-C systems close Gold and preparation method thereof.
Background technology
Copper alloy has good electrical and thermal conductivity, ductility and mechanical property, is electronic information, electric power, the energy, ship The key function material developed with important industries such as machineries.Compared with the copper alloy with high strength and high conductivity of other systems, closed in Cu-Fe systems The fusing point of gold element Fe is relatively low, is easier to melting, and non-miscible gap of Fe and Cu is small, and the deformability of alloy is preferable, can Processability is preferable, so the research about Cu-Fe systems alloy receives attention, becomes the important side of copper alloy with high strength and high conductivity development One of to.
Currently, high-strength highly-conductive Cu-Fe systems alloy mainly utilizes conventional fusion-cast method to prepare just alloy, then first alloy is carried out The processing such as subsequent heat treatment, deformation, obtain the Cu-Fe systems alloy of final use state.When founding prepares just alloy, due to Solidification cooling is very fast, it is easy to cause to be dissolved a large amount of Fe elements in Cu matrixes, the serious conduction for reducing Cu-Fe alloys Property.Although oversaturated Fe is constantly precipitated during subsequent heat treatment, thermomechanical treatment etc., the diffusion velocity of Fe under low temperature It is very slow, it is difficult to the Fe being dissolved in Cu is precipitated completely, and solid solutions of the Fe in Cu be reduce the main influences of Cu-Fe alloys because Element.So in order to improve the electric conductivity of Cu-Fe alloys, need to reduce solid solution capacities of the Fe in Cu.
Existing method not can be well solved this frequently with deformation, heat treatment, high-intensity magnetic field, multi-element alloyed etc. Problem.Such as:Ag is considered as damaging the minimum element of Cu alloy conductives effect, but carried out to Cu-Fe alloys using Ag Cu-Fe-Ag alloys prepared by alloying are still dissolved 2.5% or more Fe in as cast condition Cu matrixes.Due to the expansion of Fe under low temperature Scattered speed is very slow, although can reduce the solid solution capacity of Fe in Cu otherwise, the Fe being dissolved in Cu can not equally be subtracted It is few to arrive very low state.
Therefore, it is badly in need of a kind of method that can more efficiently reduce the Fe being dissolved in Cu.
Invention content
In order to overcome the defects of the prior art, the purpose of the present invention is to provide a kind of Cu-Ag-Fe-C systems alloy and its Preparation method.
A kind of Cu-Ag-Fe-C systems alloy, by mass percentage, Cu-Ag-Fe-C systems alloy is grouped as by following group: Ag, 0.5-3%;Fe-C prealloys, 10-15%, surplus Cu.
In above-mentioned Cu-Ag-Fe-C systems alloy, C content is in the Fe-C prealloys as a preferred implementation manner, 0.8~1.8wt% (such as:0.9wt%, 1.0wt%, 1.1wt%, 1.2wt%, 1.3wt%, 1.4wt%, 1.5wt%, 1.6wt%, 1.7wt%).
A kind of preparation method of Cu-Ag-Fe-C systems alloy, including:
Solid material Cu and Ag are carried out melting processing, obtain liquid Cu-Ag aluminium alloys by the melting step of Cu and Ag;
Fe-C prealloy powder is added in the liquid Cu-Ag aluminium alloys and is stirred by the addition step of Fe-C prealloys Processing, obtains uniformly mixed melting material;
The melting material is carried out quick solidification processing, obtains Fe-C prealloy particles and be uniformly distributed by quick coagulation step Cu-Ag-Fe-C systems alloy in Cu-Ag matrixes.
The present invention is that copper and Ag are first smelted into liquid, and smelting temperature is then maintained at more slightly higher than copper and silver point But do not reach the fusing point of Fe-C prealloy powder, then under the smelting temperature be added Fe-C prealloy powder and be uniformly mixed with Solid Fe-C prealloy powder is set to be dispersed in the copper-silver alloy liquid of liquid, last rapid cooling, present invention utilizes C and Cu Mutually exclusive effect in Fe-Cu-C ternary systems is utilized Ag ratios Fe and is first dissolved in Cu, makees to the inhibition of Fe solid solutions With the feature that Fe diffusion velocities in Cu are low under low temperature is utilized, Fe is added in solid form in Cu-Ag alloy liquids, so Rapid cooling afterwards, diffusions of the control Fe into Cu matrixes, to make Fe be dispersed in Kufil matrix, reduction is solid-solution in Fe amounts in Cu;In this process, Fe-C prealloys powder melts, and is also beneficial to reduce the Fe being dissolved in Cu liquid in this way Amount is conducive to the electric conductivity for improving alloy.
In the above preparation method, described molten as a preferred implementation manner, in the melting step of the Cu and Ag Refining is handled to be carried out in frequency induction furnace in a vacuum.
In the above preparation method, described molten as a preferred implementation manner, in the melting step of the Cu and Ag Refining processing smelting temperature be 1090~1200 DEG C, more preferably 1100~1180 DEG C (such as 1110 DEG C, 1120 DEG C, 1130 DEG C, 1140℃、1150℃、1160℃、1170℃、1175℃).Smelting temperature is excessively high to be unfavorable for being connected with next step.
In the above preparation method, described molten as a preferred implementation manner, in the melting step of the Cu and Ag Refining processing when vacuum degree be 10Pa or less (such as 9Pa, 7Pa, 5Pa, 3Pa, 1Pa, 0.5Pa, 0.1Pa, 0.05Pa).
In the above preparation method, described as a preferred implementation manner, in the addition step of the Fe-C prealloys Temperature when stir process be 1100~1180 DEG C (such as 1110 DEG C, 1120 DEG C, 1130 DEG C, 1140 DEG C, 1150 DEG C, 1160 DEG C, 1170 DEG C, 1175 DEG C), it is highly preferred that the stir process carries out under conditions of 1100 DEG C.Temperature when stir process The too high or too low Fe-C prealloys powder that is all unfavorable for is evenly dispersed in copper-silver alloy melt, is generated not to alloy property Profit influences.
In the above preparation method, described as a preferred implementation manner, in the addition step of the Fe-C prealloys Stir process is mechanical agitation or electromagnetic agitation, time of the stir process be 1~5min (such as 1.5min, 2min, 2.5min、3min、4min、4.5min);It is highly preferred that the churned mechanically mixing speed be 240-400rpm (such as 250rpm, 280rpm, 300rpm, 320rpm, 350rpm, 370rpm, 390rpm), the excitation voltage of the electromagnetic agitation is 180-220V (such as 185V, 190V, 200V, 210V, 220V).The effect of electromagnetic agitation is better than mechanical agitation, in the present invention Stirring parameter under be stirred the dispersion of Fe-C prealloy powders can be made more uniform, can further increase The performance of alloy.
In the above preparation method, as a preferred implementation manner, in the quick coagulation step, the fast rapid hardening Gu processing is water cooled copper mould casting method or melt spinning;It is highly preferred that the cooling velocity of the water cooled copper mould casting method is 50 DEG C/s~1000 DEG C/s (such as 55 DEG C/s, 100 DEG C/s, 200 DEG C/s, 300 DEG C/s, 400 DEG C/s, 500 DEG C/s, 600 DEG C/s, 700 ℃/s、800℃/s、900℃/s、950℃/s)。
In the above preparation method, the solid material Cu and Ag is purity as a preferred implementation manner, The cathode copper and Ag simple substance of 99.9wt% or more;Or the solid material Cu and Ag is Cu-Ag prealloy powder.Cu-Ag is closed in advance Bronze is commercial product, naturally it is also possible to conventionally prepare, can be prepared by vacuum atomizing stove, by required proportioning Raw material cathode copper and pure aluminum melting after be atomized into powder particle.Very few do not have of the addition of Ag reduces Fe solid solutions in matrix The effect of amount, Ag additions are excessive, not only increase cost, it is often more important that iron phase can be caused to be roughened, dropped low-alloyed using temperature Degree.
In the above preparation method, the particle size of the Fe-C prealloy powder is 60 as a preferred implementation manner, ~220nm (such as the specific point value formation of 70nm, 80nm, 100nm, 120nm, 150nm, 180nm, 190nm, 210nm or above-mentioned Any size range).The Fe-C prealloy powder is commercial product, naturally it is also possible to conventionally prepare, can lead to The preparation of vacuum atomizing stove is crossed, powder particle will be atomized into after the pure iron as raw material of required proportioning and carburant melting, then passed through again High-energy ball milling is prepared into the Fe-C prealloy powder of required granularity.The Fe-C prealloy powder particle sizes used in the present invention be 60~ 220nm, particle is excessive, and reinforcing effect is poor, too small, is easy that Fe is made to be dissolved in Cu, and electric conductivity is deteriorated, but also the group of being easy to happen It is poly-.
In the above preparation method, as a preferred implementation manner, with the Fe-C prealloy powder and the solid On the basis of the gross mass of raw material Cu and Ag, the dosage of the Fe-C prealloy powder be 10wt%~15wt% (such as 11%, 12%, 13%, 14%), the dosage of the solid material Cu be 82wt%~89.5wt% (such as 86%, 87%, 88%, 89%), the dosage of the solid material Ag be 0.5wt%~3wt% (such as 0.6wt%, 0.8wt%, 1.2wt%, 1.5wt%, 1.8wt%, 2.3wt%, 2.8wt%).
In the above preparation method, as a preferred implementation manner, in the Fe-C prealloy powder, C content be 0.8~ 1.8wt% (such as:0.9wt%, 1.0wt%, 1.1wt%, 1.2wt%, 1.3wt%, 1.4wt%, 1.5wt%, 1.6wt%, 1.7wt%).
In the alloy of the present invention, C content is too low will to lead to have more Fe to dissolve in Cu, not to the electric conductivity of alloy Profit, C content is excessively high may to form graphite or Fe3C etc..
In the above preparation method, the preparation method further includes alloy post-processing step as a preferred implementation manner, Suddenly, the Cu-Ag-Fe-C systems alloy that the quick coagulation step obtains is post-processed, obtain Cu-Ag-Fe-C systems alloy at Product.It is highly preferred that the post-processing is one or more in heat treatment, deformation process, magnetic field processing;The post-processing is normal Rule are handled.
Compared with prior art, the present invention has the advantages that:
In order to more effectively reduce the Fe contents being dissolved in Cu-Fe alloy substrates, this patent proposition is existed using C and Cu Mutually exclusive effect in Fe-Cu-C ternary systems, Fe-C is added into Cu;Ag ratios Fe is utilized first to be dissolved in Cu, to Fe The inhibiting effect of solid solution, while using the low feature of Fe diffusion velocities in Cu under low temperature, by Fe, Fe-C is added in solid form In Cu liquid, the solid solution capacity of Fe in Cu-Ag matrixes is greatly reduced in then rapid cooling, diffusions of the control Fe into Cu matrixes.This Inventive method can improve the conductivity and tensile strength of Cu-Fe alloys, and the tensile strength of obtained cast alloy is 420- 500MPa, conductivity 40-55%IACS.
Specific implementation mode
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments be only used for the present invention without For limiting the scope of the invention.Externally it should be understood that after having read present disclosure, those skilled in the art are to this hair Bright to make various changes or modifications, these equivalent forms also fall within the scope of the appended claims of the present application.
Embodiment 1
Alloy manufactured in the present embodiment is Cu-2.0wt%Ag-15wt% (Fe-C) alloy, i.e.,:In the alloy, Fe-C Content be 15wt%, the content of Cu is 83wt%, and the content of Ag is 2wt%, wherein the quality hundred of C in Fe-C alloy powders Divide than being 1wt%.Specific preparation method is as follows:
The high-purity Cu of electrolysis of 99.9wt% and simple substance Ag are subjected to melting, smelting temperature control in frequency induction furnace in a vacuum At 1100 ± 5 DEG C, vacuum degree 10Pa, the Fe-C after solid copper and silver all become liquid by particle size for 80-120nm Alloyed powder is added in copper silver melt, is still made with the mixing speed mechanical agitation 3min of 300rpm under the conditions of 1100 ± 5 DEG C Solid-state Fe-C powder alloys are evenly distributed in Kufil liquid, are then cast in water cooled copper mould and are quickly cooled down, cooling speed Degree is 100 DEG C/s, the Cu-2.0wt%Ag-15wt% obtained after cast (Fe-C) alloy.
The cast alloy product prepared to the embodiment method is tested for the property, tensile strength 465MPa, conductive Rate is 50%IACS.
Embodiment 2-4
Embodiment 2-4 is other than the mass percent of C in Fe-C alloy powders is different from embodiment 1, other techniques ginseng Number is the same as embodiment 1.The mass percent of C and the performance of obtained alloy are referring to table in the Fe-C alloy powders of embodiment 2-4 1。
The technological parameter and results of property of 1 embodiment 2-4 of table
Embodiment 5-6 and comparative example 1
Temperature (temperature when smelting temperature is equal to stirring) is no when embodiment 5-6 and comparative example 1 are in addition to smelting temperature and stirring It is same as other than embodiment 1, other technological parameters are the same as embodiment 1.It the smelting temperature of embodiment 5-6 and comparative example 1 and obtains The performance of alloy is referring to table 2.
The technological parameter and results of property of table 2 embodiment 5-6 and comparative example 1
Embodiment 7-8 and comparative example 2
Embodiment 7-8 and comparative example 2 are other than the particle size of Fe-C prealloy powder is different from embodiment 1, other works Skill parameter is the same as embodiment 1.The property of the particle size and obtained alloy of embodiment 7-8 and the Fe-C prealloy powder of comparative example 2 It can be referring to table 3.
The technological parameter and results of property of table 3 embodiment 7-8 and comparative example 2
Embodiment 9-10 and comparative example 3
Embodiment 9-10 and comparative example 3 are other than the content of Ag simple substance in alloy is different from embodiment 1, other techniques ginseng Number is the same as embodiment 1.The content of Ag simple substance and the performance of obtained alloy are referring to table in embodiment 9-10 and the alloy of comparative example 3 4。
The technological parameter and results of property of table 4 embodiment 9-10 and comparative example 3
Embodiment 11-14
Embodiment 11-14 is other than agitating mode and parameter are different from embodiment 1, other technological parameters are the same as embodiment 1. The mixing parametric of embodiment 11-14 and the performance of obtained alloy are referring to table 5.
The technological parameter and results of property of 5 embodiment 11-14 of table
Comparative example 4
Alloy prepared by this comparative example is that (i.e. the content of Fe is 15wt% to Cu-15wt%Fe alloys in the alloy, and Cu's contains Amount is 85wt%;Namely the dosage of cathode copper is the 85wt% of cathode copper and Fe powder gross masses, the dosage of Fe powder in raw material For the 15wt% of cathode copper and Fe powder gross masses), specific preparation method is as follows:
The electrolysis high-purity Cu and Fe of 99.9wt% are subjected to melting in frequency induction furnace in a vacuum, smelting temperature control exists It 1600 DEG C or so, vacuum degree 10Pa, is cast in water cooled copper mould and is quickly cooled down after the completion of melting, cooling velocity 100 DEG C/s, the Cu-15wt%Fe alloys obtained after cast.
The cast alloy product prepared to the comparative example method is tested for the property, tensile strength 310MPa, conductive Rate is 15%IACS.
Comparative example 5
This comparative example prepare alloy be Cu-15wt% (Fe-C) alloy (i.e. the content of Fe-C is 15wt% in the alloy, The content of Cu is 85wt%, and C content is 1wt% in Fe-C, and specific preparation method is as follows:
The high-purity Cu and Fe-C powder of the electrolysis of 99.9wt% is subjected to melting, smelting temperature control in frequency induction furnace in a vacuum System is cast in water cooled copper mould after the completion of 1600 DEG C or so, vacuum degree 10Pa, melting and is quickly cooled down, and cooling velocity is 100 DEG C/s, the Cu-15wt% obtained after cast (Fe-C) alloy.
The cast alloy product prepared to the comparative example method is tested for the property, tensile strength 315MPa, conductive Rate is 17%IACS.
Comparative example 6
Alloy prepared by this comparative example is that (i.e. in the alloy Fe-C contains for Cu-2.0wt%Ag-15wt% (Fe-C) alloy Amount is 15wt%, and the content of Cu is 83wt%, and the content of Ag is 2wt%, and C content is 1wt% in Fe-C, and specific preparation method is such as Under:
The high-purity Cu of electrolysis of 99.9wt%, silver-colored simple substance and Fe-C powder are subjected to melting in frequency induction furnace in a vacuum, melted Temperature control is refined at 1600 DEG C or so, vacuum degree 10Pa, melting is cast in water cooled copper mould is quickly cooled down after the completion, cold But speed is 100 DEG C/s, the Cu-2.0wt%Ag-15wt% obtained after cast (Fe-C) alloy.
The cast alloy product prepared to the comparative example method is tested for the property, tensile strength 318MPa, conductive Rate is 24%IACS.

Claims (10)

1. a kind of Cu-Ag-Fe-C systems alloy, which is characterized in that by mass percentage, Cu-Ag-Fe-C systems alloy is by as follows Group is grouped as:Ag, 0.5-3%;Fe-C prealloys, 10-15%, surplus Cu.
2. Cu-Ag-Fe-C systems according to claim 1 alloy, which is characterized in that C content is in the Fe-C prealloys 0.8~1.8wt%.
3. a kind of preparation method of Cu-Ag-Fe-C systems alloy, which is characterized in that including:
Solid material Cu and Ag are carried out melting processing, obtain liquid Cu-Ag aluminium alloys by the melting step of Cu and Ag;
Fe-C prealloy powder is added in the liquid Cu-Ag aluminium alloys and is stirred by the addition step of Fe-C prealloys, Obtain uniformly mixed melting material;
The melting material is carried out quick solidification processing, obtains Fe-C prealloy particles and be uniformly distributed in Cu- by quick coagulation step Cu-Ag-Fe-C systems alloy in Ag matrixes.
4. preparation method according to claim 3, which is characterized in that described molten in the melting step of the Cu and Ag Refining is handled to be carried out in frequency induction furnace in a vacuum.
5. preparation method according to claim 3, which is characterized in that described molten in the melting step of the Cu and Ag The smelting temperature of refining processing is 1090~1200 DEG C, preferably 1100~1180 DEG C;
It is highly preferred that the vacuum degree when melting processing is 10Pa or less.
6. preparation method according to claim 3, which is characterized in that described in the addition step of the Fe-C prealloys Temperature when stir process is 1100~1180 DEG C, it is preferable that the stir process carries out under conditions of 1100 DEG C.
7. preparation method according to claim 3, which is characterized in that described in the addition step of the Fe-C prealloys Stir process is mechanical agitation or electromagnetic agitation, and the time of the stir process is 1~5min;Preferably, the mechanical agitation Mixing speed be 240-400rpm, the excitation voltage of the electromagnetic agitation is 180-220V.
8. preparation method according to claim 3, which is characterized in that in the quick coagulation step, the fast rapid hardening Gu processing is water cooled copper mould casting method or melt spinning;Preferably, the cooling velocity of the water cooled copper mould casting method be 50 DEG C/ S~1000 DEG C/s.
9. preparation method according to claim 3, which is characterized in that former with the Fe-C prealloy powder and the solid On the basis of the gross mass for expecting Cu and Ag, the dosage of the Fe-C prealloy powder is 10wt%~15wt%, and the dosage of the Ag is The dosage of 0.5wt%~3wt%, the Cu are 82wt%~89.5wt%;
Preferably, the particle size of the Fe-C prealloy powder is 60~220nm;
It is highly preferred that the solid material Cu and Ag is the cathode copper and Ag simple substance of purity 99.9wt% or more.
10. according to claim 3-9 any one of them preparation methods, which is characterized in that in the Fe-C prealloy powder, C contains Amount is 0.8~1.8wt%.
CN201810259998.5A 2018-03-27 2018-03-27 A kind of Cu-Ag-Fe-C system alloy and preparation method thereof Expired - Fee Related CN108456797B (en)

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