CN1776827A - Titanium-coated copper bus-bar and its making method - Google Patents
Titanium-coated copper bus-bar and its making method Download PDFInfo
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- CN1776827A CN1776827A CNA200510123205XA CN200510123205A CN1776827A CN 1776827 A CN1776827 A CN 1776827A CN A200510123205X A CNA200510123205X A CN A200510123205XA CN 200510123205 A CN200510123205 A CN 200510123205A CN 1776827 A CN1776827 A CN 1776827A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/02—Single bars, rods, wires, or strips
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
- B21C37/00—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape
- B21C37/04—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of bars or wire
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/10—Electrodes, e.g. composition, counter electrode
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
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Abstract
Disclosed is a titanium-coated copper bus-bar with a good corrosion resistance and conductivity and its making method. The bus-bar is produced by connecting the titanium or titanium alloy with a good corrosion resistance and copper and copper alloy with a good conductivity. The bus-bar between the titanium-coated layer and copper inner core has an interface reaction layer owing to the solid phase reaction and low-temperature eutectic reaction. Moreover, the bus-bar has an intermediate combination alternatively or additionally.
Description
Technical field
The invention relates to a kind of have good anti-corrosion and a conductivity cover copper busbar of titanium and preparation method thereof, this copper busbar that covers titanium is to combine with the copper with high conductance (or copper alloy) by the titanium (or titanium alloy) that will have superior corrosion resistance under pressurization and/or heating condition to obtain.
Background technology
Busbar is used as the medium that transmits electric energy by connecting several circuit, and form power transmission circuit with higher current capacity, as large-scale transmission distributed lines, electrical equipment lead or telecommunication cable, be installed in power plant, building, integrated mill, large-scale department store, subway station or the new airport.The advantage of busbar is can transmit more electric energy under the identical condition of electric conductor volume, and therefore, busbar also comes to replace cable to use in big capacity allocation system recently more muchly.
The material that will have copper (Cu), aluminium (Al) or the copper facing aluminium of higher electric conductivity usually is used for busbar.Yet the corrosion resistance of copper or aluminum is relatively poor, therefore, under the heavy corrosion atmosphere that generates gas chlorination thing or sulfur dioxide gas, when copper, aluminium or copper aluminium bus bar used in electrolysis tank or electroplating bath, busbar was easy to be corroded, thereby had shortened the useful life of busbar.
Simultaneously, the titanium (or titanium alloy) with superior relatively corrosion resistance can be kept the long period under corrosive environment, but because the electric conductivity of titanium is too low, therefore can not realize high efficiency electrolysis.
In order to remedy these shortcomings, people developed a kind of by will having relative high conductance copper and titanium with relative excellent corrosion resistance in conjunction with the copper busbar that covers titanium that makes.The copper busbar that covers titanium of conduction is by hot-extrudable method, rolling, hubbing (drawing) and the preparation of blast pressing.Usually, copper bar is inserted in the titanium pipe, then by hot-extrudable method, rolling, hubbing, blast pressing with copper bar mechanical adhesion to described titanium pipe.Afterwards, the product that obtains carries out annealing in process in 650-850 ℃ temperature range, and like this, the contact interface between titanium outer covering layer and the copper kernel can metallurgical binding, makes the copper busbar that covers titanium.Ag-Cu-Sn base that can be optionally that fusing point is lower or Ag-Cu-Al base weld filler is embedded in the interface between titanium shell and the copper bar.Then the product that obtains is extruded under 700 ℃, under 650 ℃, carried out annealing in process then, make the copper busbar that covers titanium.
But, use the copper busbar that titanium is covered in these method preparations to have following shortcoming: on the interface between titanium pipe and the copper bar, to form frangible intermetallic compound, thereby reduce the bond strength between titanium pipe and the copper bar.And be difficult to Ag-Cu-Sn base or Ag-Cu-Al base weld filler are embedded on the interface between titanium shell and the copper bar equably.
In addition, when in air to copper with titanium heats or during heat treatment because to make a concerted effort to the affinity of oxygen in the surface of copper and titanium high, very easily oxidized, therefore copper that can not obtain and the effective combination between the titanium.For fear of the oxidation of copper and titanium, must be under vacuum or inert atmosphere to titanium with copper heats or heat treatment, thereby bring inconvenience and increase cost.
Summary of the invention
Therefore, an object of the present invention is to provide a kind of have relative superior corrosion resistance and a conductivity cover copper busbar of titanium and preparation method thereof.
Another object of the present invention is by using paint-on technique and make the technology preparation of the metallurgical interface combination of dissimilar metals cover the copper busbar of titanium, and it is oxidized that described paint-on technique can prevent from oxygen is had the copper and the titanium of high affinity.
The invention relates to a kind of have good anti-corrosion and a conductivity cover copper busbar of titanium and preparation method thereof, this copper busbar that covers titanium is to combine by titanium (or titanium alloy) that will have excellent corrosion resistance and the copper with high conductance (or copper alloy) to obtain.
The copper busbar that covers titanium according to the present invention has many advantages: can be as using the long period in electrolytic cell or the electroplating pool in serious corrosive environment; Has good conductive performance; In conductive process, can not cause discharge; Demonstrate good electrolysis characteristic, have higher current density and efficient.
For realize according to the object of the invention as in this concrete these or other advantage that implement and broadly described, a kind of copper busbar that covers titanium with high corrosion resistance and conductivity is provided, and this copper busbar that covers titanium comprises copper kernel, titanium coating layer and the interfacial reaction layer between described copper kernel and titanium coating layer around described copper kernel.The cross-sectional structure of this busbar is: titanium coating layer/interfacial reaction layer/copper kernel/interfacial reaction layer/titanium coating layer.Interaction on the interface between copper kernel and the titanium coating layer produces described interfacial reaction layer by titanium and copper.Described interfacial reaction layer can be the solid phase reaction layer, carries out between copper and titanium by mechanical adhesion and heat treatment that mutual material Transfer forms; It also can be the melting layer that forms by the low temperature eutectic reaction; It can also be the combination of described solid phase reaction layer and melting layer.Can use the simple metal or the alloy of titanium and copper.
May further include intermediate binder matter according to the copper busbar that covers titanium of the present invention, described intermediate binder matter is located on the interfacial reaction layer (solid phase reaction layer and/or melting layer) between titanium coating layer and the copper kernel.In this case, the cross-sectional structure of described busbar can be a) titanium coating layer/interfacial reaction layer/intermediate binder matter/interfacial reaction layer/copper kernel/interfacial reaction layer/intermediate binder matter/interfacial reaction layer/titanium coating layer; B) titanium coating layer/interfacial reaction layer/intermediate binder matter/copper kernel/intermediate binder matter/interfacial reaction layer/titanium coating layer; Or c) titanium coating layer/intermediate binder matter/interfacial reaction layer/copper kernel/interfacial reaction layer/intermediate binder matter/titanium coating layer.Described interfacial reaction layer can be solid phase reaction layer, weld layer or the combination of the two.
The present invention also provides another copper busbar that covers titanium with excellent electrical conductivity and corrosion resistance, and this busbar comprises copper kernel, the titanium coating layer around the described copper kernel and is used for intermediate binder matter in conjunction with described copper kernel and titanium coating layer.The cross-sectional structure of this busbar is titanium coating layer/intermediate binder matter/copper kernel.Can use the simple metal or the alloy of titanium and copper.
The material that has with titanium and/or copper reactive activity and good plastic deformation characteristics can be used as described intermediate binder matter, the interface of titanium and copper is easy to combination like this.
Preferably, described intermediate binder matter is selected from by gold, silver, platinum, aluminium, zinc, tin, vanadium, nickel and contains in a kind of group of forming as the alloy of main component in these elements.The form of described intermediate binder matter can be the light wall pipe or the thin slice of at least a layering, perhaps is surface being coated in titanium coating layer and/or copper kernel or the coat on all surfaces.
The thickness of described light wall pipe, sheet materials or coat can be preferably the 1-1000 micron for 1 micron to several millimeters, considers that the metal as intermediate binder matter is the very high noble metal of price, more preferably 1-5 micron.
The present invention also provides the preparation method of the copper busbar that covers titanium with excellent electrical conductivity and corrosion resistance, and this method comprises:
Copper (or copper alloy) kernel is embedded in titanium (or titanium alloy) the coating layer shell;
Titanium coating layer and copper kernel are carried out the mechanical adhesion first time;
By under 250 ℃-950 ℃ ℃ temperature, titanium coating layer and the copper kernel that adheres to being carried out the heat treatment first time with titanium coating layer and copper kernel metallurgical binding; And
Heat treated titanium coating layer and copper kernel are carried out the mechanical adhesion second time, obtain required size.
In preparation process, for the contact interface at titanium and copper causes interaction between the two, use one or more methods in extrusion molding, hubbing and the rolling carry out respectively first time and the second time mechanical bond step.If reduction percentage (or ratio) is too little, titanium and copper do not have combination, yet if reduction percentage (or ratio) is too big, then metal can be destroyed.Therefore, when carrying out mechanical bond, the reduction percentage is preferably 5-75%, more preferably 15-50%.
In order to make titanium and copper carry out mutual material Transfer they mutually combine at the interface, heat treatment for the first time 250-850 ℃ ℃, in vacuum or inert atmosphere, carried out 5-300 minute, therefore, on the interface between titanium and the copper, form the solid phase reaction layer.If heat treated temperature is lower than above-mentioned scope for the first time, then on described interface, be difficult to take place material Transfer; Yet, if temperature is higher than above-mentioned scope, the low temperature eutectic reaction takes place, can not form described solid phase reaction layer.Change along with heat treated temperature process time.That is, if heat treated temperature height, then the reaction time shortens; If heat treatment temperature is low, then the reaction time prolongs, and heat treatment can be carried out in above-mentioned gamut.
When titanium contacts with copper and when reacting each other, utilizes the low temperature eutectic reaction, titanium and copper are being lower than separately fusion under fusion point (titanium: 1675 ℃, copper: the 1084 ℃) temperature in this reaction.Heat treatment is for the first time carried out under the temperature of the minimum eutectic reaction temperature that is higher than 875 ℃ of titanium and copper, thereby the fusion at once of titanium and copper forms melting layer at their interface.Therefore, in order to form melting layer by eutectic reaction, heat treated temperature must be higher than minimum eutectic reaction temperature for the first time; Melt and take place any unwanted reaction for fear of copper, heat treated temperature also must be lower than the fusing point of copper for the first time.Therefore, heat treatment is for the first time preferably carried out more preferably 880-920 ℃ under 880-950 ℃ temperature.Reaction time changes along with heat treated temperature.If heat treated temperature height, then the reaction time shortens; If heat treatment temperature is low, then the reaction time prolongs.Reaction time is in 1-30 minute scope.
The present invention also provides the preparation method of the copper busbar that covers titanium with excellent electrical conductivity and corrosion resistance, and this method comprises:
The intermediate binder matter that will have good plastic deformability and oxidative resistance is embedded between titanium (or titanium alloy) coating layer and copper (or copper alloy) kernel;
Titanium coating layer, intermediate binder matter and copper kernel are carried out the mechanical adhesion first time;
By under 250-1000 ℃ the temperature titanium coating layer, intermediate binder matter and the copper kernel that adheres to being carried out 1-240 minute the heat treatment first time with the metallurgical interface combination between titanium coating layer, intermediate binder matter and copper (or copper alloy) kernel; And
Titanium coating layer, intermediate binder matter and the copper kernel of combination are carried out the mechanical deformation second time, obtain required size.
In order to strengthen the interface combination, described intermediate binder matter must have and titanium (or titanium alloy) and copper (or copper alloy) reactive activity, and has good plastic deformation characteristics.The choosing of fine quality of described intermediate binder is selected from by gold, silver, platinum, aluminium, zinc, tin, vanadium, nickel and contains in a kind of group of forming as the alloy of main component in these elements.The infix form of described intermediate binder matter can be the light wall pipe or the thin slice of at least a layering, perhaps is surface being coated in titanium coating layer and/or copper kernel or the coat on all surfaces.Can apply intermediate binder matter by being selected from metallization, vacuum or chemical deposition, cladding process and titanium coating pipe or copper kernel being placed in the method in the intermediate binder matter of fusing one or more.The thickness of described light wall pipe, sheet materials or coat can be preferably the 1-1000 micron, more preferably the 1-5 micron for 1 micron to several millimeters.
Can optionally use separately or unite and use a kind of several in extrusion molding, rolling and the hubbing to carry out first time and the mechanical deformation second time, the reduction percentage be 5-75%, is preferably 15-50%.If reduction percentage (or ratio) is too little, the adhesion between metal and the material is bad, yet if reduction percentage (or ratio) is too big, then metal can be destroyed.
According to the type of described intermediate binder matter, be used for metallurgical binding between titanium, copper and the intermediate binder matter the first time heat treated temperature can be different, carry out the fusing point that heat treated temperature for the first time generally is lower than employed intermediate binder matter.Particularly, heat treatment was for the first time carried out under 250-1000 ℃ temperature 1-240 minute.Reaction time changes along with heat treated temperature.If heat treated temperature height, then the reaction time shortens; If heat treatment temperature is low, then the reaction time prolongs.
If heat treated temperature is lower than 250 ℃, then reaction can not take place well, if opposite temperature is higher than the fusing point of intermediate binder matter, then intermediate binder matter will melt.The temperature of therefore, heat-treating is higher than 250 ℃ but be lower than the fusing point of intermediate binder matter.
For example, if use aluminum or aluminum alloy as intermediate binder matter, heat treatment for the first time can be carried out 10-120 minute being lower than under 660 ℃ of melting temperatures of aluminium.If use gold, silver, platinum or their alloy as intermediate binder matter, heat treatment can be carried out under 300-1000 ℃ temperature.
When middle bond matter embedded with the form of light wall pipe or thin slice, heat treatment was for the first time carried out in inertia or vacuum atmosphere.If intermediate binder matter is administered to the surface of titanium and/or copper, then heat treatment for the first time can be carried out in air, also can carry out in inertia or vacuum atmosphere.
After busbar was processed into required size, preparation method of the present invention can also be included under 200-800 ℃ the heat treatment of the copper busbar that covers titanium the being carried out 1-240 minute second time.
By the heat treatment second time, because mechanical deformation for the second time and may separate or discontinuously arranged interfacial reaction layer or intermediate binder mass-energy enough couples together, and avoid having than the intermetallic compound of fragility by force generating on the interface between titanium and intermediate binder matter and/or on the interface of intermediate binder matter and copper.
Particularly, heat treatment is for the second time carried out being lower than under 850 ℃ the temperature, is lower than minimum eutectic reaction temperature, therefore can avoid the intermetallic compound in generation fragility on the interface between titanium and intermediate binder matter and/or on the interface of intermediate binder matter and copper.For material Transfer between trigger layer, heat treatment is for the second time carried out under at least 200 ℃ or higher temperature, therefore interfacial reaction layer or intermediate binder matter (may separate when the second time mechanical deformation or discontinuously arranged) can be combined rightly.
The invention is characterized in: by heating or heat simultaneously and pressurizeing, promoted between titanium coating layer and the copper kernel or the material Transfer on the contact interface between titanium coating layer, intermediate binder matter and the copper kernel, therefore made alloying and obtain good binding.In addition, in embodiments of the present invention, have with titanium and copper reactive activity and be easy to the intermediate binder matter of plastic deformation, between titanium and copper, realized that successfully the interface combines by use.
In conjunction with the accompanying drawings, by following detailed description of the present invention, above-mentioned and other purpose, feature, content and advantage of the present invention will become more obvious.
Description of drawings
The following drawings is in order further to understand the present invention, and these accompanying drawings are incorporated the part of book as an illustration into, describes embodiments of the present invention and comes together to explain principle of the present invention with specification.
Wherein:
Figure 1A is the cutaway view according to the copper busbar that covers titanium of one embodiment of the present of invention;
Figure 1B is the cross-sectional view according to the copper busbar that covers titanium of an alternative embodiment of the invention;
Fig. 1 C is the cross-sectional view according to the copper busbar that covers titanium of another embodiment of the present invention;
Fig. 1 D is the cross-sectional view according to the copper busbar that covers titanium of an alternative embodiment of the invention;
Fig. 1 E is according to the cross-sectional view of the copper busbar that covers titanium of another embodiment in addition of the present invention;
Fig. 2 A is the picture of expression according to the cross section microstructure of the copper busbar that covers titanium of first kind of execution mode of the present invention, and this busbar comprises titanium coating layer, solid phase reaction layer and copper kernel;
Fig. 2 B is the picture of expression according to the cross section microstructure of the copper busbar that covers titanium of second kind of execution mode of the present invention, and this busbar comprises titanium coating layer, melting layer and copper kernel;
Fig. 2 C is the picture of expression according to the cross section microstructure of the copper busbar that covers titanium of the third execution mode of the present invention, and this busbar comprises titanium coating layer, solid phase reaction layer, discontinuous melting layer and copper kernel;
Fig. 3 is the picture of expression according to the cross section microstructure of the copper busbar that covers titanium of the 4th kind of execution mode of the present invention, and this busbar comprises titanium coating layer, intermediate binder matter and copper kernel; With
Fig. 4 is the picture of expression according to the cross section microstructure of the copper busbar that covers titanium of the 5th kind of execution mode of the present invention, and this busbar comprises titanium coating layer, intermediate binder matter and copper kernel.
Embodiment
Figure 1A-1E is the schematic diagram according to the copper busbar that covers titanium of embodiments of the invention.
By titanium coating layer (1) and copper kernel (2) are had following multiple structure in conjunction with the copper busbar that covers titanium that forms:
A) three-decker shown in Figure 1A: titanium coating layer (1)/solid-phase layer (4)/kernel (2), wherein, the solid phase reaction layer that is formed by the mutual fusion (transmission) of copper and titanium exists on the interface between titanium coating layer (1) and the copper kernel (2) continuously;
B) three-decker shown in Figure 1B: titanium coating layer (1)/melting layer (5)/kernel (2), wherein, the melting layer (5) that is formed by the low temperature eutectic reaction exists on the interface between titanium coating layer (1) and the copper kernel (2) continuously;
C) structure shown in Fig. 1 C: titanium coating layer (1), solid-phase layer (4), discontinuous melting layer (5), solid phase reaction layer (4) and kernel (2), wherein, melting layer (5) distributes discontinuously;
D) structure shown in Fig. 1 D: titanium coating layer (1), intermediate binder matter (3) and kernel (2);
E) structure shown in Fig. 1 E: titanium coating layer (1), melting layer (5), intermediate binder matter (3) and kernel (2).
The present invention will be described in more detail below by embodiment, is to be understood that these embodiment just play the effect of explaining, and scope of the present invention is not limited to these embodiment.
By the copper (fine copper or copper alloy) with excellent electrical conductivity being coated the copper busbar that covers titanium that preparation has excellent electrical conductivity and corrosion resistance with titanium (pure titanium or titanium alloy) clad metal with excellent corrosion resistance.
With diameter be 29 millimeters copper kernel to be embedded into overall diameter be that 32 millimeters, thickness are in 1 millimeter the titanium pipe, and to use draw-off gear be 26 millimeters with the overall diameter drawing, thus with titanium coating layer and copper kernel mechanical bond fully.For the mechanical bond between copper kernel and the titanium pipe, can also separately or unite and use extrusion molding or rolling.
With the copper busbar of the titanizing of mechanical bond under inert gas shielding 850 ℃ of following heat treatments 30 minutes, with the titanium coating layer and the copper kernel metallurgical binding of mechanical bond.
Fig. 2 A represents to cover the cross section microstructure of the copper busbar of titanium, this busbar after the drawing first time under inert gas shielding 850 ℃ of following heat treatments 30 minutes.Shown in Fig. 2 A, experienced drawing for the first time and heat treatment after, the cross section microstructure at the interface between titanium coating layer and the copper kernel is three layers: titanium coating layer (1), solid phase reaction layer (4) and copper kernel (2).
With diameter be 29 millimeters copper kernel to be embedded into overall diameter be that 32 millimeters, thickness are in 1 millimeter the titanium pipe, and to use draw-off gear be 26 millimeters with the overall diameter drawing.With the copper busbar of the titanizing of drawing under inert gas shielding 880 ℃ of following heat treatments 2 minutes, with the titanium coating layer and the copper kernel metallurgical binding of mechanical bond.
Fig. 2 B represents to cover the cross section microstructure of the copper busbar of titanium, this busbar after the drawing first time under inert gas shielding 880 ℃ of following heat treatments 2 minutes.Shown in Fig. 2 B, the cross section microstructure of titanium coating layer and copper kernel is three layers: titanium coating layer (1), melting layer (5) and copper kernel (2), and demonstrate titanium and copper combines well.
Make the copper busbar that covers titanium by carrying out drawing for the first time and heat treatment subsequently, this busbar is carried out drawing once more, obtain overall diameter and be 24 millimeters busbar, heat treatment 30 minutes again under 850 ℃ then obtains in conjunction with the good copper busbar that covers titanium.The copper busbar that covers titanium that makes shows the good metal combination.
In addition, the copper busbar that covers titanium with titanium coating layer (1), melting layer (5) and copper kernel (2) three-decker of embodiment 2 is carried out drawing once more and 700 ℃ of heat treatments 10 minutes again, makes the copper busbar that covers titanium.Fig. 2 C represents the cross section microstructure of the copper busbar that covers titanium that makes.Shown in Fig. 2 C, because hubbing is discontinuously arranged by the melting layer that compound between brittle metal forms, but demonstrate the good metal combination, described intermetallic compound is formed by the low temperature eutectic reaction.
Aluminium (or aluminium alloy) sheet as thin as a wafer is embedded between titanium pipe and the copper kernel as intermediate binder matter, the overall diameter of described titanium pipe is 32 millimeters and does not have impurity, the overall diameter of described copper kernel is 29 millimeters, use drawbench to carry out drawing, make overall diameter and be 26 millimeters the copper busbar that covers titanium.Except using aluminium (or aluminium alloy), can also use the sheet as thin as a wafer or the pipe of gold (or billon), silver (or silver alloy), platinum (or platinum alloy), zinc (or kirsite), tin (or ashbury metal) or other metal as the intermediate binder matter.
For the titanium coating layer is fully combined with the copper kernel with aluminium intermediate binder matter and aluminium intermediate binder matter, except hubbing, can also separately or unite and use extrusion molding or rolling.
The copper busbar that covers titanium of drawing for the first time carries out heat treatment for the first time in 30 minutes under 300 ℃, the interface between titanium coating layer and the aluminium intermediate binder matter and aluminium intermediate binder matter are combined with interface between the copper kernel.Their metallurgical interface is fine in combination.
Fig. 3 represents the cross section microstructure of the copper busbar that covers titanium after drawing for the first time and heat treatment are for the first time finished.As shown in Figure 3, the cross section microstructure of covering the copper busbar of titanium is three layers: titanium coating layer (1), intermediate binder matter (3) and copper kernel (2).
In addition, the copper of the drawing first time and heat treated titanizing is subsequently carried out drawing once more, make overall diameter and be 24 millimeters the copper busbar that covers titanium.With the heat treatment 30 minutes again under 300 ℃ of the copper busbar that covers titanium of drawing once more, therefore can not on interface between titanium coating layer and the aluminium intermediate binder matter and the interface between aluminium intermediate binder matter and the copper kernel, form the intermetallic compound of fragility.Heat treated once more temperature is with different variation of type of intermediate binder matter.After the first time and drawing for the second time and the first time and the heat treatment second time, the cross section microstructure of covering the copper busbar of titanium is shown as three layers: titanium coating layer (1), intermediate binder matter (3) and copper kernel (2).
Especially in this embodiment, in order to prepare the copper busbar that covers titanium with excellent electrical conductivity and corrosion resistance, the copper busbar that covers titanium of complete mechanical combination was kept in inert gas 30 minutes at 300 ℃, by material Transfer (fusion) interface between titanium coating layer and the aluminium intermediate binder matter or aluminium intermediate binder matter are combined with metallurgical interface between the copper kernel thus.Be used for type different change of the heat treatment temperature of melts combine with intermediate binder matter.
With gold (or billon), silver (or silver alloy), platinum (or platinum alloy) as intermediate binder matter be coated in diameter be 32 millimeters titanium tube-surface or diameter be 29 millimeters the copper core surface on, described titanium pipe or copper kernel do not have impurity, the copper kernel is embedded in the titanium pipe, use drawbench to carry out the drawing first time, make overall diameter and be 26 millimeters the copper busbar that covers titanium.
For intermediate binder matter being coated on titanium coating layer or the copper core surface, can separately or uniting and use chemical deposition, galvanoplastic, cladding process and infusion process.The metal layer thickness that applies is the 1-5 micron.
For the titanium coating layer that will have mid-coat layer and copper kernel, titanium coating layer and the titanium coating layer that has the copper kernel of mid-coat layer or have a mid-coat layer adhere to fully with the copper kernel with mid-coat layer, except hubbing, can also use or mix use extrusion molding or rolling separately.
The copper busbar that covers titanium of the drawing first time that will be become with copper by titanium, intermediate binder matter is heat treatment 30 minutes in inert gas under 800 ℃, with the metallurgical interface combination of intermediate binder matter and copper kernel.Heat treated temperature is with different variation of type of intermediate binder matter.
When the intermediate binder matter coat with good oxidation of the copper busbar that covers titanium as gold (or billon), silver (or silver alloy), platinum (or platinum alloy) during titanium and copper kernel or titanium cage walls surperficial, can in air, heat-treat, also can in vacuum or inert gas, heat-treat.
Fig. 4 represents the cross section microstructure of the copper busbar that covers titanium that makes by drawing and heat treatment subsequently.As shown in Figure 4, the cross section microstructure of the copper busbar that covers titanium after drawing for the first time and the heat treatment is three layers: titanium coating layer (1), intermediate binder matter (3) and copper kernel (2).
Drawing is once more carried out in the drawing first time and the heat treated copper busbar that covers titanium, and the formation overall diameter is 23 millimeters the copper busbar that covers titanium, carries out heat treatment in 30 minutes then under 300 ℃ again, makes the interface in conjunction with the copper busbar that covers titanium in good condition.
As mentioned above, the invention provides a kind of low-cost preparation and have the method for the copper busbar that covers titanium of excellent electrical conductivity and corrosion resistance, this method coats the copper (fine copper or copper alloy) with excellent electrical conductivity with the titanium (pure titanium or titanium alloy) with good corrosion resistance.
Especially, the present invention can prepare the busbar that can use in the atmosphere midium or long term of high corrosion, for example at electrolytic cell that is used to electroplate that produces chlorine or sulfuric acid gas or the medium-term and long-term busbar that uses of electroplating pool.
Therefore, described have high current density and the high-frequency copper busbar that covers titanium can be used for electrolysis, and the described copper busbar that covers titanium has good conductivity and corrosion resistance, its preparation method helps the electrolysis that contacts with all kinds corrosive deposit and the stability and the reliability of golden electroplating device, and prolongs the useful life of described equipment.
Under the prerequisite that does not depart from purport of the present invention and substantive features, the present invention can implement with several forms, should be understood that unless stated otherwise, above-mentioned execution mode is not limited to above detailed description.Should in purport that the claim of enclosing limits and scope, understand the present invention, therefore in the scope of claim or full scope of equivalents change or change and all be included in the claim of enclosing.
Claims (18)
1, a kind of copper busbar that covers titanium with good corrosion resistance and conductivity, this busbar comprises:
The copper kernel;
Titanium coating layer around described copper kernel; And
The interfacial reaction layer that interaction on their interface forms by titanium and copper, described interfacial reaction layer is for carrying out the solid phase reaction layer that mutual material Transfer forms by mechanical adhesion and/or heat treatment between copper and titanium, perhaps react the melting layer that forms by low temperature eutectic, the combination of perhaps described solid phase reaction layer and melting layer
Wherein, the cross-sectional structure of this busbar is: titanium coating layer/interfacial reaction layer/copper kernel/interfacial reaction layer/titanium coating layer, described titanium and copper use with the form of simple metal or alloy.
2, according to the busbar of claim 1, this busbar also comprises intermediate binder matter on the interface between titanium coating layer and the copper kernel, described intermediate binder matter has and titanium, copper or titanium and the two reactive activity of copper and good plastic deformation characteristics and oxidative resistance
Wherein, the cross-sectional structure of described busbar is: titanium coating layer/interfacial reaction layer/intermediate binder matter/interfacial reaction layer/copper kernel/interfacial reaction layer/intermediate binder matter/interfacial reaction layer/titanium coating layer;
Titanium coating layer/interfacial reaction layer/intermediate binder matter/copper kernel/intermediate binder matter/interfacial reaction layer/titanium coating layer; Or
Titanium coating layer/intermediate binder matter/interfacial reaction layer/copper kernel/interfacial reaction layer/intermediate binder matter/titanium coating layer.
3, a kind of copper busbar that covers titanium with good anti-corrosion and conductivity, this busbar comprises:
The copper kernel;
Titanium coating layer around described copper kernel; And
Intermediate binder matter on the interface between titanium coating layer and the copper kernel, described intermediate binder matter have and titanium, copper or titanium and the two reactive activity of copper and good plastic deformation characteristics and oxidative resistance,
Wherein, the cross-sectional structure of this busbar is titanium coating layer/intermediate binder matter/copper kernel/intermediate binder matter/titanium coating layer, and described titanium and copper use with the form of simple metal or alloy.
4, according to the busbar of claim 2 or 3, wherein, described intermediate binder matter is to be selected from by gold, silver, platinum, aluminium, zinc, tin, vanadium, nickel and to contain in a kind of group of forming as the alloy of main component in these elements, described intermediate binder matter is the light wall pipe in the interface that is embedded between titanium coating layer and the copper kernel or the form of thin slice, perhaps is the form of the coat that forms at least one surface of titanium coating layer or copper kernel.
5, according to the busbar of claim 4, wherein, the thickness of described light wall pipe, sheet materials or coat is the 1-1000 micron.
6, a kind of preparation method with copper busbar that covers titanium of excellent electrical conductivity and corrosion resistance, this method comprises:
Preparation copper or copper alloy kernel and titanium or titanium alloy coating layer,
With the economy of 5-75% with described titanium or titanium alloy coating layer and copper or copper alloy kernel mechanical bond,
By in 250-950 ℃ temperature range, carrying out the heat treatment first time, with described titanium or titanium alloy coating layer and copper or copper alloy kernel metallurgical binding, and
Titanium coating layer and the mechanical deformation of copper kernel with metallurgical binding reduce its size.
7, according to the method for claim 6, wherein, mechanical bond step and mechanical deformation step are undertaken by using extrusion molding, hubbing or rolling.
8, according to the method for claim 6, wherein, heat treatment for the first time 250-850 ℃, in vacuum or inert atmosphere, carried out 5-300 minute, on the interface between titanium or titanium alloy coating layer and copper or the copper alloy kernel, form the solid phase reaction layer.
9, according to the method for claim 6, wherein, heat treatment was for the first time carried out under 880-950 ℃ temperature 1-30 minute, formed melting layer on the interface between titanium or titanium alloy coating layer and copper or the copper alloy kernel.
10, a kind of preparation has the method for the copper busbar that covers titanium of excellent electrical conductivity and corrosion resistance, and this method comprises:
The intermediate binder matter that will have good plastic deformability and oxidative resistance is administered between titanium or titanium alloy coating layer and copper or the copper alloy kernel;
Titanium or titanium alloy coating layer and intermediate binder matter are carried out mechanical bond on their interface, intermediate binder matter and copper or copper alloy kernel are carried out mechanical bond on their interfaces,
By under 250-1000 ℃ temperature, titanium or titanium alloy coating layer, intermediate binder matter and copper or copper alloy kernel being carried out 1-240 minute the heat treatment first time, with titanium or titanium alloy coating layer, intermediate binder matter and copper or copper alloy kernel metallurgical binding; And
The titanium of metallurgical binding or titanium alloy coating layer, intermediate binder matter and copper or copper alloy kernel are carried out mechanical reduction.
11, according to the method for claim 10, wherein, light wall pipe or thin slice are embedded between titanium or titanium alloy coating layer and copper or the copper alloy kernel as intermediate binder matter, and described light wall pipe or thin slice are by being selected from by gold, silver, platinum, aluminium, zinc, tin, vanadium, nickel and containing a kind of making in a kind of group of forming as the alloy of main component in these elements.
12, according to the method for claim 10, wherein, be coated to the surface of titanium or titanium alloy coating layer or surface or the surface of titanium or titanium alloy coating layer and the surface of copper or copper alloy kernel of copper or copper alloy kernel with being selected from by gold, silver, platinum, aluminium, zinc, tin, vanadium, nickel and containing a kind of in a kind of group of forming as the alloy of main component in these elements as intermediate binder matter.
13, according to the method for claim 12, wherein, use at least a coating intermediate binder matter in metallization, vacuum or chemical deposition, cladding process or the infusion process.
14, according to the method for claim 11 or 12, wherein, the thickness of the light wall pipe of described intermediate binder matter, thin slice or coat is the 1-1000 micron.
15,, wherein,, use separately or unite one or more methods of using in extrusion molding, hubbing or the rolling for mechanical bond and mechanical reduction step according to the method for claim 10.
16, according to the method for claim 11, wherein, heat treatment is for the first time carried out under inertia or vacuum atmosphere.
17, according to the method for claim 12 or 13, wherein, heat treatment is for the first time carried out under inertia or vacuum atmosphere or in air.
18, according to the method for claim 6 or 10, wherein, this method also comprises:
Under 200-850 ℃, the copper busbar that covers titanium carried out 1-240 minute the heat treatment second time.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020040093666A KR100629445B1 (en) | 2004-11-16 | 2004-11-16 | Fabrication methid of titanium clad copper bus-bars |
| KR1020040093666 | 2004-11-16 |
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| Publication Number | Publication Date |
|---|---|
| CN1776827A true CN1776827A (en) | 2006-05-24 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNA200510123205XA Pending CN1776827A (en) | 2004-11-16 | 2005-11-15 | Titanium-coated copper bus-bar and its making method |
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| CN (1) | CN1776827A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017124428A1 (en) * | 2016-01-22 | 2017-07-27 | Abb 瑞士股份有限公司 | Metal coating copper bar and electrical equipment |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100771756B1 (en) | 2006-07-10 | 2007-10-30 | 한국생산기술연구원 | Method for producing ag-based electrical contact material by extrusion |
| KR101644814B1 (en) | 2014-11-05 | 2016-08-02 | 주식회사 성진정밀 | Clad metal bus bar having bending part and the manufacturing method therof |
| JP6735014B2 (en) * | 2018-03-22 | 2020-08-05 | 富山住友電工株式会社 | Plating equipment |
| KR102332286B1 (en) | 2021-05-17 | 2021-12-01 | 주식회사 근우 | Manufacturing method of copper busbar with improved heat generation |
| KR102332285B1 (en) | 2021-05-17 | 2021-12-01 | 주식회사 근우 | Manufacturing method of copper busbar with improved heat generation |
-
2004
- 2004-11-16 KR KR1020040093666A patent/KR100629445B1/en active IP Right Grant
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017124428A1 (en) * | 2016-01-22 | 2017-07-27 | Abb 瑞士股份有限公司 | Metal coating copper bar and electrical equipment |
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| KR20060054838A (en) | 2006-05-23 |
| KR100629445B1 (en) | 2006-09-28 |
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