Title of Invention

DEOXIDATION CASTING ALUMINIUM CASTING AND CASTING MACHINE

Abstract The method of deoxidation casting of the present invention is capable of deoxidizing the oxide film formed on the surface of the molten metal, improving wettability to inner faces of a cavity of a casting die, and casting high quality products with high casting efficiency. The method of deoxidation casting of the present invention comprises the steps of : reacting a deoxidizing compound, which is made by reacting a metallic gas on a reactive gas, on la molten metal; and deoxidizing an oxide film on la surface of the molten metal.
Full Text DEOXIDATION CASTING, ALUMINIUM CASTING AND CASTING
MACHINE
BACKGROUND OF THE INVENTION
The present invention relates to deoxidation casting, aluminium casting and a casting machine.
Many kinds of ways of casting, e.g., gravity casting, low pressure casting, die casting, squeeze casting, thixotropic casting, are known. In any ways of casting, a molten metal is poured into a cavity of a casting die to solidify and form the metal into a prescribed shape. The ways of casting are selected on the basis of a material of the molten metal and a product to be cast.
Many kinds of products are cast. In the case of casting a product having a complex shape or high performance, the cavity must be securely filled with the molten metal so as to form no casting defect, have a prescribed strength, prevent deformation and have a good external shape.
Aluminium and aluminium alloy have been widely used as the material of the molten metal. In the aluminum casting, aluminium is apt to make an oxide film. By the oxide film formed on a surface of the molten aluminium, surface tension of the molten metal is made greater, so that fluidity and a welding property of the molten metal is made lower and casting defects are sometimes caused. To solve these disadvantages, many improvements, e.g., lubricant, pouring manners, pouring speed, pouring pressure, have been studied.
For example, in the gravity casting and the low pressure casting, falling temperature of the molten metal is made slower by painting heat-insulating releasing agent, adjusting an arrangement of a gate, etc., so that bad molten metal running, crinkles, cold shut, etc., which are caused by forming the oxide film on the surface of the molten metal, can be
restricted. In the die casting, the molten metal is filled in a short time with high pressure by adjusting the pouring speed, the pouring pressure, the arrangement of the gate, etc. In squeeze casting, the purring pressure is highly pressurized during a step of the gravity casting so as to break and fuse the oxide film.
However, the conventional ways of casting have disadvantages, and no perfect ways are known. Especially, the oxide film, which is made or formed when the molten metal touches inner faces of the cavity of the casting die, forms clinking and the cold shut in a surface of a product, and the oxide film causes unsatisfied filling of the molten metal. In the case of casting parts of airplanes and vehicles, whose surface stress and broken portions seriously influence safety, etc., all cast products are examined by means for fluorescent flaw detection. Therefore, manufacturing cost of the products must be higher. Further, quality and reliability of the products cannot be fixed.
The problems of the oxide film are caused in not only the aluminium casting but also casting with other materials.
SUMMARY OF THE INVENTION
The present invention has been invented to solve the problems caused by the oxide film formed on the surface of the molten metal.
An object of the present invention is to provide a method of forming on the surface of the molten metal, improving wettability to inner faces of a cavity of a casting die, and casting high quality products with high casting efficiency.
Another object is to provide a deoxidation casting machine for executing said method.
The method of deoxidation casting of the present invention
comprises the steps of:
reacting a deoxidizing compound, which is made by reacting a metallic gas on a reactive gas, on a molten metal; and
deoxidizing an oxide film on a surface of the molten metal.
A metal for the metallic gas may be selected on the basis of the molten metal. For example, magnesium nitride compound (Mg3 N2), which is made by reacting a magnesium gas on a nitrogen gas, may be employed as an effective deoxidizing compound, which is capable of deoxidizing the oxide film formed on the surface of the molten metal. Magnesium is stable from room temperature to high temperature and capable of easily subliming. Therefore, magnesium can be properly used in the method. The magnesium nitride compound high deoxidizing property, so that the oxide film on the surface of the molten metal can be effectively deoxidized.
The deoxidation casting of the present invention relates to the method, which is capable of deoxidizing the oxide film formed on the surface of the molten metal so as to make the pure molten metal. Therefore, in the case of casting with a molten metal on which the oxide film is apt to be formed, the method of the present invention is capable of effectively deoxidizing the oxide film and properly casting with the pure molten metal.
By deoxidizing the oxide film on the surface of the molten metal, the surface tension of the molten metal can be lower, fluidity of the molten metal can be higher and the wettability with respect to the inner faces of the cavity of the casting die can be higher. Since the pure molten metal touches the inner faces of the cavity, the molten metal can easily flow in the casting die, the molten metal running property can be improved and the molten metal can securely fill the cavity including minute spaces thereof.
In a conventional casting method, lubricant or heat-insulating releasing agent are used to warm a casting die and keep fuidity of a molten metal. In the present invention, the fluidity of the molten metal is made higher, so that no lubricant or no heat-insulating releasing agent are required. Therefore, preparation and adjustment of the casting die can be easily, and casting efficiency can be made higher.
In the conventional casting method, the casting die is heated until reaching high temperature so as to keep the fluidity of the molten metal. The molten metal is poured into the heated casting die. The molten metal is solidified by cooling the casting die. On the other hand, in the present invention, the fluidity of the molten metal is very high, so the casting die need not be heated. Therefore, the molten metal can be solidified in a short time, the product can be quickly solidified, toughness of the product can be greater, deformation of the product, e.g., sink mark, extension, can be prevented and quality of the product can be higher. The casting die may be used at the room temperature.
In the conventional gravity casting, a feeding head is formed in a casting die, and the molten metal is introduced into a cavity, by its own weight, from the feeding head. In the present invention, the fluidity of the molten metal in the casting die is very high, so capacity of the feeding head can be reduced. In the conventional die, the capacity of the feeding head is 50-60 % of capacity of the die. In the present invention, since the fluidity of the molten metal can be higher, the capacity of the feeding head can be reduced to 10-20 % of the capacity of the casting die. Therefore, the molten metal can be efficiently used, and the casting die can be made easily. By reducing the capacity of the feeding head, the solidification of the molten metal can be accelerated, so that a cycle time of casting can be shorter and the casting efficiency can be improved. Further, in the present invention, the product can be easily separated from
the casting die, so that the product can be taken out quickly and the casting efficiency can be improved.
There are two ways of reacting the molten metal on the deoxidizing compound in the cavity of the casting die. One way comprises the steps of: making the deoxidizing compound outside of the casting die; introducing the deoxidizng compound into the cavity; and pouring the molten metal into the cavity. The other way comprises the steps of: making the deoxidizing compound in the cavity of the casting die; and pouring the molten metal into the cavity.
The deoxidizing compound is precipitated on the inner faces of the cavity so as to react the deoxidizing compound on the molten metal thereon. To effectively precipitate the deoxidizing compound on the inner faces of the cavity, a metallic gas, which is made by evaporating a metal for making the deoxidizing compound, and a reactive gas, e.g., nitrogen gas, are reacted.
The deoxidizing compound may be introduced into or made in the cavity, in which a non-oxygen atmosphere is produced, so as not to decline deoxidizing function of the deoxidizing compound. The non-oxygen atmosphere may be produced by decompressing the cavity, introducing an inert gas into the cavity to purge air therefrom, etc..
The method of the present invention can be properly applied to the casting, in which aluminium or aluminium alloy is used as the molten metal. In the aluminium casting, a magnesium nitride compound, which is made by reacting a magnesium gas on a nitrogen gas, and the molten aluminium are reacted so as to easily deoxidize the oxide film formed on the surface of the molten aluminium. In the case of aluminium, the oxide film is apt to be formed on the surface of the molten metal. By deoxidizing the oxide film by the magnesium nitride compound, high quality products can be produced.
In the aluminium casting too, there are two ways of reacting the molten metal on the deoxidizing compound in the cavity of the casting die. One way comprises the steps of: previously making the magnesium nitride compound by reacting the magnesium gas on the nitrogen gas; introducing the magnesium nitride compound into the cavity; and pouring the molten aluminium into the cavity. The other way comprises the steps of: respectively introducing the magnesium gas and the nitrogen gas into the cavity of the casting die so as to make the magnesium nitride compound; and pouring the molten aluminium into the cavity. The magnesium nitride compound, which is the deoxidizing compound, is precipitated on the inner faces of the cavity including a core, then the molten aluminium is poured therein. When the molten aluminium touches the inner faces of the cavity, on which the deoxidizing compound has been precipitated, oxygen is removed from the oxide film on the surface of the molten aluminium by deoxidizing function of the deoxidizing compound, so that the surface of the molten aluminium can be pure aluminium.
The oxide film formed on the surface of the molten aluminium is removed by the deoxidation when the molten aluminium touches the inner faces of the cavity, so that crinkles and surface defects, which are formed on the surface of the products, can be prevented. Especially, in the case of casting products having complex shapes, it was impossible to remove the surface defects. However, in the present invention, good products having no surface defects can be cast due to high wettability and a capillary phenomenon of the molten aluminium.
In the case of making the magnesium nitride compound in the cavity, firstly the magnesium gas is introduced into the cavity, then the nitrogen gas is introduced thereinto. Magnesium is heated in an inert gas, e.g., argon gas, or a deoxidizing gas, e.g., hydrogen, until the magnesium
is sublimed, so that the magnesium gas is made. The magnesium gas is introduced into the cavity. The magnesium gas is introduced together with a non-oxidizing carrier gas. Pressure and amount of the carrier gas are properly adjusted. Preferably, the carrier gas is an inert gas, e.g., argon. Magnesium is sublimed at temperature of 700-850° C, and the magnesium gas can be easily introduced into the cavity by the carrier gas.
When the magnesium gas is introduced into the cavity, the cavity is in the non-oxygen atmosphere. To produce the non-oxygen atmosphere, the cavity is previously decompressed or purged with the nitrogen gas, etc.. Oxygen in the cavity can be removed, and the magnesium gas can be uniformly introduced into the cavity.
After the magnesium gas is introduced into the cavity, the nitrogen gas is introduced into the cavity so as to make the magnesium nitride compound. The magnesium nitride compound is mainly precipitated on the inner faces of the cavity as powders.
When the nitrogen gas is introduced into the cavity, pressure and amount of flow of the nitrogen gas are properly adjusted. To easily react the nitrogen gas on the magnesium gas, the nitrogen gas may be preheated to warm the casting die. Reaction time may be 5-90 seconds. If the reaction time is too long, temperature of the casting die falls, so proper reaction time is 15-60 seconds.
When the nitrogen gas is introduced into the cavity to make the magnesium nitride compound, it is important to prevent the magnesium nitride compound from reacting on the casting die. The molten metal directly touches the inner faces of the cavity, so a surface condition of the molten metal highly influences a surface condition of the product. Therefore, the deoxidizing function of the magnesium nitride compound must works on the inner faces of the cavity.
The inner faces of the cavity must not react on the magnesium
nitride compound. If oxygen radical, etc., which is easily react on the magnesium nitride compound, exists on the inner faces of the cavity, the deoxidizing function is lost before pouring the molten metal into the cavity. Therefore, it is improper to coat the inner faces of the cavity with an oxide material, e.g., lubricant, a releasing agent. The inner faces of the cavity may be coated with a non-oxide material, e.g., graphite. Further, metal surfaces may be exposed in the inner faces of the cavity without coating with lubricant, etc., and the exposed metal surfaces may be treated with heat or nitrided. While the magnesium nitride compound exists on the inner faces of the cavity, the molten aluminium is poured into the cavity, then the magnesium nitride compound on the inner faces of the cavity reacts on the molten metal, so that oxygen is removed from the oxide film and the oxide film is deoxidized. With this reaction, the wettability of the molten aluminium is made much greater, the fluidity on the inner faces of the cavity is made higher and the capillary phenomenon is made active. Since the surface of the molten metal is made pure aluminium, the products have good external shape having no crinkles and no surface detects.
BRIEF DESCRIPTION OF THE DRAWINGS
Embodiments of the present invention will now be described by way of examples and with reference to the accompanying drawings, in which:
Fig. 1 is an explanation view of the deoxidation casting machine of a first embodiment of the present invention;
Fig. 2A is a sectional view of a connecting section of a casting die;
Fig. 2B is a front view of the connecting section;
Fig. 3 is an explanation view of the deoxidation casting machine of a second embodiment of the present invention;
Fig. 4 is an explanation view of the deoxidation casting machine of a third embodiment of the present invention;
Fig. 5 is a sectional view of another example of the casting die;
Fig. 6 is an explanation view of a magnesium feeding mechanism;
Fig. 7 is an explanation view of another example of a furnace;
Fig. 8 is an explanation view of another example of the furnace;
Fig. 9 is an explanation view of the deoxidation casting machine of a fourth embodiment of the present invention;
Fig. 10 is an explanation view of the deoxidation casting machine of a fifth embodiment of the present invention;
Fig. 11 is an explanation view of the deoxidation casting machine of a sixth embodiment of the present invention;
Fig. 12 is an explanation view of the deoxidation casting machine of a seventh embodiment of the present invention;
Fig. 13 is an explanation view of a manner of reacting a molten metal on a deoxidizing compound;
Fig. 14 is an explanation view of a manner of reacting a molten metal, which is reservoired in a reservoir;
Fig. 15 is a microphotograph of a surface of a product, which is made by the method of the present invention; and
Fig. 16 is a microphotograph of a surface of a product, which is made by the conventional method.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Preferred embodiments of the present invention will now be
described in detail with reference to the accompanying drawings.
Firstly, a basic theory of the present invention will be explained. A
deoxidizing compound can be made react on a molten metal by many
ways. For example, the deoxidizing compound may be made react on the
molten metal at a pouring mouth of a casting die when the molten metal is poured therefrom, the deoxidizing compound may be made react on the molten metal in a ladle, and the deoxidizing compound may be made react on the molten metal in a reservoir, in which the molten metal is reservoired. In Fig. 13, inlets 202 and 204 are formed in the vicinity of the pouring mouth of the casting die 200. A magnesium gas and a nitrogen gas are respectively introduced into the pouring mouth so as to react the gasses on the molten metal, which is poured into the purring mouth. Magnesium nitride compound, which is the deoxidizing compound, is made in the pouring mouth, and the magnesium nitride compound can react on the molten metal. With this structure, the oxide film formed on the surface of the molten metal can be deoxidized when the molten metal is poured into the casting die, so that high quality products can be cast.
In Fig. 13, the molten metal is reservoired in a ladle 208. The oxide film on the surface of the molten metal may be deoxidized or removed by adding the deoxidizing compound into the molten metal in the ladle 208. Further, the deoxidizing compound may be added to the molten metal in a reservoir.
Fig. 14 shows another example of reacting the deoxidizing compound on the molten metal. The molten metal 206 is reservoired in a reservoir 210. The deoxidizing compound is made in a bubbling member 212, whose lower end is dipped in the molten metal 206, and introduced into the molten metal 206. The deoxidizing compound is made by introducing the magnesium gas and the nitrogen gas into the bubbling member 212, so that the deoxidizing compound can be introduced into the molten metal 206 and the oxide film on the surface of the molten metal 206 can be deoxidized and removed. By removing the oxide film, the fluidity of the molten metal 206 can be higher, so that high quality
products can be cast.
Fig. 15 is a microphotograph of a surface of an aluminium product, which is cast by the method of the present invention; Fig. 16 is a microphotograph of a surface of an aluminium product cast by the conventional method. In Fig. 16, crinkles are observed on the surface of the product. On the other hand, in Fig. 15, the product is cast by the method of the present invention, and the product has a very smooth surface and no crinkles.
Next, some embodiments of the present invention will be explained with reference to Figs. 1-5. In the embodiments, the magnesium gas and the nitrogen gas are respectively introduced into the cavity to make the deoxidizing compound, then the molten aluminium is poured into the cavity.
Fig. 1 shows an outline of a casting machine 10 of a first embodiment. A casting die 12 is connected to a reservoir 14. By moving a plug 16 upward, a prescribed amount of molten aluminium 18 is poured from the reservoir 14. Metal faces are exposed in inner faces of a cavity 12a. A nitrogen cylinder 20 is communicated to the casting die 12 via a pipe 22. The nitrogen gas is introduced into the casting die by opening a valve 24 so as to discharge air in the casting die 12. An argon gas cylinder 25 is communicated to a furnace 28 via a pipe 26. An argon gas is introduced into the furnace 28 by opening a valve 30. Heaters 32 heat the furnace 28. Temperature in the furnace rises to 800°C or more so as to sublime magnesium powders.
The argon gas cylinder 25 is also communicated to a tank 36, in which the magnesium powders are stored, via a pipe 34, to which a valve 33 is provided. The tank 36 is communicated to the pipe 26 via a pipe 38, whose end is connected to the pipe 36 at a position under the valve 30. A valve 40 is provided to the pipe 38. The furnace 28 is communicated to
the casting die 12 via a pipe 42 and a pipe 44, which is pierced through the plug 16. A valve 45 is provided to the pipe 42.
Figs. 2A and 2B show a connecting section 13 of the casting die 12, to which the pipe 22 is connected.
As shown in Fig. 2A, the connecting section 13 is formed into a female-tapered hole, whose inner diameter is gradually made greater toward outside. A tapered connecting plug (not shown), which is provided to a front end of the pipe 22, is detachably connected to the connecting section 13. The connecting section 13 is communicated to the cavity 12a via air ventilation holes 15.
The casting method executed by the casting machine 10 will be explained.
Firstly, the valve 24 is opened so as to introduce the nitrogen gas into the casting die 12 from the cylinder 20 via the pipe 22. By introducing the nitrogen gas, air in the casting die 12 can be purged or discharged. The air is discharged from air ventilation holes (not shown), which are formed in an upper part of the casting die 12, so that a non-oxygen atmosphere is produced in the casting die 12. After the air is purged from the casting die 12, the valve 24 is once closed. While the air is purged from the casting die 12, the valve 30 is opened to introduce the argon gas into the furnace 28, so that a non-atmosphere is produced in the furnace 28 too.
Next, the valve 30 is closed and the valve 40 is opened so as to supply the magnesium powders, which has been stored in the tank 36, into the furnace 28 by pressure of the argon gas. At that time, amount of flow and pressure of the argon gas may be adjusted by a flow adjuster. Since the furnace 28 is heated, by the heaters 32, to 800°C or more so as to sublime the magnesium powders, the magnesium powders supplied are sublimed and the magnesium gas is generated.
Then, the valve 40 is closed and the valves 30 and 45 are opened so as to introduce the magnesium gas into the casting die 12 via the pipes 42 and 44. At that time, the amount of flow and the pressure of the argon gas is adjusted. After the magnesium gas is introduced into the casting die 12, the valve 45 is closed and the valve 24 is opened so as to introduce the nitrogen gas into the casting die 12. By introducing the nitrogen gas into the casting die 12, the magnesium gas and the nitrogen gas react in the cavity 12a of the casting die 12, so that the magnesium nitride compound (Mg3N2) is made. The magnesium nitride compound is precipitated on the inner faces of the cavity 12a as powders.
In this state, the plug 16 is moved upward to pour the molten metal 18, which has been reservoired in the reservoir 14, into the casting die 12. The molten aluminium 18, which has been poured into the casting die 12, reacts on the magnesium nitride compound, which has been precipitated on the inner faces of the cavity 12a, on the inner faces of the cavity 12a. By the reaction, the magnesium nitride compound removes oxygen from the oxide film formed on the surface of the molten aluminum 18, so that the surface of the molten aluminium 18 is deoxidized and the pure aluminium surface is formed. Oxygen, which has been left if the casting die 12 or included in the molten aluminium 18, becomes magnesium oxide or magnesium hydroxide and will be involved in the molten aluminium 18. Amount of the magnesium oxide or the magnesium hydroxide is very small, so it does not badly influence aluminium products.
Since the magnesium nitride compound, which has been precipitated on the inner faces of the cavity 12a, removes oxygen from the oxide film formed on the surface of the molten aluminium 18 and makes the pure aluminum when the aluminium solidifies, the aluminium can be cast without forming the oxide film. The metal faces are exposed
in the inner faces of the cavity 12a, so that the magnesium nitride compound can be held on the inner faces of the cavity 12a without loss and the molten metal can be deoxidized securely. Surface condition of the inner faces of the cavity 12a much influences an external shape of the product, so the product can be cast with a good external shape because the magnesium-nitrogen compound can be securely made and held on the inner faces of the cavity 12a.
The magnesium-nitrogen compound prevents the oxide film from forming on the surface of the molten aluminum 18, so that surface tension of the molten metal 18 can be small, the wettability, fluidity, running property and smoothness of the molten metal 18 can be improved. Therefore, high quality aluminium products having no crinkles can be cast.
Note that, in the present embodiment, the nitrogen gas is introduced into the cavity 12a from the gas cylinder 20 so as to discharge the air in the cavity 12a. An inert gas, e.g., argon gas, may be used instead of the nitrogen gas so as to discharge the air. The air is discharged so as to prevent the magnesium nitride compound from reacting on oxygen in the cavity 12a.
To discharge the air from the cavity 12a, the nitrogen gas of the argon gas is introduced into the cavity 12a. Further, the cavity 12a may be decompressed by a decompression pump 52 so as to produce the non-oxygen atmosphere in the cavity 12a. In this case, the valve 19 is opened to decompress the cavity 12a via the pipe 17, then the valve 19 is closed and the magnesium gas is introduced into the cavity 12a (see Fig. 1).
When the nitrogen gas is introduced into the cavity 12a to make the magnesium nitride compound therein, the cavity 12a is pressurized by the argon gas, which acts as the carrier gas of the magnesium gas, and the nitrogen gas, which is supplied to make the magnesium nitride compound.
But there are formed the air ventilation holes, which discharge the air when the molten metal 18 is poured, in the casting die 12, so the pressure in the cavity 12a gradually reduces after the molten metal 18 is poured. By reducing the pressure, fresh air is capable of invading into the cavity 12a. To prevent the air invasion, the valve 24 is opened to supply the nitrogen gas into the cavity 12a from the gas cylinder 20 while the molten metal 18 is poured. Amount of supplying the nitrogen gas may be equal to the sum of amount of the air discharged and amount of nitrogen gas consumed to make the magnesium nitride compound. The amount of consuming the nitrogen gas can be known on the basis of amount of the magnesium gas supplied to the cavity 12a. The amount of supplying the nitrogen gas is controlled by a flow meter 21 and the valve 24, which are provided to the pipe 22.
In the above described embodiment, the method of the present invention is applied to the gravity casting. The deoxidation casting method of the present invention is not limited to the gravity casting.
A second embodiment of the present invention will be explained with reference to Fig. 3. The casting die 12 is constituted by an upper die section 50 and a press die section 51. Namely, the method of the present invention is applied to high pressure casting. Unlike the casting die of the gravity casting explained in the first embodiment, the casting die 12 of the second embodiment has high airtightness.
In the second embodiment, a pipe 53 is branched from the pipe 22, which communicate the nitrogen gas cylinder 20 to the casting die 12, and communicated to the decompression pump 52. A valve 54 is provided to a mid portion of the pipe 22. The cavity 12a is communicated to outside by a pipe 55, and a valve 56 is provided to the pipe 55.
In the casting machine of the present embodiment, firstly the valves 24 and 56 are closed and the valve 54 is opened, then the
decompression pump 52 is driven to decompress the casting die 12 and produce the non-oxygen atmosphere therein. Simultaneously, the argon gas is introduced into the furnace 28 from the cylinder 25, and the valve 33 is opened to introduce the argon gas into the tank 36 so as to send the magnesium powders from the tank 36 to the furnace 28. The magnesium powders are sublimed in the furnace 28, and the magnesium gas is generated. In a state of closing the valves 54 and 56, the valve 45 is opened to introduce the magnesium gas into the casting die 12 together with the argon gas.
Next, the valve 54 is closed and the valves 24 and 54 are opened to introduce the nitrogen gas into the casting die 12 from the cylinder 20. By introducing the nitrogen gas into the casting die 12, the magnesium gas and the nitrogen gas are mutually reacted, so that powders of the magnesium-nitrogen compound are precipitated on the inner faces of the cavity 12a.
In this state, the molten aluminium is cast in the cavity 12a by moving the press die section 51 upward. At that time, the inner faces of the cavity 12a, which is constituted by the inner faces of the upper die section 50 and the inner face of the press die section 51, is covered with the magnesium nitride compound, forming the oxide film on the molten aluminium 18 can be prevented while casting as well as the first embodiment.
In the present embodiment, the inner faces of the cavity 12a are heat-treated to form triiron tetroxide. In Fig. 3, a symbol 12b stands for the heat-treated layer of triiron tetroxide. The layer of triiron tetroxide does not react on the magnesium nitride compound on the inner faces of the cavity 12a. Therefore, the deoxidizing function of the magnesium nitride compound can be maintained, so that the oxide film on the molten aluminium 18 can be effectively deoxidized. Besides the heat-treatment,
the inner faces of the cavity 12a can be effectively treated by nitriding. When the molten metal 18 is poured and the press die section 51 pressurizes to cast, the valve 56 is opened to easily pour the molten aluminium 18.
The casting machine 10 of a third embodiment will be explained with reference to Fig. 4. In the above described embodiments, the magnesium gas is made outside of the casting die 12. In the third embodiment, as shown in Fig. 4, a heater section 32a, which includes a heat conducting member 71, a heater 72 for heating the heat conducting member 71 and a heat insulator for preventing heat conduction to the casting die 12 and maintain temperature of the heat conducting member 800°C or more, is provided to a bottom part of the casting die 12. With this structure, the magnesium in the casting die 12 can be sublimed, and the magnesium gas can be generated therein.
In the present embodiment, the cavity 12a of the casting die 12 is decompressed by the decompression pump 52, or an inert gas, e.g., argon gas, is introduced into the cavity 12a so as to purge the air therefrom. Then, the magnesium is heated and sublimed in the cavity 12a of the casting die 12, and the nitrogen gas is introduced into the cavity 12a from the cylinder 20 so as to precipitate the magnesium nitride compound on the inner faces of the cavity 12a.
The inner faces of the cavity 12a are coated with a non-oxidizing material 12c. When the magnesium nitride compound is made, the non-oxidizing material 12c does not react on the magnesium nitride compound, so that the deoxidizing function of the magnesium nitride compound can be maintained. When the molten aluminium 18 is poured into the casting die 12, the oxide film formed on the surface of the molten aluminium 18 can be deoxidized and removed, so that the casting can be executed with pure aluminium. By casting with the pure aluminium, high
quality products, which have no crinkles and surface defects, can be cast.
Another example of the casting die 12, which has an inlet of the magnesium gas and an inlet of the nitrogen gas, will be explained with reference to Fig. 5. In the casting die 12, the plug 16 is attached in a sprue 11a and capable of moving in the vertical direction. The sprue 11a is communicated to the cavity 12a via a pouring path 11b. The magnesium inlet 44a is communicated to a mid portion of the pouring path 11b and connected to the pipe 42. The cavity 12a is formed between headers 23a and 23b, which are vertically arranged. The nitrogen inlet 22a and/or a decompression hole 17a is formed in the headers 23a and 23b. The headers 23a and 23b and the cavity 12a are communicated via a communication path 15. Preferably, one of the magnesium inlet 44a, the nitrogen inlet 22a and the decompression hole 17a is used as an air ventilation hole, from which the air in the cavity 12a is discharged, when the molten metal 18 is poured into the cavity 12a.
In the casting die 12 of the present example too, the nitrogen gas is introduced into the cavity 12a via the nitrogen inlet 22a so as to purge the air from the cavity 12a, then the magnesium gas is introduced into the cavity 12a via the magnesium inlet 44a together with the argon carrier gas. Further, the nitrogen gas is introduced into the cavity 12a so as to make the magnesium nitride compound in the cavity 12a. In the case of previously decompressing the cavity 12a, the decompression may be executed via the decompression hole or holes 17a.
As shown in Fig. 5, the magnesium gas and the nitrogen gas are introduced into the cavity 12a of the casting die 12 via the different routes, so that closing the pipes 22 and 42 with depositions can be prevented, maintenance can be easy and casting efficiency can be improved.
Figs. 6-8 show other examples, in which the metal, e.g.,
magnesium, is evaporated, and the evaporated metallic gas is introduced into the cavity of the casting die.
In Fig. 6, a fixed amount of the magnesium powders are supplied to the furnace 28. A tank 120, in which the magnesium powders are stored, is communicated to the furnace 28 via a pipe 122, valves 124 and 126 are provided to the pipe 122, and a fixed amount storing section 128 is provided between the valves 124 and 126. The fixed amount storing section 128 is formed into a cylindrical shape, and amount of the magnesium stored therein can be controlled by adjusting a length and/or an inner diameter of the fixed amount storing section 128.
The magnesium is supplied from the fixed amount storing section 128 to the furnace 28. Firstly, the valve 124 is closed and the valve 126 is opened, and the argon gas is introduced into the tank 120 from the cylinder 25 so as to supply a fixed amount of the magnesium powders from the tank 120 to the fixed amount storing section 128. Then, the valve 33 is closed and the valves 30 and 124 are opened so as to introduce the magnesium powders into the furnace 28. At that time, amount and pressure of the argon gas sent from the cylinder 25 are observed by a flow meter 129. With above described structure, the magnesium powders can be securely supplied to the furnace 28.
In Fig. 7, an outer casing 100 is constituted by a heat insulating material, and an upper face is opened. A furnace proper 101 of the furnace 28 is made of a heat-resisting material. A lid 102 covers over the furnace proper 101, and the lid 102 is fixed to a flange section 104 by bolts 103. A heater 105 is provided in a space between the furnace 102 and the outer casing 100 so as to heat the furnace proper 101.
The lid 102 has three opening sections 106, 107 and 108, which are communicated to the furnace proper 101. An introducing pipe 109 is connected to a pipe 26, which is communicated to the tank 36, the
introducing pipe 109 runs through the opening section 106 and goes into the furnace proper 101. A lower end of the introducing pipe 109 is opened near an inner bottom face of the furnace proper 101. A thermocouple 110 runs through the opening section 107 and goes into the furnace proper 101. A discharge pipe 111 is connected to the pipe 42, which communicates to the casting die 12, and runs through the opening section 108. A top end of the pipe 111 is located above the furnace proper 101 and opened in the air.
Six plates 112a-112f, which are made of a heat-resisting material, are arranged, in parallel with prescribed separations, in the vertical direction. The introducing pipe 109 is pierced through thorough-holes bored in the plates 112a-112f. The lower end of the introducing pipe 109 is opened in a space between the inner bottom face of the furnace proper 101 and the lowest plate 112a.
A through-hole 114a is bored in the lowest plate 112a and separated away the introducing pipe 109. The plates 112a-112f respectively have through-holes 114a, 114b and 114, which are arranged zigzag in the vertical direction.
There is provided a partition 116b on a bottom face of the plate 112b. The partition 116b divides a space between the plates 112a and 112b into two parts: one part is communicated to the through-hole 114a; the other part is communicated to the through-hole 114b. Note that, a small gap is formed between a bottom face of the partition 116b and an upper face of the plate 112a. Therefore, the two parts are mutually communicated via the small gap. Partitions 116 are respectively provided in spaces between the adjacent plates 112b-112f, and small gaps are also formed in the spaces as well.
The magnesium gas can be made in the furnace proper 101. Firstly the magnesium powders are supplied into the furnace proper 101 from the
tank 36 by pressure of the argon gas via the pipes 26 and 109. Since the magnesium powders are very light, the magnesium powders are sprayed toward a lower part of the furnace proper 101 together with the argon gas and cattered therein. But an inner space of the furnace is formed into a zigzag space by the plates 112a-112f, so the magnesium powders are sublimed and the magnesium gas is made while the magnesium powders ascend in the zigzag space. It takes a prescribed time to perfectly sublime all magnesium powders. In the furnace 28, the inner space of the furnace proper 101 is vertically divided into a plurality of sub-spaces, and the magnesium powders are supplied, together with the argon gas, to the lowest sub-space of the furnace proper 101, so that scattering the magnesium is limited and it takes the prescribed time to ascend the magnesium powders. With this structure, the magnesium powders can be fully heated and perfectly sublimed, and no magnesium powders are supplied to the casting die 12 via the pipe 111. The magnesium gas in the furnace 28 may be supplied to the cavity 12a of the casting die together with the argon gas, which acts as the carrier gas.
In Fig. 8, magnesium pieces 140 are supplied into the furnace 28, and the magnesium pieces 140 are melted and evaporated therein, so that the magnesium gas can be made and introduced into the cavity of the casting die 12. A gas lock chamber 142, which is airtightly closed and stores the magnesium pieces 140, is formed in an upper part of the furnace 28. A prescribed amount of the magnesium pieces 140 are fallen and supplied into the furnace 28. The magnesium pieces 140 are supplied into the furnace 28 from the gas lock chamber 142 by opening a shutter 144. The magnesium pieces 140 are melted in the furnace 28. After the prescribed amount of the magnesium pieces 140 are supplied to the gas lock chamber 142, a lid 146 is closed and the argon gas is introduced into the gas lock chamber 142 from the cylinder 25. Then, air in the gas lock
chamber 142 is discharged from a discharge pipe 148, so that the non-oxygen atmosphere can be produced in the gas lock chamber 142. The magnesium gas in the furnace 28 can be supplied to the cavity of the casting die 12 together with the argon gas, which is sent from the cylinder 25 and acts as the carrier gas.
Fourth to sixth embodiments, in each of which the magnesium gas and the nitrogen gas are previously reacted outside of the casting die 12 to make the magnesium nitride compound (Mg3N2) and the magnesium nitride compound is introduced into the cavity before pouring the molten metal into the cavity, will be explained with reference to Figs. 9-11.
The casting machine 10 of the fourth embodiment is shown in Fig. 9. The casting die 12 is communicated to the reservoir 14, in which the molten metal 18 is reservoired. By moving the plug 16 upward, a prescribed amount of the molten aluminium 18 is poured into the casting die 12. The nitrogen gas cylinder 20 is connected to the casting die 12 via the pipe 22. The nitrogen gas is introduced into the casting die 12 by opening the valve 24, so that air in the casting die 12 is purged. The gas cylinder 20 is connected to the furnace 28 via the pipe 26, so the nitrogen gas is introduced into the furnace 28 by opening the valve 30. The heater 32 heats the furnace until reaching temperature of 800°C or mote so as to sublime the magnesium powders. The gas cylinder 20 is connected to the tank 36, in which the magnesium powders are stored, via the pipe 34. The tank 36 is connected to a part of the pipe 26, which is located on the furnace 28 side of the valve 30, by the pipe 38. The valve 40 is provided to the pipe 38. The furnace 28 is communicated to the casting die 12 via the pipe 42 and the pipe 44, which is pierced through the plug 16 and projected into the casting die 12. The structure of the connecting section 13, which connects the pipe 22 to the casting die 12, is equal to that of the first embodiment shown in Fig. 2.
The method of deoxidation casting executed in the casting machine 10 will be explained.
Firstly, the valve 24 is opened to introduce the nitrogen gas into the casting die 12 from the cylinder 20 via the pipe 22 until the casting die 12 is fully filled with the nitrogen gas. Air in the casting die 12 is purged and discharged outside via air ventilation holes (not shown). Then, the valve 30 is opened to introduce the nitrogen gas into the furnace 28.
Next, the valves 24 and 30 are closed, and a connecting plug of the pipe 22 is disconnected from the connecting section 13. The valve 40 is opened to introduce the magnesium powders into the furnace 28 from the tank 36 together with the nitrogen gas. The magnesium powders are sublimed in the furnace 28, and the magnesium gas reacts on the nitrogen gas, so that the magnesium nitride compound gas is introduced into the casting die 12 via the pipes 42 and 44. The magnesium nitride compound precipitates on the inner faces of the cavity 12a of the cavity 12 as powders.
Then the plug 16 is moved upward, and the molten aluminium 18 is poured into the casting die 12. The molten aluminium 18 and the magnesium nitride compound react on the inner faces of the cavity 12a of the casting die 12, so that the magnesium nitride compound remove oxygen from the oxide film formed on the surface of the molten aluminium 18 and the the molten aluminuum 18 becomes the pure aluminium. Some oxygen, which has left in the cavity or been included in the molten aluminium 18, becomes magnesium oxide or magnesium hydroxide, but it is involved in the molten aluminium 18. Amount of the magnesium oxide and the magnesium hydroxide are very small and they are chemically stable compounds, so they do not badly influence the aluminium products. An excess gas is discharged outside of the casting die 12 via the air ventilation holes (not shown).
As described above, the magnesium nitride compound removes oxygen from the oxide film formed on the surface of the molten aluminium 18, and oxygen, which has left in the cavity or been included in the molten aluminium 18, becomes the magnesium oxide or the magnesium hydroxide and is involved in the molten aluminium 18. Therefore, no oxide film is formed on the surface of the molten aluminium 18.
By forming no oxide film, the surface tension of the molten aluminium 18 is not made greater, the fluidity, the running property and the wettability of the molten aluminium 18 are improved, and high quality aluminium products having high smoothness can be cast.
Amount and density of the magnesium nitride compound in the casting die 12 is not restricted. Even if the density of the magnesium nitride compound is low, the nitrogen gas and the magnesium nitride compound fill the casting die 12, so that amount of the oxygen in the casting die 12 can be highly reduced and forming the oxide film can be highly prevented.
The nitrogen gas need not be previously introduced in the casting die 12. Namely, a mixed gas of the nitrogen gas and the magnesium nitride compound may be directly introduced into the casting die 12 to discharge the air therefrom.
In the fourth embodiment the deoxidation casting of the present invention is applied to the gravity casting. The method of the present invention is not limited to the embodiment.
The fifth embodiment will be explained with reference to Fig. 10. The casting die 12 for the high pressure casting includes the upper die section 50 and the press die section 51. Unlike the casting die of the fourth embodiment shown in Fig. 9, the casting die 12 shown in Fig. 10 has higher airtightness. The cavity 12a of the casting die 12 is
communicated to the decompression pump 52 via the pipe 53 instead of connecting the pipe 22 (see Fig. 9) for introducing the nitrogen gas. The pipe 55 communicates the cavity 12a to outside of the casting die 12. The valves 54 and 56 are respectively provided to the pipes 52 and 55.
In the present embodiment, the valve 54 is opened and the valve 56 is closed to vacuum the air from the casting die 12 and produce the non-oxygen atmosphere therein before precipitating the magnesium nitride compound in the casting die 12. In this case too, deoxidation does not begin when the magnesium nitride compound is precipitated in the casting die 12, so the magnesium nitride compound can be efficiently used to deoxidize the oxide film formed on the surface of the molten metal 18. Note that, the valve 56 may be opened to easily pour the molten metal 18 into the casting die 12 when the molten metal 18 is poured and the high pressure casting is executed.
The sixth embodiment will be explained with reference to Fig. 11. The tank 36, in which the magnesium powders are stored, is connected to the furnace 28, and the nitrogen gas cylinder 20 and the argon gas cylinder 25 are connected to the furnace 28. The pipe 26, which is connected to the tank 36 and the cylinder 25, and the pipe 22, which is connected to the cylinder 20, are extended near the inner bottom face of the furnace 28. Parts of the 22a and 26a of the pipes 22 and 26 are extended in the furnace 28. A lower end of the pipe 42, which connects the furnace 28 to the casting die 12, is opened in an upper part of the furnace 28.
In the sixth embodiment, firstly the valves 24 and 45 are opened so as to introduce the nitrogen gas into the furnace 28 and the casting die 12 via the pipes 22 and 42, so that the air in the furnace 28 and the casting die 12 are purged or discharged. Then, the valves 24 and 45 are once closed. Note that, the air in the furnace 28 and the casting die 12 may be
purged by opening the valve 30 and introducing the argon gas thereinto.
Next, the valve 30 is closed and the valves 33, 40 and 45 are opened so as to supply the magnesium powders, together with the argon gas, from the tank 36 to the furnace 28. Simultaneously, the valve 24 is opened to introduce the nitrogen gas into the furnace 28. The furnace 28 is heated at temperature of 800°C or more so as to sublime the magnesium powders. The magnesium powders introduced in the furnace 28 are sublimed and the magnesium gas is made, so that the magnesium gas reacts on the nitrogen gas and the magnesium nitride compound, which is an example of deoxidizing compounds, is made. The argon gas sends the magnesium nitride compound to the cavity of the casting die 12 as the carrier gas, and the magnesium nitride compound precipitates on the inner faces of the cavity as powders.
While the magnesium nitride compound precipitates on the inner faces of the cavity, the molten aluminium is poured into the cavity. In the cavity, the molten aluminium reacts on the magnesium nitride compound on the inner faces of the cavity, so that the oxide film formed on the surface of the molten aluminium can be deoxidized while casting.
A seventh embodiment, in which a magnesium gas generating device is separated from a reaction chamber, e.g., the furnace 28, will be explained with reference to Fig. 12. A casing of a main part 151 of the magnesium gas generating device 150 is made of a heat insulating material. The main part 151 is heated, by the heater 32a, to temperature of 800°C or more. The pipe 26, which is connected to the tank, in which the magnesium powders are stored, and the argon gas tank, is connected to the main part 151. The main part 151 is connected to the furnace 28 by a pipe 152. The nitrogen gas cylinder 20 is communicated to the furnace 28 via the pipe 22.
In the present embodiment, the magnesium powders are supplied
into the magnesium gas generating device 150, by the argon gas, via the pipe 26. The magnesium powders supplied are heated and sublimed, so that the magnesium gas is generated. The magnesium gas is introduced into the furnace 28 via the pipe 152. Preferably, the pipe 152 is heated by a heater 154 to maintain temperature of the magnesium gas.
The nitrogen gas is introduced into the furnace 28 via the pipe 22. The pipes 152 and 22 are opened and mutually faced in the furnace 28, so that the magnesium gas and the nitrogen gas collide in the furnace 28. By introducing the magnesium gas and the nitrogen gas into the furnace 28, the both gasses react, and the magnesium nitride compound (the deoxidizing compound) is made.
The high temperature of the furnace 28 is maintained by the heater 33, so the reaction of the both gasses is accelerated, and the active deoxidizing compound is introduced into the cavity 12a of the casting die 12 with high temperature. Therefore, the deoxidizing compound efficiently react on the molten metal. Preferably, the furnace 28 is provided on the casting die 12 to make a distance to the cavity 12a short. A communicating path 156 communicates the furnace 28 to the sprue of the casting die 12 or a part near the cavity 12a. Since the molten metal reacts on the deoxidizing compound immediately before the molten metal enters the cavity 12a, the fluidity of the molten metal in the cavity 12a can be improved, so that the molten metal can be effectively cast.
In the above described embodiments, the pure aluminium is used as the molten metal, but other metallic materials, e.g., aluminium alloy including silicon, magnesium, copper, nickel, in, may be used as the casting metal. In the present invention, the word "aluminium" includes aluminium alloy.
Besides the aluminium and the aluminium alloy, other metals, e.g., magnesium, iron, and their alloy can be cast in the present invention.
The invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
What is clamed is
1. A method of deoxidation casting, comprising the steps of:
reacting a deoxidizing compound, which is made by reacting a metallic gas on a reactive gas, on a molten metal; and
deoxidizing an oxide film on a surface of the molten metal.
2. The method according to claim 1,
wherein said deoxidizing compound is made by respectively introducing said metallic gas and said reactive gas to a cavity of a casting die and reacting said both gasses, and
casting is executed by pouring said molten metal into the cavity.
3. The method according to claim 2,
wherein the said metallic gas and said reactive gas are respectively introduced into the cavity 12a via introducing holes, which are formed in the casting die and communicated to the cavity.
4. The method according to claim 2,
wherein said deoxidizing compound is precipitated on an inner face of the cavity of the casting die.
5. The method according to claim 2,
wherein an inert gas is used, as a carrier gas, for introducing said metallic gas into the cavity of the casting die.
6. The method according to claim 2,
wherein said gas is introduced into the cavity of the casting die
after a non-oxygen atmosphere is produced in the cavity.
7. The method according to claim 6,
wherein the non-oxygen atmosphere is produced by decompressing the cavity of the casting die.
8. The method according to claim 6,
wherein the non-oxygen atmosphere is produced by introducing an inert gas into the cavity of the die and purging air therefrom.
9. The method according to claim 2,
wherein the cavity is pressurized by a gas, which reacts on said deoxidizing compound in the cavity, and
the molten metal is poured into the pressurized cavity.
10. The method according to claim 1,
wherein said metallic gas and said reactive gas are reacted outside of the casting die so as to make said deoxidizing compound, and
said deoxidizing compound is introduced into the cavity of the casting die, then the molten metal is poured into the cavity.
11. The method according to claim 10,
wherein an inner gas introduces said deoxidizing compound into the cavity of the casting die as a carrier gas.
12. The method according to claim 10,
wherein a non-oxygen atmosphere is produced in the cavity, then said deoxidizing compound is introduced into the cavity.
13. The method according to claim 12,
wherein the non-oxygen atmosphere is produced by decompressing the cavity of the casting die.
14. The method according to claim 12,
wherein the non-oxygen atmosphere is produced by introducing an inert gas into the cavity and purging air therefrom.
15. The method according to claim 10,
wherein the cavity is pressurized by a gas, which reacts on said deoxidizing compound in the cavity, and
the molten metal is poured into the pressurized cavity.
16. The method according to claim 1,
wherein said deoxidizing compound reacts on the molten metal so as to deoxidize the oxide film on the surface of the molten metal when the molten metal is poured into the cavity.
17. A method of aluminium casting,
comprising the steps of:
reacting a magnesium nitride compound, which is made by reacting a magnesium gas on a nitrogen gas, on a molten aluminium; and
deoxidizing an oxide film on a surface of the molten aluminium by said magnesium nitride compound.
18. The method according to claim 17,
wherein said magnesium nitride compound is made by respectively introducing said magnesium gas and said nitrogen gas to a cavity of a casting die and reacting said both gasses, and
casting is executed by pouring said molten aluminium into the cavity.
19. The method according to claim 18,
wherein an argon gas is used, as a carrier gas, for introducing said magnesium gas into the cavity of the casting die.
20. The method according to claim 17,
wherein said magnesium gas and said nitrogen gas are reacted outside of the casting die so as to make said magnesium nitride compound, and
said magnesium nitride compound is introduced into the cavity of the casting die, then the molten aluminium is poured into the cavity.
21. The method according to claim 20,
wherein an argon gas is used, as a carrier gas, for introducing said magnesium gas into the cavity of the casting die.
22. A deoxidation casting machine, in which a magnesium nitride compound, which is made by reacting a magnesium gas on a nitrogen gas, is reacted on a molten aluminium and an oxide film on a surface of the molten aluminium is deoxidized by the magnesium nitride compound,
comprising:
a casting die having a cavity, into which a molten alminium is poured so as to cast the aluminium into a prescribed shape;
means for introducing the nitrogen gas into the cavity;
a furnace for generating the magnesium gas by heating and subliming a magnesium; and
means for introducing the magnesium gas from said furnace to the
cavity of said casting die together with a carrier gas so as to make the magnesium nitride compound by reacting the magnesium gas on the nitrogen gas in the cavity.
23. A deoxidation casting machine, in which a magnesium nitride compound, which is made by reacting a magnesium gas on a nitrogen gas, is reacted on a molten aluminium and an oxide film on a surface of the molten aluminium is deoxidized by the magnesium nitride compound,
comprising:
a casting die having a cavity, into which a molten alminium is poured so as to cast the aluminium into a prescribed shape;
a reaction chamber being separated from said casting die;
means for introducing the nitrogen gas and magnesium into said reaction chamber; and
. means for introducing the magnesium nitride compound, which is made in said reaction chamber by reacting the magnesium gas, which is generated by heating and subliming the magnesium, on the nitrogen gas, into the cavity together with a carrier gas.
This invention relates to a device for casting strips of metal, in particular steel, in
twin-roll continuous casting machines having counter-rotating casting rolls.
Liquid metal is fed into a space bound by two side walls, between the rotating
casting rolls. The gaps, which are formed between the side walls. The rotating
casting rolls are sealed by a sealing means for generating electrodynamic forces,
that, following the gap profile, act essentially parallel to the casting-roll surface.
The sealing means is constructed so as to continuously adapt the electrodynamic
forces to the metallostatic pressure or approximately to the metallostatic
pressure of the liquid metal.

Documents:

00388-cal-2001-abstract.pdf

00388-cal-2001-claims.pdf

00388-cal-2001-correspondence.pdf

00388-cal-2001-description (complete).pdf

00388-cal-2001-drawings.pdf

00388-cal-2001-form 1.pdf

00388-cal-2001-form 18.pdf

00388-cal-2001-form 2.pdf

00388-cal-2001-form 26.pdf

00388-cal-2001-form 3.pdf

00388-cal-2001-letter patent.pdf

388-CAL-2001-FORM-27.pdf


Patent Number 210814
Indian Patent Application Number 388/CAL/2001
PG Journal Number 41/2007
Publication Date 12-Oct-2007
Grant Date 10-Oct-2007
Date of Filing 11-Jul-2001
Name of Patentee NISSIN KOGYO CO. LTD.
Applicant Address 840 OOAZA KOKOBU, UEDA-SHI, NAGANO 386-8505
Inventors:
# Inventor's Name Inventor's Address
1 BAN KEISUKE 840 OOAZA KOKOBU, UEDA-SHI, NAGANO 386-8505
2 OGIWARA KOICHIA -DO-
PCT International Classification Number c 22 c 001/00
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 NA