Patent Application
20050262968
1. Field of the Invention
The present invention relates to methods for continuously manufacturing low-oxygen copper, containing a suppressed level of oxygen content, by continuously casting molten copper produced in a melting furnace.
2. Description of the Related Art
Low-oxygen copper (called “oxygen-free copper” in some cases) in which the content of oxygen is controlled to 20 ppm or less, and more preferably, to 1 to 10 ppm, is widely used for producing various shapes, e.g., ingot forms such as billets and cakes, rolled sheets, wires and cut forms. As a method for manufacturing low-oxygen copper, a method is typically used in which molten copper is produced in a high-frequency furnace such as a channel furnace or a coreless furnace, the molten copper is transferred to a continuous casting machine while held in an airtight atmosphere and the casting is then performed.
When low-oxygen copper is produced by using a high-frequency furnace as described above, there are advantages in that a higher temperature can be easily obtained by a simple operation, and the qualities of the products are very uniform since no chemical reaction occurs in production of the molten copper. However, there are disadvantages in that the construction cost and the operating cost are high, and productivity is low.
In order to perform mass production of low-oxygen copper at lower cost, a method using a gas furnace such as a shaft kiln is preferably employed. However, when such a gas furnace is used, since combustion is performed in the furnace, i.e., oxidation occurs, the oxidized molten copper must be processed by a reducing treatment. This is the disadvantage of the gas furnace, which is not observed when a high-frequency furnace is used. As a result, low-oxygen copper cannot be produced unless oxygen contained in the molten copper is decreased by using a reducing gas and/or an inert gas in a step of transferring the molten copper before the molten copper is fed to a continuous casting machine.
In addition, even when the deoxidizing step described above is performed, holes will be formed in the low-oxygen copper and may result in generating defects such as blisters in some cases. As a result, the quality of the low-oxygen copper is degraded. In particular, when copper wire is manufactured, the holes described above will cause defects in a rolling step, and hence the copper wire has poor surface qualities. Accordingly, in general, it is believed that production of high quality low-oxide copper is difficult to perform using a gas furnace, and hence most of low-oxide copper is produced using a high-frequency furnace.
The holes described above are formed by bubbles of steam (H2O) produced by combination of hydrogen and oxygen due to the decease in solubility of the gases in the molten copper when it is solidified. The bubbles are trapped in the molten copper during cooling and solidification and remain in the low-oxide copper, and hence holes are generated. From a thermodynamic point of view, the concentrations of hydrogen and oxygen in molten copper can be represented by the equation shown below.
[H]2[O]=pH2O $ K Equation (A)
In the equation (A), [H] represents the concentration of hydrogen in molten copper, [O] represents the concentration of oxygen in molten copper, pH2O represents a partial pressure of steam in the ambience, and K represents an equilibrium constant.
Since the equilibrium constant K is a function of temperature and is constant at a constant temperature, the concentration of oxygen in molten copper is inversely proportional to the concentration of hydrogen. Accordingly, in accordance with the equation (A), the concentration of hydrogen is increased by performing a deoxidizing treatment by reduction, and as a result, holes are easily generated during solidification, whereby only an ingot of low-oxygen copper having poor quality can be manufactured.
On the other hand, molten copper containing hydrogen at a low concentration can be obtained by melting copper in a state near complete combustion using an oxidation-reduction method, which is a general degassing method. However, in a subsequent deoxidizing step, a long moving distance of the molten copper is required, and hence the method described above cannot be practically used.
In consideration of the problems described above, an object of the present invention is to provide a method for manufacturing low-oxide copper, in which a dehydrogenating treatment can be performed without requiring a long moving distance of molten copper, in which the generation of holes in solidification is suppressed, and in which high quality low-oxide copper having superior surface quality can be obtained.
A method for continuously manufacturing ingots of low-oxygen copper from molten copper according to the present invention comprises a step of preparing a starting material for low-oxygen copper; a step of performing combustion of the starting material in a reducing atmosphere in a melting furnace so as to produce molten copper; a step of sealing the molten copper in a non-oxidizing atmosphere in a casting trough; a step of transferring the molten copper to a turn-dish by using the casting trough; a degassing step of passing the molten copper through a degasser provided in the casting trough so as to dehydrogenate the molten copper; a step of feeding the molten copper to a continuous casting machine so as to continuously produce cast copper; and a step of cutting the cast copper into the ingots of low-oxygen copper each having a predetermined length.
In the method described above according to the present invention, the dehydrogenation in the degassing step is performed by stirring the molten copper.
In addition, in the method described above according to the present invention, the stirring in the degassing step is performed by passing the molten copper through a meandering flow path.
A method for continuously manufacturing a low-oxygen copper wire according to the present invention, comprises a step of preparing a starting material for low-oxygen copper; a step of performing combustion of the starting material in a reducing atmosphere in a melting furnace so as to produce molten copper; a step of sealing the molten copper in a non-oxidizing atmosphere in a casting trough; a step of transferring the molten copper to a turn-dish by using the casting trough; a degassing step of passing the molten copper through a degasser provided in the casting trough so as to dehydrogenate the molten copper; a step of feeding the molten copper to a belt caster type continuous casting machine so as to continuously produce cast copper; and a step of rolling the cast copper so as to manufacture the low-oxygen copper wire.
In the method for continuously manufacturing the low-oxygen copper wire, the dehydrogenation in the degassing step is performed by stirring the molten copper.
In addition, in the method for continuously manufacturing the low-oxygen copper wire, the stirring in the degassing step is performed by passing the molten copper through a meandering flow path.
A method for continuously manufacturing a wire composed of a low-oxygen copper alloy of the present invention comprises a step of preparing a starting material for low-oxygen copper; a step of performing combustion of the starting material in a reducing atmosphere in a melting furnace so as to produce molten copper; a step of sealing the molten copper in a non-oxidizing atmosphere in a casting trough; a step of transferring the molten copper to a turn-dish by using the casting trough; a degassing step of passing the molten copper through a degasser provided in the casting trough so as to dehydrogenate the molten copper; a step of adding silver to the dehydrogenated molten copper; a step of feeding the molten copper to a belt caster type continuous casting machine so as to continuously produce a cast copper alloy; and a step of rolling the cast copper alloy so as to manufacture the wire composed of the low-oxygen copper alloy.
In the method for continuously manufacturing the wire composed of the low-oxygen copper alloy, the dehydrogenation in the degassing step is performed by stirring the molten copper.
In addition, in the method for continuously manufacturing the wire composed of the low-oxygen copper alloy, the stirring in the degassing step is performed by passing the molten copper through a meandering flow path.
A method for continuously manufacturing a base low-oxygen copper material containing phosphorus for use in copper plating of the present invention comprises a step of preparing a starting material for low-oxygen copper; a step of performing combustion of the starting material in a reducing atmosphere in a melting furnace so as to produce molten copper; a step of sealing the molten copper in a non-oxidizing atmosphere in a casting trough; a step of transferring the molten copper to a turn-dish by using the casting trough; a degassing step of passing the molten copper through a degasser provided in the casting trough so as to dehydrogenate the molten copper; a step of adding phosphorus to the dehydrogenated molten copper; a step of feeding the molten copper to a belt caster type continuous casting machine so as to continuously produce a cast base copper material; and a rolling step of rolling the cast base copper material so as to manufacture the base low-oxygen copper material containing phosphorus for use in copper plating.
In the method for continuously manufacturing the base low-oxygen copper containing phosphorus, the dehydrogenation in the degassing step is performed by stirring the molten copper.
In the method for continuously manufacturing the base low-oxygen copper containing phosphorus described above, the stirring in the degassing step is performed by passing the molten copper through a meandering flow path.
The method for manufacturing the base low-oxygen copper material of the present invention further comprises a step of cutting the base low-oxygen copper material containing phosphorus obtained in the rolling step so as to continuously manufacture short base low-oxygen copper materials containing phosphorus for use in copper plating.
The method for manufacturing the base low-oxygen copper material containing phosphorus of the present invention further comprises a step of washing the short base low-oxygen copper material containing phosphorus for use in copper plating.
In the methods for manufacturing the low-oxygen copper described above, the combustion is performed in a reducing atmosphere in a melting furnace, and hence the molten copper is deoxidized. The deoxidized copper is sealed in a non-oxidizing atmosphere in the casting trough and is then transferred to the turn-dish. Since the concentration of oxygen is inversely proportional to the concentration of hydrogen as described above, the concentration of hydrogen in the molten copper deoxidized in the melting furnace is increased. When the molten copper passes through the casting trough, containing hydrogen at a high concentration, the dehydrogenation is performed by the degasser. Accordingly, the amount of gas evolved in casting is decreased, the generation of holes in a cast copper is suppressed, and as a result the defects on the surface of the low-oxygen copper are reduced.
In addition, when the molten copper is stirred in the degassing step, the hydrogen contained in the molten copper is forced out therefrom, whereby dehydrogenation can be performed. That is, since a copper stirrer is provided in the casting trough, the molten copper contacted by the stirrer is stirred before it reaches the turn-dish, and as a result the molten copper is brought into good contact with an inert gas blown to the casting trough for forming a non-oxidizing atmosphere. In the step described above, since a partial pressure of hydrogen in the inert gas is very low compared to that in the molten copper, the hydrogen in the molten copper is absorbed in the non-oxidizing atmosphere formed by the inert gas, whereby the dehydrogenation of the molten copper can be performed.
Furthermore, when a dike is provided in the casting trough at which the molten copper passes, the molten copper flows meanderingly in the degassing step, and is stirred by the vigorous flow thereof. That is, the molten copper can be automatically stirred by the flow thereof. As described above, since the molten copper vigorously flows up and down, and right to left, the molten copper passing through the casting trough has good opportunity to be brought into contact with the inert gas, and as a result the efficiency of the degassing treatment can be further increased.
In the case described above, the dike provided in the flow path for the molten copper is preferably in the form of a bar, a plate or the like. In addition, a plurality of dikes may be provided along the flow direction of the molten copper or in the direction perpendicular thereto. Furthermore, when dikes are formed of, for example, carbon, the deoxidizing treatment can also be performed efficiently due to the contact between the molten copper and the carbon.
Hereinafter, the embodiments of methods for manufacturing low-oxygen copper according to the present invention will be described in detail with reference to the figures. In the embodiments described below, “low-oxygen copper” means copper or an alloy thereof containing oxygen at a concentration of 20 ppm or less, and preferably, of 1 to 10 ppm.
A first embodiment will first be described with reference to
An apparatus for manufacturing an ingot of low-oxygen copper (an apparatus for manufacturing low-oxygen copper) 101 is composed of a melting furnace A, a soaking furnace B, a casting trough C, a continuous casting machine D, a cutter E, and a transfer device F.
As the melting furnace A, a gas furnace having a cylindrical furnace body, such as a shaft furnace, is preferably used. Under the melting furnace A, a plurality of burners (not shown) are provided in the circumferential direction of the melting furnace A, and the burners are piled one on the other corresponding to the amount of copper to be melted. In the melting furnace A, combustion is performed in a reducing atmosphere so as to form molten copper (molten liquid). The reducing atmosphere can be obtained by, for example, increasing a fuel ratio in a mixed gas of a natural gas and air. In particular, compared to a waste gas generally containing carbon monoxide (CO) at a concentration of 0.2 to 0.6%, the air-fuel ratio is controlled so as to be 2 to 5%. As described above, since the combustion is performed in a reducing atmosphere, molten copper is deoxidized.
The soaking furnace B is a furnace for temporarily storing the molten liquid supplied from the melting furnace A and for supplying the molten liquid to the casting trough C while the temperature of the molten liquid is maintained.
The casting trough C seals the molten liquid supplied from the soaking furnace B in a non-oxidizing atmosphere and transfers the molten liquid to the turn-dish 5a. As shown in
As shown in
The dikes 33a are provided at the upper side of the flow path 31 for the molten copper, that is, at the cover 8. In addition, the dikes 33b are provided at the lower side of the flow path 31 for the molten copper, the dikes 33c are provided at the left side of the flow path 31 for the molten copper, and the dikes 33d are provided at the right side of the dikes 33c in the flow path 31 for the molten copper. By the dikes 33a, 33b, 33c, and 33d provided in the manner described above, the molten liquid flows up and down, and left to right, toward the direction indicated by the arrow in
The dikes 33c and 33d make the moving distance of the molten liquid longer than the actual flow path 31 for the molten copper, and hence even if the casting trough C is short, the efficiency of the degassing treatment can be improved. In addition, the dikes 33a and 33b serve to prevent gases in the non-oxidizing atmosphere before and after the degassing treatment from being mixed with each other, and in a manner similar to that, the dikes 33a and 33b serve to prevent the molten copper before the degassing treatment from being mixed with the molten copper after the degassing treatment.
The stirrer 33 primarily performs a dehydrogenating treatment; however, the stirrer 33 can also drive out the oxygen remaining in the molten liquid by stirring. That is, the dehydrogenating treatment and a second deoxidizing treatment are performed in the degassing treatment. When the dikes 33a, 33b, 33c, and 33d are formed of, for example carbon, the deoxidizing treatment can be efficiently performed by the contact of the molten copper with the carbon.
The degassing treatment must be performed in a step of transferring the molten copper after it passes the soaking furnace B. The reason for this is that since combustion in a reducing atmosphere or a deoxidizing treatment by using a reducing agent is performed in the soaking furnace B in order to manufacture ingots of low-oxygen copper, the concentration of hydrogen in the molten copper is inevitably increased in the soaking furnace B in accordance with the equilibrium equation (A) described above.
In addition, the degassing treatment is not preferably performed at the turn-dish 5a located at just in front of the continuous casting machine D. The reason for this is that when the molten liquid is moved so as to be vigorously stirred by, for example, bubbling, the surface of the molten liquid is violently vibrated, a head pressure of the molten liquid flowing from a teeming nozzle (not shown) varies, and as a result the molten copper cannot be fed stably to the continuous casting machine D. In contrast, when the surface of the molten liquid is not violently vibrated, the satisfactory effect of the degassing treatment cannot be obtained. Accordingly, the degassing treatment is preferably performed in the transfer step from the soaking furnace B to the turn-dish 5a.
The turn-dish 5a is provided with the teeming nozzle (not shown) at the downstream end of the flow path of the molten liquid so that the molten liquid is supplied from the turn-dish 5a to the continuous casting machine D.
The continuous casting machine D is connected to the soaking furnace B via the casting trough C. The continuous casting machine D is a so-called vertical casting machine having a mold 41 and pinch rollers 42, in which, while the molten copper is cooled, the molten copper is drawn downward in an approximately vertical direction so as to form cast copper 21a having a predetermined cross-sectional shape. The shapes and the locations of the mold 41 and the pinch rollers 42 are optionally selected in accordance with the shape of an ingot 23a of low-oxygen copper (low-oxygen copper) obtained as a product. For example, when the ingot 23a of low-oxygen copper is formed into a billet having an approximately cylindrical form, the mold 41 having a cylindrical cross-sectional shape and the pinch rollers 42 having shapes corresponding thereto may be used. When a cake having an approximately regular cubic shape is formed, the mold 41 having an approximately rectangular shape and the pinch rollers 42 having the shapes corresponding thereto may be used. In
In this embodiment, a vertical continuous casting machine is used as an example; however, a horizontal continuous casting machine for producing an ingot in the horizontal direction may also be used.
The cutter E is to cut the cast copper 21a produced by the continuous casting machine D into a predetermined length. As an example of the cutter E, there may be mentioned a flying saw having a rotary disk blade, although other structures capable of cutting the cast copper 21a may also be used.
The transfer device F is composed of a basket 51, an elevator 52, and a conveyor 53. The basket 51 is located approximately right under the continuous casting machine D, receives the ingot 23a of low-oxygen copper having a predetermined length formed by the cutter E, and places the ingot 23a on the elevator 52. The elevator 52 lifts the ingot 23a of low-oxygen copper placed thereon by the basket 51 to the level at which the conveyor 53 is located. The conveyor 53 then transfers the ingot 23a of low-oxygen copper lifted up by the elevator 52.
Next, a method for manufacturing an ingot of low-oxygen copper will be described using a manufacturing apparatus 101 having the structure described above.
Combustion is first performed in a reducing atmosphere in the melting furnace A so as to produce molten copper while being deoxidized (step of producing molten copper). The deoxidized molten copper transferred to the casting trough C via the soaking furnace B is sealed in a non-oxidizing atmosphere and is then transferred to the turn-dish 5a (step of transferring molten copper). Since the concentration of oxygen is inversely proportional to that of hydrogen, the concentration of hydrogen in the molten copper deoxidized in the melting furnace A is increased. The molten copper having a high hydrogen concentration is dehydrogenated by the stirrer 33 while passing through the casting trough C (degassing step).
According to the steps described above, the content of oxygen in the molten copper is controlled to 20 ppm or less, and the content of hydrogen is controlled to 1 ppm or less. As a result, the amount of gas evolved in casting is decreased and the generation of holes in the cast copper 21a can be suppressed.
In addition, according to the equilibrium equation (A), since the gas concentration in the molten copper is decreased when the partial pressure of steam is decreased, in the case in which the molten copper before processed by dehydrogenation is ideally separated from the dehydrogenated molten copper, the degassing effect can be further improved. The improved degassing effect described above can be realized by, for example, providing the stirrer 33 described above in the step of transferring the molten copper. That is, the stirrer 33 described above also serves to prevent the gases in the atmospheres before and after the degassing treatment from being mixed with each other and serves to prevent the molten copper before the degassing treatment from being mixed with the molten copper after the degassing treatment.
The molten copper transferred from the melting furnace A to the soaking furnace B is heated and is then supplied to the continuous casting machine D via the casting trough C and the turn-dish 5a. Subsequently, the molten copper is drawn downward through the mold 41 by the pinch rollers 42, is cooled and solidified, and is then continuously cast so as to produce the cast copper 21a (continuous casting step).
The cast copper 21a is cut by the cutter E, thereby continuously yielding the ingots 23a of low-oxygen copper, each having a predetermined length (cutting step).
The ingots 23a of low-oxygen copper obtained by cutting the cast copper 21a is transferred by the transfer device F (transfer step). That is, the ingots 23a of low-oxygen copper are received in the basket 51 located approximately right under the continuous casting machine D, are lifted to the level at which the conveyor 53 is located by the elevator 52 and is then transferred by the conveyor 53.
In the method for manufacturing the ingots of low-oxygen copper by using the manufacturing apparatus 101 according to this embodiment, the combustion is performed in a reducing atmosphere in the melting furnace A so that the molten copper is deoxidized, and the deoxidized molten copper is sealed in a non-oxidizing atmosphere in the casting trough C and is then transferred to the turn-dish 5a. Since the concentration of oxygen in the molten copper is inversely proportional to that of hydrogen, the concentration of hydrogen in the deoxidized molten copper is increased. However, the molten copper is dehydrogenated by the stirrer 33 used in the subsequent degassing step. Accordingly, without requiring a long moving distance of the molten copper, the concentration of hydrogen, which is increased by a deoxidizing treatment performed by reduction in accordance with the equilibrium equation (A), can be decreased, and hence the generation of holes in the molten copper can be suppressed. As a result, by using a gas furnace in which combustion is performed, the generation of holes can be suppressed in cooling and solidification, and hence mass production of high quality ingots of low-oxygen copper can be continuously performed at lower cost.
In addition, since the degassing step is performed by the stirrer 33 for stirring the molten copper, the dehydrogenating treatment can be forcibly performed in a short period, and hence the dehydrogenating treatment can be efficiently performed by using a simple structure.
Furthermore, when the stirrer 33 is composed of the dikes which meander the flow path for the molten copper, the molten copper is automatically stirred by the flow thereof, and hence the dehydrogenating treatment can be efficiently performed by a simple structure without using an additional agitator or the like. In addition, the operation of the apparatus 101 for manufacturing the ingots of low-oxygen copper can be easily controlled, and hence production costs can be further decreased.
In this connection, the location at which the separation is performed by the stirrer 33 is not limited to one location, and in accordance with the moving distance of the molten copper, a plurality of stirrers may be optionally provided. In addition, the embodiment is not limited to the production of the ingots of low-oxygen copper and may be applied to the production of ingots of low-oxygen copper alloy by adding an appropriate element.
As the stirrer 33, the dikes 33a, 33b, 33c, and 33d are respectively provided at the top and bottom, and the right and left, of the flow path 31 for the molten copper; however, the number and the locations of the dikes may be optionally changed in accordance with the length and the width of the casting trough C.
Furthermore, a so-called vertical continuous casting machine D is used in this embodiment; however, a so-called horizontal continuous casting machine may be used instead. In this case, a hoist such as the elevator 52 is not required.
Next, a second embodiment will be described with reference to
In this embodiment, since the melting furnace and the soaking furnace have the structures equivalent to those described in first embodiment, respectively, the same reference levels of the elements in first embodiment designate the same constituent elements in this embodiment, and detailed descriptions thereof will be omitted.
The casting trough C2 seals the molten liquid in a non-oxidizing atmosphere supplied from the soaking furnace B and transfers the sealed molten liquid to a turn-dish 5b. The turn-dish 5b is provided with a teeming nozzle 9 at the end of the flow direction of the molten liquid so that the molten liquid is supplied from the turn-dish 5b to the belt caster type continuous casting machine G.
The casting trough C2 and the turn-dish 5b have shapes and the like slightly different from those of first embodiment described above so as to be applied to the production of low-oxygen copper wires; however, the basic structures thereof are approximately equivalent to those in first embodiment, respectively. That is, the casting trough C2 is provided with a stirrer 33 shown in
The belt caster type continuous casting machine G is connected to the soaking furnace B via the casting trough C2. The belt caster type continuous casting machine G is composed of an endless belt 11 moving around and a casting wheel 13 rotated by the endless belt 11 which is in contact with a part of the casting wheel 13, in which a cast copper 21b is continuously produced. The belt caster type continuous casting machine G is also connected to the rolling machine H.
The rolling machine H rolls the cast copper 21b in the form of a bar, supplied from the belt caster type continuous casting machine G, so as to produce low-oxygen copper wires (low-oxygen copper) 23b. The rolling machine H is connected to the coiler I via a shear (cutter) 15 and a defect detector 19.
The shear 15, provided with a pair of rotary blades 16, cuts the cast copper 21b rolled by the rolling machine H; that is, the shear 15 cuts the low-oxygen copper wire 23b into wires having shorter lengths. For example, immediately after the belt caster type continuous casting machine G is started, the internal texture of the cast copper 21b is not stable, and hence low-oxygen copper wire 23b cannot be produced with stable quality. Accordingly, in the case described above, the low-oxygen copper wire 23b supplied from the rolling machine H is sequentially cut by the shear 15 so that the low-oxygen copper wire 23b is not transferred to the defect detector 19 and to the coiler I until the quality of the cast copper 21b is stabilized. When the quality of the cast copper material 21b stabilizes, the rotary blades 16 are separated from each other so as to permit transfer of the low-oxygen copper wire 23b to the defect detector 19 and the coiler I.
Next, a method for manufacturing the low-oxygen copper wire will be described, using the apparatus 102 for manufacturing the low-oxygen copper wire having the structure described above.
Combustion is first performed in a reducing atmosphere in the melting furnace A so as to produce molten copper while being deoxidized (step of producing molten copper). The deoxidized molten copper transferred to the casting trough C2 via the soaking furnace B is sealed in a non-oxidizing atmosphere and is then transferred to the turn-dish 5b (step of transferring molten copper). Since the concentration of oxygen is inversely proportional to that of hydrogen, the concentration of hydrogen in the molten copper deoxidized in the melting furnace A is increased. The molten copper having a high hydrogen concentration is then dehydrogenated by the stirrer 33 while passing through the casting trough C2 (degassing step).
According to the steps described above, the content of oxygen in the molten copper is controlled to 20 ppm or less, and the content of hydrogen is controlled to 1 ppm or less. As a result, the amount of gas evolved in casting is decreased, and the generation of holes in the cast copper 21b can be suppressed.
In addition, according to the equilibrium equation (A), since the gas concentration in the molten copper is decreased when the partial pressure of steam is decreased, the molten copper which has not been processed by dehydrogenation is ideally separated from the dehydrogenated molten copper, and so the degassing effect can be further improved. The improved degassing effect described above can be realized by, for example, providing the stirrer 33 described above in the step of transferring the molten copper. That is, the stirrer 33 also serves to prevent the gases in the atmospheres before and after the degassing treatment from being mixed with each other and serves to prevent the molten copper before the degassing treatment from being mixed with the molten copper after the degassing treatment.
The molten copper transferred from the melting furnace A to the soaking furnace B is heated and is then supplied to the belt caster type continuous casting machine G from the teeming nozzle 9 of the turn-dish 5b via the casting trough C2. Subsequently, the molten copper is then continuously cast by the belt caster type continuous casting machine G, thereby yielding cast copper 21b at the end thereof (continuous casting step).
The cast copper 21a is rolled by the rolling machine H, thereby yielding low-oxygen copper wire 23b (low-oxygen copper) having superior surface quality (rolling step). When the low-oxygen copper wire (low-oxygen copper) 23b has stable quality, and after defects are detected by the defect detector 19, the low-oxygen copper wire 23b is wound around the coiler I while a lubricant oil such as wax, is coated on the wire 23b, and the low-oxygen copper wire in wound form is transferred to a subsequent step.
In the method for manufacturing the low-oxygen copper wire described above, since the content of oxygen in the molten copper is controlled to 20 ppm or less, and the content of hydrogen is controlled to 1 ppm or less prior to the steps of casting and rolling, the amount of gas evolved in casting is decreased, the generation of holes in the cast copper 21b can be suppressed, and the defects on the surface of the low-oxygen copper wire can be decreased.
In addition, the low-oxygen copper wire manufactured by the method described above has superior characteristics of gas evolution.
When a low-oxygen copper wire or a low-oxygen copper alloy wire, in which an amount of gas evolved therefrom is large, is used under a high vacuum condition or at a high temperature, the surface quality thereof may be degraded due to the generation of blisters on the surface of the wire, or the gas evolved may be discharged outside so as to pollute the environment in some cases. Since the amount of gas evolved from the low-oxygen copper wire manufactured by the method according to this embodiment is very small, the wire may be applied to a particle accelerator operated under a high vacuum condition or to a microwave oven in which a temperature is increased.
In the method for manufacturing the low-oxygen copper wire by using the manufacturing apparatus 102 according to this embodiment, combustion is performed in a reducing atmosphere in the melting furnace A so that the molten copper is deoxidized, and the deoxidized molten copper is sealed in a non-oxidizing atmosphere in the casting trough C2 and is then transferred to the turn-dish 5b. Since the concentration of oxygen in the molten copper is inversely proportional to that of hydrogen, the concentration of hydrogen is increased in this molten copper. However, the molten copper is dehydrogenated by the stirrer 33 used in the subsequent degassing step. Accordingly, without requiring a long moving distance of the molten copper, the concentration of hydrogen, which is increased by a deoxidizing treatment performed by reduction in accordance with the equilibrium equation (A), can be decreased, and hence the generation of holes in the molten copper can be suppressed. As a result, by using a gas furnace in which combustion is performed, the generation of holes can be suppressed in cooling and in solidification, and hence production of high quality, low-oxygen copper wires can be continuously performed at lower cost.
In addition, since the degassing step is performed by the stirrer 33 for stirring the molten copper, the dehydrogenating treatment can be forcibly performed in a short period, and hence the dehydrogenating treatment can be efficiently performed by using a simple structure.
Furthermore, when the stirrer 33 is composed of the dikes which meander the flow path for the molten copper, the molten copper is automatically stirred by the flow thereof, and hence the dehydrogenating treatment can be efficiently performed by a simple structure without using an additional agitator or the like. In addition, the operation of the apparatus 102 for manufacturing the low-oxygen copper wire can be easily controlled.
In this connection, in order to stabilize a temperature of the molten liquid, an electric furnace may be provided between the soaking furnace B and the turn-dish 5b.
In addition, an adder for adding an element other than copper to the molten copper may be provided at any location from the end of the casting trough C2 to the end of the turn-dish 5b.
Next, a third embodiment will be described with reference to
The inventors of the present invention discovered through intensive research that by adding a small amount of Ag to molten copper, holes generated in the cast copper alloy containing Ag become finely dispersed micro holes, and that the micro holes thus formed disappear in rolling and do not cause any defects. Accordingly, the generation of holes which is harmful to the wire composed of the low-oxygen copper alloy can be suppressed. In the method for adding Ag, there is still another advantage in that a decrease in the conductivity of wire composed of the low-oxygen copper alloy can also be suppressed.
In the apparatus 103 for manufacturing the wire composed of the low-oxygen copper alloy, a casting trough C3 is provided instead of the casting trough C2 in the apparatus 102 for manufacturing the low-oxygen copper wire.
In the vicinity of the end of the casting trough C3, a Ag adder 3 is provided so that Ag can be added to a molten liquid. By this Ag adder 3, Ag can be added to the molten liquid which is deoxidized and dehydrogenated, and by the turbulence of the molten copper in a turn-dish 5b, generated right after the addition of Ag, the Ag and the molten copper are preferably mixed with each other.
In this embodiment, the location at which the Ag adder 3 is provided is not limited to the vicinity of the end of the casting trough C3. That is, so long as the Ag added to the dehydrogenated molten liquid is uniformly diffused therein, the Ag adder 3 may be provided at any location from the end of the casting trough C3 to the end of the turn-dish 5b.
In addition, the structure of the casting trough C3 is equivalent to that of the casting trough C2 except that the Ag adder 3 is provided. That is, the casting trough C3 is provided with a stirrer 33 shown in
Next, a method for manufacturing the wire composed of the low-oxygen copper alloy will be described, using a manufacturing apparatus 103 having the structure described above.
Combustion is first performed in a reducing atmosphere in a melting furnace A so as to produce molten copper while being deoxidized (step of producing molten copper). The deoxidized molten copper transferred to the casting trough C3 via a soaking furnace B is sealed in a non-oxidizing atmosphere and is then transferred to the turn-dish 5b (step of transferring molten copper). Since the concentration of oxygen is inversely proportional to that of hydrogen, the concentration of hydrogen in the molten copper deoxidized in the melting furnace A is increased. The molten copper having a high hydrogen concentration is dehydrogenated by the stirrer 33 while passing through the casting trough C3 (degassing step).
According to the steps described above, the content of oxygen in the molten copper is controlled to 1 to 10 ppm, and the content of hydrogen is controlled to 1 ppm or less. Subsequently, Ag is added to the molten copper, in which the concentrations of oxygen and hydrogen are controlled, by the Ag adder 3 so that the content of the Ag in the molten copper is 0.005 to 0.2 wt % (step of adding Ag).
When the content of Ag is less than 0.005 wt %, the effect of suppressing the defects on the surface of the wire does not occur. In contrast, when the content of Ag is more than 0.2 wt %, the effect of suppressing the defects is not significantly changed compared to that observed when the Ag content is 0.005 to 0.2 wt %, but the strength of the wire composed of the low-oxygen copper alloy is increased, and so rolling, fabrication and the like of the cast copper alloy may not be preferably performed. Accordingly, the content of Ag is preferably controlled in the range described above.
The molten copper containing Ag transferred from the melting furnace A to the soaking furnace B is heated and is then supplied to a belt caster type continuous casting machine G via the casting trough C3 and the turn-dish 5b. Subsequently, the molten copper containing Ag is continuously cast by the belt caster type continuous casting machine G, thereby yielding a cast copper alloy 21c at the end thereof (continuous casting step).
The cast copper alloy 21c is rolled by a rolling machine H, thereby yielding the wire 23c composed of the low-oxygen copper alloy (low-oxygen copper) containing a predetermined amount of Ag and having superior surface quality (rolling step). Subsequently, the wire 23c is wound around a coiler I.
As described above, since the concentrations of oxygen and hydrogen in the molten copper are controlled, and a predetermined amount of Ag is added to the molten copper prior to the steps of casting and rolling, the amount of gas evolved in casting is decreased, the generation of holes in the cast copper alloy 21c can be suppressed and the defects on the surface of the wire composed of the low-oxygen copper alloy can be decreased.
The inspection results of defects on the surface of the wire 23C, composed of the low-oxygen copper alloy obtained by the method using the apparatus 103 described above is shown in
When the number of grain boundaries can be increased by adding an element which forms finer crystal grains of copper, the concentration of a gas component per grain boundary is decreased. Accordingly, when a local equilibrium of hydrogen, oxygen and steam in the cast copper alloy 21c is considered, an apparent concentration of the gas component in the case described above is significantly decreased compared to the case in which larger grains are formed, and as a result it is believed that large holes are unlikely to be generated.
According to research by the inventors of the present invention, Ag is a preferable element to be added, and when 0.005 wt % or more of Ag is contained, holes formed in the cast copper alloy 21c are finely dispersed micro holes, and hence the number of defects on the surface of the wire 23c formed by rolling the low-oxygen copper alloy 21c can be reduced. In addition, when 0.03 wt % or more of Ag is contained, the defects can be significantly reduced, and when 0.05 wt % or more of Ag is contained, the defects can be further significantly reduced.
In the method for manufacturing the wire composed of the low-oxygen copper alloy by using the manufacturing apparatus 103 according to this embodiment, combustion is performed in a reducing atmosphere in the melting furnace A so that the molten copper is deoxidized, and the molten copper is then sealed in a non-oxidizing atmosphere in the casting trough C3 and is transferred to the turn-dish 5b. Since the concentration of oxygen in molten copper is inversely proportional to that of hydrogen, the concentration of hydrogen in the deoxidized molten copper is increased. However, the molten copper is dehydrogenated by the stirrer 33 used in the subsequent degassing step. Accordingly, the concentration of hydrogen, which is increased by a deoxidizing treatment performed by reduction in accordance with the equilibrium equation (A), is decreased, and hence the generation of holes in solidification can be suppressed. In addition, Ag is added by the Ag adder 3 to the molten copper in which holes are hardly generated by the deoxidizing and the dehydrogenating treatments, whereby finely dispersed micro holes can be formed.
Accordingly, by using the belt caster type continuous casting machine G, long cast copper alloys can be continuously manufactured at lower cost, in which decrease in conductivity is suppressed, and the number of harmful holes is decreased. In addition, even when the degassing step is simplified, a wire composed of low-oxygen copper alloy having excellent surface quality can be manufactured, in which defects on the surface of the wire are significantly reduced. As a result, in order to perform a dehydrogenating treatment, an expensive and specified device, such as a vacuum-degassing device, is not required, and hence the structure of device can be simplified and a wire composed of low-oxygen copper alloy can be manufactured at lower cost.
In addition, since the degassing step is performed by the stirrer 33 for stirring the molten copper, the dehydrogenating treatment can be forcibly performed in a short period, and hence the dehydrogenating treatment can be efficiently performed by using a simple structure.
Furthermore, when the stirrer 33 is composed of the dikes which meander the flow path of the molten copper, the molten copper is automatically stirred by the flow thereof, and hence the dehydrogenating treatment can be efficiently performed by a simpler structure without using an additional agitator or the like. In addition, the operation of the apparatus 103 for manufacturing the wire composed of the low-oxygen copper alloy can be easily controlled.
Since the wire 23c composed of the low-oxygen copper alloy contains 0.005 to 0.2 wt % of Ag, a decrease in conductivity can be suppressed, and a high quality wire can be manufactured having a small number of defects on the surface, i.e., superior surface quality.
Next, a fourth embodiment will be described with reference to
The base low-oxygen copper material is formed into various shapes, such as a bar, a wire and a ball, and is preferably used as, for example, an anode for copper plating forming a wiring pattern on a printed circuit board. That is, a wiring pattern can be preferably formed on a printed circuit board by copper plating, and more preferably, by copper sulfate plating. In copper sulfate plating, a copper material containing phosphorus (low-oxygen copper containing approximately 0.04% of phosphorus) is used as an anode. The phosphorus contained in the copper material promotes smooth dissolution of a copper anode, whereas when an anode for copper plating contains no phosphorus is used, uniform adhesiveness of a plating film is degraded.
In the apparatus 104 for manufacturing the base copper material containing phosphorus for use in copper plating, a casting trough C4 is provided instead of the casting trough C2 in the apparatus 102 for manufacturing the low-oxygen copper wire.
In the vicinity of the end of the casting trough C4, a P (phosphorus) adder 4 is provided so that phosphorus can be added to the molten liquid. By this P adder 3, phosphorus can be added to the molten liquid which is deoxidized and dehydrogenated, the reaction between phosphorus and oxygen is prevented, and by the turbulence of the molten copper in a turn-dish 5b generated right after the addition of phosphorus, the phosphorus and the molten copper are preferably mixed with each other.
In this embodiment, the location at which the P adder 4 is provided is not limited to the vicinity of the end of the casting trough C4. That is, so long as the P added to the molten liquid after a dehydrogenating treatment is uniformly diffused therein, the P adder 3 may be provided at any location from the end of the casting trough C4 to the end of the turn-dish 5b.
In addition, the structure of the casting trough C4 is equivalent to that of the casting trough C2 except that the P adder 4 is provided. That is, the casting trough C4 is provided with a stirrer 33 shown in
Next, a method for manufacturing the base copper material containing phosphorus for use in copper plating will be described, using an apparatus 104 having the structure described above.
Combustion is first performed in a reducing atmosphere in a melting furnace A so as to produce molten copper while being deoxidized (step of producing molten copper). The deoxidized molten copper, transferred to the casting trough C4 via a soaking furnace B, is sealed in a non-oxidizing atmosphere and is then transferred to the turn-dish 5b (step of transferring molten copper). Since the concentration of oxygen is inversely proportional to that of hydrogen, the concentration of hydrogen in the molten copper deoxidized in the melting furnace A is increased. The molten copper having a high hydrogen concentration is dehydrogenated by the stirrer 33 while passing through the casting trough C4 (degassing step).
According to the steps described above, the content of oxygen in the molten copper is controlled to 20 ppm or less, and the content of hydrogen is controlled to 1 ppm or less. Subsequently, phosphorus is added by the P adder 4 to the molten copper in which the concentrations of oxygen and hydrogen are controlled, so that the content of the phosphorus in the molten copper is 40 to 1,000 ppm (step of adding P).
In this embodiment, when the concentration of oxygen, the concentration of hydrogen and the content of phosphorus are out of the range described above, the following problems may occur. That is, when the concentration of oxygen is more than 20 ppm in the molten copper, the workability is poor, and cracking may occur in a cast base copper material. When the concentration of hydrogen is more than 1 ppm, the amount of gas evolved is large and cracking may occur in the cast base copper material. When the content of phosphorus is less than 40 ppm, uniform solubility cannot be obtained when the base copper material is used as an anode, and hence the base copper material cannot be a material for forming a copper ball. In addition, when the content of phosphorus is more than 1,000 ppm, workability is degraded.
As described above, since the concentrations of oxygen and hydrogen in the molten copper are controlled, and phosphorus is added to the molten copper prior to the steps of casting and rolling, the amount of gas evolved in casting is decreased, the generation of holes in a cast base copper material 21d is suppressed, and the defects on the surface of a wire are decreased.
As described above, after the molten copper transferred from a melting furnace A to a soaking furnace B is heated, the molten copper is supplied to a belt caster type continuous casting machine G via the casting trough C4 and the turn-dish 5b and is then cast by the continuous casting machine G, whereby the cast base copper material 21d can be obtained at the end of the continuous casting machine G. The cast base copper material 21d is rolled by a rolling machine H, whereby a base copper material (low-oxygen copper) 23d containing a predetermined amount of phosphorus for use in copper plating having superior surface quality is formed. The presence of defects in the base copper material 23d containing phosphorus is inspected by a defect detector 19, and the base copper material 23d is then wound around a coiler I while coated by a lubricant such as wax. The base copper material 23d containing phosphorus is then transferred to another step and is then optionally formed into, for example, copper balls.
In the method for manufacturing the base copper material containing phosphorus by using the manufacturing apparatus 104, according to this embodiment, combustion is performed in a reducing atmosphere in the melting furnace A so that the molten copper is deoxidized, and the deoxidized molten copper is sealed in a non-oxidizing atmosphere in the casting trough C4 and is then transferred to the turn-dish 5b. Since the concentration of oxygen is inversely proportional to that of hydrogen, the concentration of hydrogen in the molten copper is increased. However, the molten copper is dehydrogenated by the stirrer 33 used in the subsequent degassing step. Accordingly, the concentration of hydrogen, which is increased in accordance with the equilibrium equation (A) by a deoxidizing treatment performed by reduction, can be decreased without requiring a long moving distance of the molten copper, and hence the generation of holes in the molten copper can be suppressed. As a result, by using the belt caster type continuous casting machine G, a high quality cast base copper material 21d can be continuously manufactured at lower cost, having a small number of defects on the surface thereof. In addition, since the amount of gas evolved is small, and the number of defects on the surface can be decreased by suppressing the generation of holes, the cast base copper material 21d is not cracked, and hence a base copper material 23d, containing phosphorus for use in copper plating and having excellent surface quality can be obtained. In addition, since a cast base copper material 21d can be obtained having high flexural strength, cracking which occurs when an anode in the form of a ball for use in copper plating is manufactured can be prevented. Furthermore, since the belt caster type continuous casting machine G is used, hot rolling is performed after casting, and hence the remaining cast texture which is produced when an anode for copper plating is formed by direct casting can be eliminated. In addition, an anode for copper plating having a uniform texture can be obtained by recrystallization. Consequently, mass production of high quality anodes for copper plating can be performed at lower cost.
When the degassing step is performed by the stirrer 33 for stirring the molten copper, the dehydrogenating treatment can be forcibly performed in a short period, and hence the dehydrogenating treatment can be efficiently performed by a simpler structure.
In addition, when the stirrer 33 is composed of the dikes which meander the flow path for the molten copper, the molten copper is automatically stirred by the flow thereof, and as a result, the dehydrogenating treatment can be efficiently performed by a simpler structure without using an additional agitator or the like. Furthermore, the operation of the apparatus 104 for manufacturing the base copper material, containing phosphorus for use in copper plating, can be easily controlled.
In addition to the method described above, a short base copper material 23e containing phosphorus for use in copper plating may be directly formed by a cutter having a shear 15. The manufacturing method mentioned above will be described as another example of this embodiment according to the present invention.
In the method described above, an apparatus 104b for manufacturing the base copper material 23e which is composed of the apparatus 104 described above and an alcohol bath (washing means) 18 provided under the shear 15 is used.
In the manufacturing method using the apparatus 104b, as shown in
The base copper material 23d ejected from the rolling machine H is still hot, and the surface thereof is oxidized by air, that is a thin oxide film is formed on the surface. However, since the base copper materials 23e are immersed in the alcohol 18a, the surfaces thereof are washed, and in addition the oxide films formed thereon are reduced, whereby the surface quality, and in particular the brilliance thereof, can be improved. As the alcohol 18a, isopropyl alcohol (IPA) is preferable.
In this example, the rotary blades 16 each have four cutting portions 16a; however the number of the cutting portions 16a can be optionally changed.
As described above, in the manufacturing method using the apparatus 104b for manufacturing the base copper material containing phosphorus for use in copper plating, since the short base copper material 23e can be directly formed by cutting the base copper material 23d into a predetermined length, a step of winding the base copper material 23d around the coiler I, which is a necessary step of manufacturing the long base copper material 23d, can be eliminated and hence the number of manufacturing steps can be reduced. As a result, for example, copper balls can be easily manufactured at lower cost.
In addition, since a lubricant which is used when the base copper material 23d is wound around the coiler I is not required, a risk which may significantly decrease the quality of copper balls, i.e., the quality of anodes for copper plating, can be eliminated, whereby high quality copper balls can be manufactured, and in addition the stability of the quality can be significantly improved.
Furthermore, when the base copper material 23e having a short length is washed by using an alcohol 18a, such as IPA, a base copper material 23e can be obtained having superior surface quality, in particular, superior brilliance.
As a washing solution, acids may also be used in addition to alcohols; however alcohols are preferable due to the easy handling and disposal thereof compared to those of acids.
In the second to fourth embodiments, the belt wheel type continuous casting machine is used as an example of the belt caster type continuous casting machine; however, other belt caster type continuous casting machines may also be used. As a belt caster type continuous casting machine, a twin belt type continuous casting machine having two endless belts may be mentioned.
As has thus been described, according to the method for manufacturing low-oxygen copper of the present invention, a dehydrogenating treatment can be performed without requiring a long moving distance of molten copper, and the generation of holes in solidification is suppressed, whereby high quality low-oxygen copper having superior surface quality can be obtained.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2000-109828 | Apr 2000 | JP | national |
| 2000-207488 | Jul 2000 | JP | national |
| 2000-207490 | Jul 2000 | JP | national |
| 2000-356325 | Nov 2000 | JP | national |
| 2000-356326 | Nov 2000 | JP | national |
| 2000-48005 | Feb 2000 | JP | national |
| 2000-109827 | Apr 2000 | JP | national |
This application is a division of and claims the benefit of priority under 35 USC § 120 from U.S. application Ser. No. 09/791,767, filed Feb. 26, 2001, and claims the benefit of priority under 35 USC § 119 from Japanese patent Application Nos. 2000-109827, filed on Apr. 11, 2000, Japanese patent Application No. 2000-48005, filed on Feb. 24, 2000, Japanese patent Application No. 2000-109828, filed on Apr. 11, 2000, Japanese patent Application No. 2000-207488, filed on Jul. 7, 2000, Japanese patent Application No. 2000-207490, filed Jul. 7, 2000, Japanese patent Application No. 2000-356325, filed on Nov. 22, 2000 and Japanese patent Application No. 2000-356326, filed on Nov. 22, 2000, the entire contents of which are incorporated herein by reference.
| Number | Date | Country | |
|---|---|---|---|
| Parent | 09791767 | Feb 2001 | US |
| Child | 11194568 | Aug 2005 | US |
