CN101255510A - High-strength high-conductive chromium-copper and preparation thereof - Google Patents
High-strength high-conductive chromium-copper and preparation thereof Download PDFInfo
- Publication number
- CN101255510A CN101255510A CNA2008100882463A CN200810088246A CN101255510A CN 101255510 A CN101255510 A CN 101255510A CN A2008100882463 A CNA2008100882463 A CN A2008100882463A CN 200810088246 A CN200810088246 A CN 200810088246A CN 101255510 A CN101255510 A CN 101255510A
- Authority
- CN
- China
- Prior art keywords
- alloy
- conductivity
- copper alloy
- copper
- hardness
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- ZTXONRUJVYXVTJ-UHFFFAOYSA-N chromium copper Chemical compound [Cr][Cu][Cr] ZTXONRUJVYXVTJ-UHFFFAOYSA-N 0.000 title 1
- 239000010949 copper Substances 0.000 claims abstract description 70
- 239000000956 alloy Substances 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 48
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 45
- 239000011651 chromium Substances 0.000 claims abstract description 44
- 229910052802 copper Inorganic materials 0.000 claims abstract description 38
- 229910000881 Cu alloy Inorganic materials 0.000 claims abstract description 36
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000009718 spray deposition Methods 0.000 claims abstract description 28
- 229910003470 tongbaite Inorganic materials 0.000 claims abstract description 27
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 20
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 14
- 238000003723 Smelting Methods 0.000 claims abstract description 10
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 10
- 230000032683 aging Effects 0.000 claims description 38
- 239000002131 composite material Substances 0.000 claims description 30
- 230000008018 melting Effects 0.000 claims description 14
- 238000002844 melting Methods 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 239000010439 graphite Substances 0.000 claims description 13
- 229910002804 graphite Inorganic materials 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 8
- 238000010891 electric arc Methods 0.000 claims description 8
- 230000003014 reinforcing effect Effects 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 239000002923 metal particle Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 22
- 239000000470 constituent Substances 0.000 abstract 1
- 238000005728 strengthening Methods 0.000 description 13
- 238000003483 aging Methods 0.000 description 8
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000001550 time effect Effects 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 229910017813 Cu—Cr Inorganic materials 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000005489 elastic deformation Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002431 foraging effect Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910017526 Cu-Cr-Zr Inorganic materials 0.000 description 1
- 229910017810 Cu—Cr—Zr Inorganic materials 0.000 description 1
- 229910001122 Mischmetal Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Images
Landscapes
- Conductive Materials (AREA)
- Contacts (AREA)
Abstract
The invention discloses a high-strength high-conductivity chromium-containing copper alloy and the prepariation thereof. The copper alloy includes 0.35wt% to 0.9wt% of Cr3C2. The copper alloy also includes some mount of Zr and rare earth. The preparation is mainly includes the process of master alloy smelting, and further includes the process of preparing Cu-Cr3C2-Zr-rare earth alloy by spray casting method, and the processing process after spray casting the alloy, and a alloy for vlsivery large scale integrated circuit lead frame is prepared by the preparation. The invention can realize good match of the hardness and the conductivity of the copper alloy, which embody high temperature stability, the copper alloy has high electrical property and hardness, the comprehensive performance has already reaches the idea main performance index of vlsivery large scale integrated circuit lead frame. The invention expands the selection direction of high-strength high-conductivity copper-based material hardening constituent, and provides more perfect and better preparing process.
Description
Technical Field
The invention relates to a copper alloy and a preparation method thereof.
Background
The high-strength high-conductivity copper-based material can be divided into two main categories of high-strength high-conductivity copper alloy material and high-strength high-conductivity copper-based composite material. For high-strength and high-conductivity copper alloy materials, a Cu-Cr-Zr system with OMCL-1 developed by Mitsubishi corporation as a background is a key point of current research and development in recent years; high-strength high-conductivity copper-based composite material and Al2O3Dispersion Strengthened Copper (DSC) is the most representative, and the strengthening phase has a tendency toward carbides at present. Various preparation technologies are developed around the two main types of high-strength and high-conductivity copper-based materials, and a plurality of basic researches on mechanicalness are carried out.
Generally, the conductivity and strength of copper alloy prepared by conventional process are contradictory, and high conductivity results in very low strength, while high strength results in difficulty in improving conductivity. The addition of the alloying elements all reduce the conductivity of copper to varying degrees. Therefore, special reinforcement must be used to increase the strength as much as possible while ensuring high conductivity. The commonly used strengthening methods are: deformation strengthening, dispersion strengthening, solid solution strengthening plus precipitation strengthening, fine grain strengthening and fiber composite strengthening.
Cr3C2The molecular weight is 180, the crystal is gray black orthorhombic, the crystal has metallic luster, microhardness HV2700 and high-temperature oxidation resistance, is the most high-temperature oxidation resistant one in metal carbide, and is acid-resistant, alkali-resistant and insoluble in water. Is commonly used for engineering ceramics and wear-resistant coatings, is widely used on aircraft engines and petrochemical engineering mechanical devices, and is used for spraying semiconductorsAnd (3) a membrane. The alloy is usually used as a grain refiner, hardly forms a solid solution in a Cu base as a strengthening phase, and Cr is present at 1811 DEG C3C2There is only about 0.05 wt% solid solution in Cu. The carbide strengthening phase has certain conductivity and good interface compatibility, and is expected to develop wider application prospect in the field of high-strength and high-conductivity copper-based materials.
Disclosure of Invention
The first technical problem to be solved by the invention is to provide a high-strength high-conductivity chromium-containing copper alloy, which has good matching relation between hardness and conductivity, and simultaneously, the hardness and the conductivity can reflect higher temperature stability.
The second technical problem to be solved by the present invention is: the chromium-containing copper alloy prepared by the method has good hardness and conductivity relation, and the hardness and the conductivity can show higher temperature stability.
The third technical problem to be solved by the invention is: provides a method for preparing Cr3C2The method for reinforcing the copper-based lead frame composite material has the advantages that the chromium-containing copper alloy prepared by the method is well matched with the conductivity, the hardness and the conductivity can reflect higher temperature stability, and the lead frame composite material prepared by the method can reach the ideal main performance index of the lead frame material of the super-large-scale integrated circuit.
In order to solve the first technical problem, the invention adopts the following technical scheme: a high-strength high-conductivity chromium-containing copper alloy contains 0.35-0.9 wt% of Cr3C2。
Preferably: the copper alloy also contains 0.001-0.06 wt% of Zr and 0.001-0.06 wt% of rare earth.
Preferably: the rare earth is 55 wt% of La and 45 wt% of Ce.
In order to solve the second technical problem, the invention adopts the following technical scheme: a method for preparing a high-strength high-conductivity chromium-containing copper alloy, comprising:
the master alloy smelting process comprises the following steps: in a vacuum arc furnace, a graphite container is used for isolating a copper mould electrode, each element particle is added according to certain mass percent, and arc melting is started after pre-vacuumizing and filling argon to obtain the uniform spherical crown master alloy. Then, the master alloy is subjected to aging treatment. The graphite container is usually a graphite crucible.
Preferably: pure metal particles of each element are added according to the mass percentage of Cu, Cr, Zr and rare earth of 97-99: 0.3-0.9: 0.05-0.5: 0.02-0.08.
Preferably: the electric arc melting current is 10A-15A, the voltage is 150V-200V, the melting is repeated for 10 min-20 min each time, and the uniform spherical crown master alloy is obtained.
In order to solve the third technical problem, the present invention provides a method for preparing Cr3C2The method for reinforcing the copper-based lead frame composite material comprises a master alloy smelting process, an alloy preparation process by a spray casting method and a treatment process after alloy spray casting;
the alloy preparation process by the spray casting method comprises the following steps: carrying out vacuum spray forming on the master alloy in a vacuum spray casting system to prepare a round bar-shaped alloy;
the treatment process after the alloy spray casting comprises the following steps: and (3) directly carrying out cold deformation on the alloy obtained by spray casting, then carrying out aging treatment, and taking out the alloy after furnace cooling.
Preferably: aging the alloy after cold deformation at 460-530 ℃ for 60-90 min.
The invention has the following beneficial effects:
the Cr-containing alloy3C2The copper alloy has good matching relation between the hardness and the conductivity, the conductivity is increased to be close to the highest level when the hardness reaches the maximum, and the hardness and the conductivity reflect higher temperature stability.The lead frame material has higher electrical property and hardness, and the comprehensive performance of the lead frame material reaches the ideal main performance index of the lead frame material of the ultra-large scale integrated circuit. The invention expands the selection direction of the reinforced phase of the high-strength high-conductivity copper-based material and provides a more perfect and excellent preparation process.
Drawings
FIG. 1 shows Cr3C2Hardness and conductivity vs. aging temperature curves for Cu deformation aged 65% for 1 h.
FIG. 2 shows Cr3C2Cu deformation 65% hardness and conductivity vs. aging time curves at 520 ℃.
FIG. 3 shows Cr3C2Cu deformation of 65% and 520 ℃ aging, stress-strain curve at 20min, hardness and conductivity change with temperature.
FIG. 4 shows Cr3C2Hardness and conductivity vs. aging temperature curves for Cu deformation aged 65% for 1 h.
FIG. 5 shows Cr3C2Cu deformation 65% at 490 ℃, hardness and conductivity vs. aging time curve.
FIG. 6 shows Cr3C2Cu deformation of 65% and 490 ℃ aging, stress-strain curve at 55 min.
Detailed Description
The invention provides a high-strength high-conductivity chromium-containing copper alloy, which contains 0.35-0.9 wt% of Cr3C2I.e. Cr3C2The content of Cr in the copper alloy accounts for 0.30-0.78 wt% of the copper alloy, and the content of C accounts for 0.047-0.12 wt% of the copper alloy. The copper alloy can also comprise 0.001-0.06 wt% of Zr and 0.001-0.06 wt% of rare earth, and the component in the rare earth Y is preferably 55 wt% of La and 45 wt% of Ce.
The invention also provides a method for preparing the high-strength high-conductivity chromium-containing copper alloy, which comprises the following steps:
smelting a master alloy: in a vacuum arc furnace, a graphite crucible is used for isolating a copper mould electrode, and pure metal particles of each element are added according to the mass percentage of Cu, Cr, Zr and rare earth of 97-99: 0.3-0.9: 0.05-0.5: 0.02-0.08. Starting arc melting after pre-vacuumizing and filling argon, repeatedly melting for 4-6 times (10-20 min each time) at a melting current of 10-15A and a voltage of 150-200V to obtain uniform spherical crown Cu-Cr3C2-Zr-Y master alloy. Then carrying out aging treatment. Wherein Cr is converted to Cr in whole or in part3C2。
The invention also provides a method for preparing Cr3C2The method for reinforcing the copper-based lead frame composite material comprises a master alloy smelting process and a Cu-Cr spray casting method3C2-Zr-rare earth alloy process and treatment process after alloy spray casting; wherein,
Cu-Cr preparation method by spray casting3C2the-Zr-rare earth alloy process comprises the following steps: vacuum spray forming is carried out on the master alloy in a vacuum spray casting system to prepare the round rod-shaped Cu-Cr3C2-Zr-rare earth alloys;
the treatment process after the alloy spray casting comprises the following steps: the alloy obtained by spray casting is directly subjected to cold deformation, then is subjected to aging treatment at 460-530 ℃ for 60-90 min, and is taken out after furnace cooling.
High-performance Cr prepared by smelting method in vacuum arc furnace by using graphite crucible to separate copper mould electrode3C2The reinforced Cu-based high-strength high-conductivity composite material has good strength and electrical properties.
EXAMPLE 1 preparation of Cr in graphite vessel arc furnace3C2The reinforced phase high-strength high-conductivity copper-based composite material and detection and analysis thereof are as follows:
(1) the embodiment is as follows:
an electric arc furnace (ZGJL001-40-4) produced by a Jinzhou transformer electric furnace factory is adopted to cast an alloy with 50g of nominal composition Cu-0.6Cr-0.2Zr-0.04RE (55 wt% La +45 wt% Ce), and the detailed process is as follows: the metal raw material with nominal composition is placed in a hemispherical shell-shaped pure graphite crucible, then the graphite crucible is hermetically placed in a copper mould electrode crucible for fusion casting, and the graphite crucible is used for maintaining the isolation state between the metal raw material and the copper mould electrode crucible. The electric arc melting is started after the vacuum is pre-pumped and the argon is filled for about 0.02MPa, the melting current is 15A, and the voltage is 180V. In order to ensure that the base material is as uniform as possible, the smelting is repeated for 4 times, each time for 10min, about 50g of the copper-based material with a more uniform spherical crown shape is prepared, and the density can reach 100%. And performing nitrogen protection aging treatment by using an SK2-1-10 tubular resistance furnace, wherein the temperature fluctuation of a normal working furnace is +/-2 ℃. Observing metallographic microstructure and high-temperature metallographic microstructure with AX10-imager. A1m high-temperature metallographic microscope, and analyzing metallographic structure with 10ml HNO3+15mlH2SO4+1g CrO3+60ml H2The solution formulated with O erodes for 6 seconds. The analysis of the components was carried out by means of a scanning electron microscope SEM (Tiny-SEM 1710, Hitachi S-3000N). Hardness test was performed using HXS-1000AK microhardness instrument load 100g, and conductivity test was performed using eddy current conductivity meter 7501, manufactured by Xiamen second electronics Instrument factory.
The Cu-0.6Cr-0.2Zr-0.04RE (55 wt% La +45 wt% Ce) nominal component is adopted for preparation, and the purity of each substance is Cu block: 99.999%, Cr fragment: 99.9%, small pieces of Zr: 99%, 55% wt La and 45% wt Ce misch metal pieces: 99.9%, and the melting points of the added substances are, in order, Ce: 795 ℃, La: 920 ℃, Cu: 1083 ℃, Zr: 1852 ℃, Cr: 1857 ℃, and obtaining Cr after smelting in an electric arc furnace3C2And Cr3C2-a Cu alloy based composite material. In the test process, Zr reacts with C in the graphite crucible to generate ZrC, and the observation shows that the ZrC does not diffuse into Cu melt, but adheres to the surface of graphite and acts as a molecular sieve attenuation layer for contacting Cr and graphite.
(2)、Cr3C2The electrical and mechanical properties of the/Cu copper-based composite material are as follows:
FIG. 1 shows Cr3C2The hardness-aging temperature curve a and the conductivity-aging temperature curve b of the/Cu-based composite material after aging for 1 h. It can be seen from curve a that during ageing a distinct age-hardening peak occurs, followed by a rapid decrease in hardness with increasing temperature, and that after ageing at 470 ℃ for 1h, the peak hardness is HV 198.7, at which time from curve b the electrical conductivity rises to 78.9 IACS%, followed by an increasing and gradual increase in conductivity with increasing temperature. The relation between the hardness peak value and the conductivity is better than that of high-strength high-conductivity copper alloy, and the conductivity is increased to a higher level when the hardness reaches the maximum. According to the definition of the softening temperature: the temperature at which the hardness of the material after annealing for 1h drops to 80% of the original hardness is generally referred to as the softening temperature. Cr can be calculated from the maximum value in the curve a3C2The softening temperature of the Cu-based composite material can reach 540 ℃, and is calculated as follows: the hardness between 198.7 and 159HV is calculated according to the hardness decrease curve between temperatures, wherein the hardness is lower than 178.7HV at 520 ℃ and higher than 143.5HV at 570 ℃.
The time-effect hardening characteristics of the composite material are obviously different from those of the common dispersion-strengthened composite material, and the time-effect hardening peak is very prominent because of Cr dissolved in Cu base3C2The result of a large amount of precipitation shows that a larger Cu electrode and a strong water cooling system below the electric arc furnace can obtain a larger cooling speed, so that the solidification of the Cu-based material is greatly deviated from the balance, and the phase Cr is strengthened3C2The solid solubility of the chromium-free chromium oxide is greatly improved, so that the Cr content in the matrix after aging treatment is improved3C2The quantity of the reinforcing phase is more fine and the distribution is more dispersed, which is beneficial to obviously improving the Cr content under the condition of keeping high conductivity3C2Strength of the/Cu copper-based composite material. Meanwhile, the rapid cooling speed of the electric arc furnace can refine grains to a certain degree, so that a certain strengthening effect is achieved, and the 65% cold deformation performed before aging is of course helpful for improving the strength.
Based on FIG. 1, it can be seen that the optimum temperature for aging is between 470 ℃ and 520 ℃, and FIG. 2 shows Cr3C2Cu copper matrixThe hardness of the composite material at 520 ℃ is shown in a curve c, and the conductivity is shown in a curve d. It can be seen from curve c that a distinct age hardening peak is also observed during aging, then the hardness decreases rapidly and slowly with aging time, and finally becomes gentle, and aging is performed for 20min at 520 ℃ with peak hardness of HV 184.8, at which time the electrical conductivity rises to 78.9 IACS% from curve d, and then slowly rises with aging time, and finally becomes gentle. As shown in FIG. 3, the tensile strength at this time was 591 MPa. The relation between the peak value of hardness and the conductivity is better than that of high-strength high-conductivity copper alloy, and the conductivity is increased to be close to the highest level when the hardness reaches the maximum. The hardness and the conductivity both represent good temperature stability, the hardness is only reduced by 7 percent and the conductivity is increased by 13 percent after nearly 3 hours of aging after the highest value of the hardness.
FIG. 3 shows Cr3C2Stress-Strain (Stress-Strain) curves at 65% Cu deformation and 20min aging at 520 ℃. Tests show that equiaxial tough pits are fully distributed on the section of the master alloy, the master alloy presents the characteristic of ductile fracture, and the fracture belongs to ductile fracture. It can be seen from fig. 3 that the elastic deformation zone is very wide and the elasticity of the material is better. The linear hardening zone was not evident, indicating that the effect of the stretch hardening was not evident. There is no apparent yield point, which is a characteristic that Cu-based FCC crystals should have. The elongation rate is approximately equal to 95 percent, and the material has good plasticity.
The invention adopts the spray deposition forming technology to successfully prepare the high-performance Cr for the first time3C2The Cu-based lead frame composite material is enhanced, and the ideal main performance indexes of the lead frame material of the super-large-scale integrated circuit are achieved, namely: the tensile strength sigma b is more than 600MPa, the microhardness Hv is more than 180, the conductivity is more than 80 percent IACS (international annealed copper standard), and the softening temperature is more than 500 ℃. The relevant test was as in example 2.
Second, example 2 spray-Molding of high-Strength, high-conductivity Cr3C2Detection and analysis of the Cu-based composite material:
(1) the embodiment is as follows:
an electric arc furnace (ZGJL001-40-4) produced by a Jinzhou transformer electric furnace factory is adoptedLine 0.8 wt% Cr3C2And casting the Cu mother copper-based composite material. And starting arc melting after pre-vacuumizing and filling argon gas to about 0.02MPa, and repeatedly melting for 4 times and 10 minutes each time to obtain about 50g of a more uniform spherical crown-shaped mother copper-based material in order to ensure that the mother material is as uniform as possible. The SYKY vacuum spray casting system produced by a scientific power supply electromechanical equipment factory is adopted for vacuum spray forming, and about 50g of round bar-shaped Cr can be prepared3C2The density of the Cu-based composite material reaches 94.1 percent. The density of the cold deformation reaches 98.9 percent after 65 percent. And performing nitrogen protection aging treatment by using an SK2-1-10 tubular resistance furnace, wherein the temperature fluctuation of a normal working furnace is +/-2 ℃. Microscopic structure was observed by using AX10-imager. A1m metallographic microscope, and 10ml of HNO was used for analysis of the microstructure3+15ml H2SO4+1g CrO3+60ml H2The solution formulated with O erodes for 6 seconds. The composition analysis and tensile fracture analysis were carried out by means of a scanning electron microscope SEM (Tiny-SEM 1710, Hitachi S-3000N). Hardness test was performed using HXS-1000AK microhardness instrument load 100g, and conductivity test was performed using eddy current conductivity meter 7501, manufactured by Xiamen second electronics Instrument factory. The homogenization test and observation of the sputtered metallic phase were carried out by glow spectroscopy (GDA750), and the tensile strength test was carried out by a universal electronic tester (WDW).
(2)、Cr3C2The electrical and mechanical properties of the/Cu copper-based composite material are as follows:
FIG. 5 shows Cr3C2The hardness-aging temperature curve e and the conductivity-aging temperature curve f of the/Cu-based composite material after aging for 1 h. It can be seen from curve e that during ageing a distinct age-hardening peak occurs, followed by a first, faster and more gradual decrease in hardness with increasing temperature, and that after 1h ageing at 490 c the peak hardness is HV210.8, at which point the electrical conductivity rises to 80.7 IACS%, followed by an increasing electrical conductivity with increasing temperature, as seen from curve f. The relation between the hardness peak value and the conductivity is better matched with that of the high-strength high-conductivity copper alloy, and the conductivity is also increased to a higher level when the hardness reaches the maximum. According to the definition of the softening temperature: the temperature at which the hardness of the material after annealing for 1h drops to 80% of the original hardness is generally referred to as the softening temperature. Cr can be calculated from the maximum value in the curve e3C2The softening temperature of the/Cu copper-based composite material can reach 590 ℃, and the softening temperature is calculated as follows: 210.8 × 80% ═ 153HV, hardness of less than 154.5HV at 590 ℃.
The time-effect hardening characteristics of the composite material are obviously different from those of the common dispersion-strengthened composite material, and the time-effect hardening peak is very prominent due to Cr dissolved in Cu base3C2The large precipitation results in that the large cooling speed of the spray deposition greatly deviates the solidification of the Cu-based material from the balance, and the strengthening phase Cr3C2The solid solubility of the chromium-free chromium oxide is greatly improved, so that the Cr content in the matrix after aging treatment is improved3C2The quantity of the reinforcing phase is more fine and the distribution is more dispersed, which is beneficial to obviously improving the Cr content under the condition of keeping high conductivity3C2Strength of the/Cu copper-based composite material. Meanwhile, smaller grains can be obtained at a higher cooling rate of spray deposition, so that a certain degree of fine-grain strengthening effect is achieved, and the 65% cold deformation which is performed before aging is of course helpful for improving the strength.
Based on FIG. 5, it can be seen that the optimum temperature for aging is 490 deg.C, and FIG. 6 shows Cr3C2The hardness of the/Cu copper-based composite material at 490 ℃ is represented by an aging time curve g and the conductivity is represented by an aging time curve h. From curve g in fig. 6, a distinct age hardening peak is also observed during aging, then the hardness decrease increases with aging time, is first rapid and then slow, and finally tends to be flat, and aging is carried out for 55min at 490 ℃, the peak hardness of which is HV 219.5, at this time, as seen from curve h in fig. 5, the conductivity rises to 82.5 IACS%, then increases with aging time, the conductivity rises slowly, and finally tends to be flat. The tensile strength at this time was 664.5MPa, as shown in FIG. 7. The relation between the hardness peak value and the conductivity is better than that of high-strength high-conductivity copper alloy, and the conductivity is increased to be close to the highest level when the hardness reaches the maximum. The hardness and the conductivity both reflect good temperature stability, the hardness is only reduced by 12 percent and the conductivity is increased by 10 percent after more than 3 hours of aging after the highest value of the hardness.
FIG. 7 shows Cr3C2Stress-strain curve at 65% Cu deformation and 55min aging at 490 ℃. After the experimentAccording to experimental observation, equiaxial dimples are distributed on the fracture surface and show the characteristic of ductile fracture from the SEM appearance of the fracture, wherein some relatively flat dimples show the sign of intergranular fracture, and the fracture mainly belongs to ductile fracture and simultaneously has an unobvious tendency of intergranular fracture. It can be seen from fig. 7 that the elastic deformation zone is wide and the elasticity of the material is good. The linear hardening zone was not evident, indicating that the effect of the stretch hardening was not evident. There is no apparent yield point, which is a characteristic that Cu-based FCC crystals should have. The elongation rate is approximately equal to 10.6 percent, and the material has certain plasticity.
Claims (8)
1. The high-strength high-conductivity chromium-containing copper alloy is characterized in that: the copper alloy contains 0.35 wt% -0.9 wt% of Cr3C2。
2. The high-strength high-conductivity chromium-containing copper alloy according to claim 1, wherein: the copper alloy also contains 0.001-0.06 wt% of Zr and 0.001-0.06 wt% of rare earth.
3. The high-strength high-conductivity chromium-containing copper alloy according to claim 2, wherein: the rare earth is 55 wt% of La and 45 wt% of Ce.
4. A method for preparing high-strength high-conductivity chromium-containing copper alloy is characterized by comprising the following steps:
the master alloy smelting process comprises the following steps: in a vacuum arc furnace, a graphite container is used for isolating a copper mould electrode, each element particle is added according to certain mass percent, and arc melting is started after pre-vacuumizing and filling argon to obtain the uniform spherical crown master alloy.
5. The method for preparing the high-strength high-conductivity chromium-containing copper alloy according to claim 4, wherein the method comprises the following steps: pure metal particles of each element are added according to the mass percentage of Cu, Cr, Zr and rare earth of 97-99: 0.3-0.9: 0.05-0.5: 0.02-0.08.
6. The method for preparing the high-strength high-conductivity chromium-containing copper alloy according to claim 4, wherein the method comprises the following steps: the electric arc melting current is 10-15A, the voltage is 150-200V, the melting is repeated for 10-20 min each time, and the uniform spherical crown master alloy is obtained.
7. Used for preparing Cr3C2The method for reinforcing the copper-based lead frame composite material is characterized by comprising the following steps of: the method comprises a master alloy smelting process, an alloy preparation process by a spray casting method and a treatment process after alloy spray casting; wherein,
the alloy preparation process by the spray casting method comprises the following steps: carrying out vacuum spray forming on the master alloy in a vacuum spray casting system to prepare a round bar-shaped alloy;
the treatment process after the alloy spray casting comprises the following steps: and (3) directly carrying out cold deformation on the alloy obtained by spray casting, then carrying out aging treatment, and taking out the alloy after furnace cooling.
8. The method for preparing Cr according to claim 73C2The method for reinforcing the copper-based lead frame composite material is characterized by comprising the following steps of: coldThe deformed alloy is aged for 60-90 min at 460-530 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200810088246 CN101255510B (en) | 2008-03-26 | 2008-03-26 | High-strength high-conductive chromium-copper and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200810088246 CN101255510B (en) | 2008-03-26 | 2008-03-26 | High-strength high-conductive chromium-copper and preparation thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101255510A true CN101255510A (en) | 2008-09-03 |
| CN101255510B CN101255510B (en) | 2013-01-23 |
Family
ID=39890605
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200810088246 Expired - Fee Related CN101255510B (en) | 2008-03-26 | 2008-03-26 | High-strength high-conductive chromium-copper and preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101255510B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107541611A (en) * | 2016-06-27 | 2018-01-05 | 天津明源机械设备有限公司 | A kind of high-strength high-conductive chromium-copper |
| CN107586977A (en) * | 2017-08-24 | 2018-01-16 | 西安理工大学 | A kind of preparation method of copper alloy with high strength and high conductivity bar |
| CN108425032A (en) * | 2018-03-30 | 2018-08-21 | 中国科学院金属研究所 | The solidification preparation method of Cu-Cr contact alloys with diffusion-type composite solidification tissue |
| CN108611520A (en) * | 2018-05-08 | 2018-10-02 | 上海理工大学 | A kind of copper-based in-situ composite material and preparation method thereof |
| CN109371281A (en) * | 2018-12-24 | 2019-02-22 | 宁波颂杰电器有限公司 | A kind of brass alloys of high temperature heat-resistant corrosion and its fire cover of preparation |
| CN109576516A (en) * | 2018-12-19 | 2019-04-05 | 湘潭大学 | A kind of preparation method of electromagnetic wave shielding copper-iron alloy partitioned wire short route |
| CN112941398A (en) * | 2021-01-28 | 2021-06-11 | 淮阴工学院 | Graphite reinforced self-lubricating copper alloy and preparation method thereof |
| CN113073217A (en) * | 2021-03-10 | 2021-07-06 | 宁波金田铜业(集团)股份有限公司 | Grain refiner and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1323179C (en) * | 2003-09-01 | 2007-06-27 | 昆明贵金属研究所 | High-strength, High-conductivity copper-base alloy material and preparing method thereof |
| CN1818109A (en) * | 2006-03-14 | 2006-08-16 | 河南科技大学 | Copper alloy materials with high-strength and conducting performances and production thereof |
-
2008
- 2008-03-26 CN CN 200810088246 patent/CN101255510B/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107541611A (en) * | 2016-06-27 | 2018-01-05 | 天津明源机械设备有限公司 | A kind of high-strength high-conductive chromium-copper |
| CN107586977A (en) * | 2017-08-24 | 2018-01-16 | 西安理工大学 | A kind of preparation method of copper alloy with high strength and high conductivity bar |
| CN107586977B (en) * | 2017-08-24 | 2019-04-26 | 西安理工大学 | A kind of preparation method of copper alloy with high strength and high conductivity bar |
| CN108425032A (en) * | 2018-03-30 | 2018-08-21 | 中国科学院金属研究所 | The solidification preparation method of Cu-Cr contact alloys with diffusion-type composite solidification tissue |
| CN108611520A (en) * | 2018-05-08 | 2018-10-02 | 上海理工大学 | A kind of copper-based in-situ composite material and preparation method thereof |
| CN108611520B (en) * | 2018-05-08 | 2019-05-31 | 上海理工大学 | A kind of copper-based in-situ composite material and preparation method thereof |
| CN109576516A (en) * | 2018-12-19 | 2019-04-05 | 湘潭大学 | A kind of preparation method of electromagnetic wave shielding copper-iron alloy partitioned wire short route |
| CN109576516B (en) * | 2018-12-19 | 2020-11-03 | 湘潭大学 | Short-process preparation method of copper-iron alloy plate wire for electromagnetic wave shielding |
| CN109371281A (en) * | 2018-12-24 | 2019-02-22 | 宁波颂杰电器有限公司 | A kind of brass alloys of high temperature heat-resistant corrosion and its fire cover of preparation |
| CN112941398A (en) * | 2021-01-28 | 2021-06-11 | 淮阴工学院 | Graphite reinforced self-lubricating copper alloy and preparation method thereof |
| CN113073217A (en) * | 2021-03-10 | 2021-07-06 | 宁波金田铜业(集团)股份有限公司 | Grain refiner and application thereof |
| CN113073217B (en) * | 2021-03-10 | 2022-06-03 | 宁波金田铜业(集团)股份有限公司 | Grain refiner and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101255510B (en) | 2013-01-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101255510B (en) | High-strength high-conductive chromium-copper and preparation thereof | |
| CN108866417B (en) | High-strength corrosion-resistant medium-entropy alloy and preparation method thereof | |
| EP3650567B1 (en) | High-strength and high-toughness magnesium alloy and preparation method thereof | |
| CN107739956B (en) | A kind of Nb microalloying Ni-Co-Fe-Cr-Al high-entropy alloy | |
| CN104630556B (en) | High anti-corrosion CuNiSiNbSn series elastic copper alloy of a kind of ultra-high-strength/tenacity and preparation method thereof | |
| CN113174509B (en) | High-strength beryllium copper alloy bar and preparation process thereof | |
| US20040191111A1 (en) | Er strengthening aluminum alloy | |
| CN110592445B (en) | 720-doped 740MPa cold extrusion Al-Zn-Mg-Cu-Ti aluminum alloy and preparation method thereof | |
| CN107419141B (en) | A kind of Al-Si-Fe-RE-B alloy conductor material and preparation method | |
| CN111004957B (en) | Non-equal atomic ratio high-entropy alloy and preparation method thereof | |
| CN100532599C (en) | Fatigue resistant Cu-Ti alloy and producing method thereof | |
| CN113943874B (en) | Copper alloy material for 5G base station power connector and preparation method thereof | |
| CN112725677A (en) | High-strength high-toughness TiZrHfNbSc refractory high-entropy alloy and preparation method thereof | |
| Lei et al. | Effects of electromagnetic stirring on microstructure and mechanical properties of super light Mg-Li-Al-Zn alloy | |
| CN116287857A (en) | High-elasticity high-strength high-conductivity Cu-Ni-Sn alloy and preparation method thereof | |
| CN114645159B (en) | High-temperature oxidation-resistant high-strength nickel-tungsten-cobalt-chromium alloy and preparation method thereof | |
| CN114672716B (en) | CoCrNi with high strength and toughness in heat treatment state2(V2B)xEutectic high-entropy alloy and preparation method thereof | |
| CN110629081B (en) | Novel heat-resistant high-strength high-plasticity corrosion-resistant Al-Cu-Mg-Zn-Ti series aluminum alloy and preparation method thereof | |
| CN109881060B (en) | Si-containing corrosion-resistant magnesium alloy and preparation method thereof | |
| JPH07258804A (en) | Production of copper alloy for electronic equipment | |
| CN107460378B (en) | A kind of Al-Si-Fe-Mg-Cu alloy conductor material and preparation method thereof | |
| Skai et al. | Effect of Sn addition on the mechanical and electrical properties of Cu-15% Cr in-situ composites | |
| CN111254317A (en) | Nickel-based casting alloy and preparation method thereof | |
| KR920006827B1 (en) | Stainless maraging steel and the making process | |
| CN110629068A (en) | Zirconium microalloyed multi-element complex cast aluminum bronze alloy |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130123 Termination date: 20190326 |