CN101775509B - Method for improving corrosion resistance of copper by adding oxygen group alloy elements - Google Patents
Method for improving corrosion resistance of copper by adding oxygen group alloy elements Download PDFInfo
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- CN101775509B CN101775509B CN2010101017285A CN201010101728A CN101775509B CN 101775509 B CN101775509 B CN 101775509B CN 2010101017285 A CN2010101017285 A CN 2010101017285A CN 201010101728 A CN201010101728 A CN 201010101728A CN 101775509 B CN101775509 B CN 101775509B
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Abstract
The invention relates to a method for improving corrosion resistance of copper by adding oxygen group alloy elements, comprising the following steps: respectively mixing S, Se and Te with Cu, repeatedly smelting copper in an arc furnace to prepare Cu-S, Cu-Se or Cu-Te alloy and annealing the alloy in a heating furnace, preserving the heat for a certain time and cooling to room temperature to prepare corrosion resistant steel. The method has the following benefits: after the copper is corroded, the surface of the copper is covered by acicular whiskers and the density of the whiskers is high, after being added, the alloy elements are to partially replace oxygen to enter into the oxide lattices of the copper, thus weakening the forming capability of vacancy in the copper, blocking the lattices of the copper to spread, improving the protection capability of the copper oxide on the surface and ensuring the corrosion resistance of the alloy copper to be stronger than that of the pure copper; not only the corrosion resistance of the copper can be improved but also the production cost can be lowered by taking full advantage of the residual Se and Te in the copper smelting process; the packaging temperature of the packaging materials in the existing integrated circuits is lower than 673K, and not only the corrosion resistance of the packaging materials is improved but also the package cost is reduced by using the Cu-Se or Cu-Te alloy as the lead frame material.
Description
Technical field:
The present invention relates to the erosion-resisting method in a kind of metallic surface, especially during melting copper by adding the resistance to corrosion that the chalcogen alloying element improves circuit lead frame material copper components and parts surface.
Background technology:
Copper has physics-chem characteristics such as good electrical conductivity, thermal conductivity, erosion resistance and ductility.Conductivity and heat conductivility are only second to silver, and fine copper can pull into very thin copper wire, make very thin Copper Foil.Because copper has above-mentioned premium properties, so purposes widely arranged industrial.Comprise aspects such as electric utility, machinofacture, traffic, building.At present, copper is mainly used in this field of Electrical and Electronic industry makes electric wire, communication cable and other finished products such as electric motor, generator amature and electronic machine, instrument etc., and this part consumption accounts for about half of industrial aggregate demand.Copper and copper alloy all occupy critical role in equipment devices such as computer chip, unicircuit, transistor, printed circuit board.For example, lead of transistor with the chrome zirconium copper alloy of high conduction, high heat conduction.Recently, the international well-known IBM of Computer Company has adopted the aluminium in the copper replacement silicon, and this indicates the up-to-date breakthrough of the most ancient metal of the mankind in the semiconductor technology application facet.In various household equipments and utensil,, all to use copper for conductive and heat-conductive.Copper is widely used in electrical system, and its intensity, ductility and solidity to corrosion make it become the excellence conductor of circuit, and it still makes the material of electric motor and transformer also as the power cable of high, medium and low voltage.In Personal Computer and hardware, be extensive use of the copper connection cable.In roof construction,, be worth with copper in order to resist extreme climate.Be exposed to the copper in this climatope, the surface forms verdigris (ventilation breather), and this is the characteristics of this application of copper.The main copper of using of transportation equipment, for example boats and ships, automobile and aircraft.Hull can prevent the formation of biofouling with cupronickel, lowers resistance, and the thermal conductivity of copper, intensity make it can be used as automobile radiators.Copper is owing to have bigger thermal conductivity, thus also be widely used in the high temperature cooling system, and big electric current such as nuclear power generating equipment, in the powerful environment, the heat transfer tube of using on evaporator-condenser is all made of copper basically.
Copper unavoidably will corrode in Working environment, because the corrosion thing of copper does not have self-protective, fine copper at high temperature resistance to corrosion is more weak, copper is further corroded, thereby influence its works better, has limited the further application of copper.In the past, people mainly are by producing high-purity copper, and then add metal alloy unit and usually improve its corrosion resistance.Because high purity copper costs an arm and a leg, therefore this method cost is higher.Se and Te are the impurity that is difficult for removal in the copper smelting process.By this patent, we find that oxygen family element Se and Te have the resistance to corrosion that improves copper as alloying element.Like this, we can regulate its content to improve its resistance to corrosion by means such as an amount of interpolations again by utilizing Se residual in the copper smelting process and Te fully.So just can solve above-mentioned employing high purity copper as expensive problem that raw material brought.
Summary of the invention
Purpose of the present invention is exactly at above-mentioned the deficiencies in the prior art, provides a kind of by adding the method for chalcogen alloying element raising corrosion resistance of copper.
The objective of the invention is to be achieved through the following technical solutions:
By adding the method for chalcogen alloying element raising corrosion resistance of copper, comprise following order and step:
A, the S with 0.05～0.5wt.% purity 99.99wt.%, Se, Te are that the pure Cu of 99.99wt.% mixes with the purity of 99.5～99.95wt.% respectively;
B, mixed respectively material is placed electric arc furnace respectively, then body of heater is vacuumized, feed high-purity argon gas, it is 3000～6000cm that high-purity argon gas feeds flow
3/ min, air pressure are a normal atmosphere;
C, startup electric arc furnace make the copper fusing at 1133 ℃～183 ℃ by glow discharge, melt back 6-8 time, and Cu-S, Cu-Se or Cu-Te alloy are made in each melting 5 minutes;
D, the alloy that will make Cu-S, Cu-Se or Cu-Te are put into the process furnace that is connected with high-purity hydrogen respectively and are annealed 400 ℃～700 ℃ temperature;
E, in annealing temperature, be incubated 360min～1440min, in being connected with the environment of high-purity hydrogen, be cooled to room temperature, be prepared into corrosion protected copper.
Purpose of the present invention can also be achieved through the following technical solutions:
The glow discharge power that step c states is 2～10kW; Melt back 6～8 times, each melting all makes electric arc furnace be warmed up to 1133 ℃～1183 ℃, each melting stopped melting after 5 minutes, reduced to room temperature, open stove, the upset material will originally be gone up on the translating into of bottom, and originally went below the translating into of top, refuse is smelted then, and so melt back is 6～8 times.The gas feeding amount of the described feeding high-purity hydrogen of steps d is 50cm
3/ min.
Beneficial effect: the erosion rate of fine copper is very fast; but after having added the chalcogen alloying element; these elements will the part replace oxygen enter into the corrosion thing lattice of copper; weakened the formation ability in copper room; hindered the lattice diffusion of copper; thereby improve the protective capability of surface corrosion thing, suppress the further corrosion of alloyed copper, make the resistance to corrosion of alloyed copper be better than fine copper.Make full use of Se residual in the copper smelting process and Te, can improve the resistance to corrosion of copper, can reduce production costs again.The package temperature of packaged material is lower than 673K in the existing integrated circuits, uses Cu-Se, Cu-Te alloy to make the resistance to corrosion that blaster fuse frame material has not only improved packaged material, has also reduced packaging cost.
Description of drawings:
Accompanying drawing 1 is that pure Cu, Cu-S, Cu-Se, Cu-Te alloy are at 300 ℃ of surperficial electromicroscopic photographs that corrode 8h.
Accompanying drawing 2 is that pure Cu, Cu-S, Cu-Se, Cu-Te alloy are at 500 ℃ of surperficial electromicroscopic photographs that corrode 8h.
Accompanying drawing 3 is Cu-S, Cu-Se and the Cu-Te alloy comparative graph in 300 ℃～500 ℃ surrosion and the surrosion of pure Cu.
Embodiment:
Be described in further detail below in conjunction with drawings and Examples:
By the method for interpolation chalcogen alloying element raising corrosion resistance of copper,, comprise following order and step:
A, the S with 0.05～0.5wt.% purity 99.99wt.%, Se, Te are that the pure Cu of 99.99wt.% mixes with the purity of 99.5～99.95wt.% respectively;
B, mixed respectively material is placed electric arc furnace respectively, then body of heater is vacuumized, feed high-purity argon gas, it is 3000～6000cm that high-purity argon gas feeds flow
3/ min, air pressure are a normal atmosphere;
C, startup electric arc furnace, by glow discharge, discharge power is 2-10kW, make copper and chalcogen alloying element be warming up to 1133 ℃～1183 ℃ thawings, melt back 6-8 time, each melting all makes electric arc furnace be warmed up to 1133 ℃～1183 ℃, each melting stopped melting after 5 minutes, reduce to room temperature, open stove, the upset material, to originally on the translating into of bottom, go up, originally go below the translating into of top, refuse is smelted then, and so Cu-S, Cu-Se or Cu-Te alloy are made in melt back for 6-8 time;
D, the alloy that will make Cu-S, Cu-Se or Cu-Te are put into the process furnace that is connected with high-purity hydrogen respectively and are annealed 400 ℃～700 ℃ temperature;
E, being incubated 360min～1440min in annealing temperature, is 50cm in the feeding amount
3Be cooled to room temperature in the environment of the high-purity hydrogen of/min, be prepared into corrosion protected copper.
Embodiment 1
A, be that the pure Cu of 99.99wt.% mixes with S and the purity of 99.5wt.% of 0.5wt.% purity 99.99wt.%;
B, mixed material is placed electric arc furnace, then body of heater is vacuumized, feed high-purity argon gas, it is 3000cm that high-purity argon gas feeds flow
3/ min, air pressure are a normal atmosphere;
C, startup electric arc furnace, by glow discharge, discharge power is made as 2kW, make copper and chalcogen alloying element be warming up to 1133 ℃ of thawings, melting stopped melting after 5 minutes, reduced to room temperature, open stove, the upset material will originally be gone up on the translating into of bottom, originally below the translating into of top, go, overturn and closed upper furnace door, then body of heater has been vacuumized, fed high-purity argon gas, refuse is smelted then, and so melt back is made the Cu-S alloy 6 times;
D, the Cu-S alloy of making is put into the process furnace that is connected with high-purity hydrogen anneal 400 ℃ of temperature;
E, being incubated 360min in annealing temperature, is 50cm in the feeding amount
3Be cooled to room temperature in the environment of the high-purity hydrogen of/min, be prepared into corrosion protected copper.
Embodiment 2
A, be that the pure Cu of 99.99wt.% mixes with Se and the purity of 99.9wt.% of 0.1wt.% purity 99.99wt.%;
B, mixed respectively material is placed electric arc furnace respectively, then body of heater is vacuumized, feed high-purity argon gas, it is 4000cm that high-purity argon gas feeds flow
3/ min, air pressure are a normal atmosphere;
C, startup electric arc furnace, by glow discharge, discharge power is made as 5kW, make copper and chalcogen alloying element be warming up to 1150 ℃ of thawings, melting stopped melting after 5 minutes, reduced to room temperature, open stove, the upset material will originally be gone up on the translating into of bottom, originally below the translating into of top, go, overturn and closed upper furnace door, then body of heater has been vacuumized, fed high-purity argon gas, refuse is smelted then, and so melt back is made the Cu-Se alloy 7 times;
D, the Cu-Se alloy of making is put into the process furnace that is connected with high-purity hydrogen anneal 600 ℃ of temperature;
E, being incubated 1000min in annealing temperature, is 50cm in the feeding amount
3Be cooled to room temperature in the environment of the high-purity hydrogen of/min, be prepared into corrosion protected copper.
Embodiment 3
A, be that the pure Cu of 99.99wt.% mixes with Te and the purity of 99.95wt.% of 0.05wt.% purity 99.99wt.%;
B, mixed respectively material is placed electric arc furnace respectively, then body of heater is vacuumized, feed high-purity argon gas, it is 6000cm that high-purity argon gas feeds flow
3/ min, air pressure are a normal atmosphere;
C, startup electric arc furnace, by glow discharge, discharge power is made as 10kW, make copper and chalcogen alloying element be warming up to 1183 ℃ of thawings, melting stopped melting after 5 minutes, reduced to room temperature, open stove, the upset material will originally be gone up on the translating into of bottom, originally below the translating into of top, go, overturn and closed upper furnace door, then body of heater has been vacuumized, fed high-purity argon gas, refuse is smelted then, and so melt back is made the Cu-Te alloy 8 times;
D, the Cu-Te alloy of making is put into the process furnace that is connected with high-purity hydrogen anneal 700 ℃ of temperature;
E, being incubated 1440min in annealing temperature, is 50cm in the feeding amount
3Be cooled to room temperature in the environment of the high-purity hydrogen of/min, be prepared into corrosion protected copper.
Embodiment 4
A, be that the pure Cu of 99.99wt.% mixes with Se and the purity of 99.7wt.% of 0.3wt.% purity 99.99wt.%;
B, mixed respectively material is placed electric arc furnace respectively, then body of heater is vacuumized, feed high-purity argon gas, it is 5000cm that high-purity argon gas feeds flow
3/ min, air pressure are a normal atmosphere;
C, startup electric arc furnace, by glow discharge, discharge power is made as 7kW, make copper and chalcogen alloying element be warming up to 1160 ℃ of thawings, melting stopped melting after 5 minutes, reduced to room temperature, open stove, the upset material will originally be gone up on the translating into of bottom, originally below the translating into of top, go, overturn and closed upper furnace door, then body of heater has been vacuumized, fed high-purity argon gas, refuse is smelted then, and so melt back is made the Cu-Se alloy 6 times;
D, the Cu-Se alloy of making is put into the process furnace that is connected with high-purity hydrogen anneal 500 ℃ of temperature;
E, being incubated 1200min in annealing temperature, is 50cm in the feeding amount
3Be cooled to room temperature in the environment of the high-purity hydrogen of/min, be prepared into corrosion protected copper.
A, be that the pure Cu of 99.99wt.% mixes with Te and the purity of 99.8wt.% of 0.2wt.% purity 99.99wt.%;
B, mixed respectively material is placed electric arc furnace respectively, then body of heater is vacuumized, feed high-purity argon gas, it is 5000cm3/min that high-purity argon gas feeds flow, and air pressure is a normal atmosphere;
C, startup electric arc furnace, by glow discharge, discharge power is made as 8kW, make copper and chalcogen alloying element be warming up to 1170 ℃ of thawings, melting stopped melting after 5 minutes, reduced to room temperature, open stove, the upset material will originally be gone up on the translating into of bottom, originally below the translating into of top, go, overturn and closed upper furnace door, then body of heater has been vacuumized, fed high-purity argon gas, refuse is smelted then, and so melt back is made the Cu-Te alloy 6 times;
D, the Cu-Te alloy of making is put into the process furnace that is connected with high-purity hydrogen anneal 550 ℃ of temperature;
E, being incubated 800min in annealing temperature, is 50cm in the feeding amount
3Be cooled to room temperature in the environment of the high-purity hydrogen of/min, be prepared into corrosion protected copper.
Claims (4)
1. the method by interpolation chalcogen alloying element raising corrosion resistance of copper is characterized in that, comprises following order and step:
A, be that the pure Cu of 99.99wt.% mixes with the purity of 99.5-99.95wt.% respectively with the chalcogen alloying element of 0.05-0.5wt.% purity 99.99wt.%, described chalcogen alloying element is S, Se, Te;
B, mixed respectively material is placed electric arc furnace respectively, then body of heater is vacuumized, feed high-purity argon gas, it is 3000-6000cm that high-purity argon gas feeds flow
3/ min, air pressure are a normal atmosphere;
C, start electric arc furnace, at 1133 ℃---1183 ℃ make the copper fusing by glow discharge, melt back 6-8 time, and melting is 5 minutes at every turn, makes Cu-S, Cu-Se or Cu-Te alloy;
D, the alloy that will make Cu-S, Cu-Se or Cu-Te put into respectively be connected with high-purity hydrogen process furnace at 400 ℃---700 ℃ of temperature are annealed;
E, in annealing temperature, be incubated 360～1440min, in being connected with the environment of high-purity hydrogen, be cooled to room temperature, be prepared into corrosion protected copper.
2. described a kind of by adding the method for chalcogen alloying element raising corrosion resistance of copper according to claim 1, it is characterized in that the described melt back of step c 6-8 time, be that each melting all makes electric arc furnace be warmed up to 1133 ℃---1183 ℃, each melting stopped melting after 5 minutes, reduced to room temperature, open stove, the upset material with originally on the translating into of bottom, originally goes below the translating into of top, refuse is smelted then, and so melt back is 6-8 time.
3. described a kind of by adding the method for chalcogen alloying element raising corrosion resistance of copper according to claim 1, it is characterized in that the described glow discharge power of step c is 2-10kW.
4. described a kind of by adding the method for chalcogen alloying element raising corrosion resistance of copper according to claim 1, it is characterized in that the gas feeding amount of the described feeding high-purity hydrogen of steps d is 50cm
3/ min.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1648266A (en) * | 2004-04-30 | 2005-08-03 | 何政 | Specific high conductivity alloy material |
| CN1993487A (en) * | 2004-08-10 | 2007-07-04 | 三宝伸铜工业株式会社 | Copper alloy casting article excellent in machinability, strength, wear resistance and corrosion resistance and method for casting thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1648266A (en) * | 2004-04-30 | 2005-08-03 | 何政 | Specific high conductivity alloy material |
| CN1993487A (en) * | 2004-08-10 | 2007-07-04 | 三宝伸铜工业株式会社 | Copper alloy casting article excellent in machinability, strength, wear resistance and corrosion resistance and method for casting thereof |
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| JP特开2005-226097A 2005.08.25 |
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Granted publication date: 20110413 Termination date: 20120128 |