KR20110122442A - Method for manufacturing plate article made of armophous alloy or armophous composite - Google Patents

Abstract

PURPOSE: A method for manufacturing a plate-type product of amorphous alloy or amorphous composite is provided to minimize casting defects and achieve good exterior appearances by applying forging effect. CONSTITUTION: A method for manufacturing a plate-type product of amorphous alloy or amorphous composite comprises steps of: casting molten metal into a rod or plate type amorphous alloy insert, heating the insert within a range from the glass transition temperature to the crystallization temperature, and molding the heated insert into a plate shape and cooling the plate. The molding of the insert is implemented by one or more rotary roll pairs, each comprising two rotary rolls that rotate in opposite directions. The temperature of the rotary rolls is maintained below the glass transition temperature of amorphous alloy.

Description

METHODS FOR MANUFACTURING PLATE ARTICLE MADE OF ARMOPHOUS ALLOY OR ARMOPHOUS COMPOSITE}

The present invention relates to a method for manufacturing a sheet of amorphous alloy or amorphous composite material, and more specifically, it can be produced in a beautiful appearance, to minimize casting defects, and to easily control the thickness of the plate, various requirements required for commercialization It relates to a method for producing a plate-shaped product of amorphous alloys or amorphous composite materials that can satisfy the requirements.

As the materials used in the modern industrial society are advanced in industries such as automobiles, aviation, heavy equipment, and electronics, the development of metal materials that exceed the limit characteristics of existing metal materials is absolutely required.

In response to these demands, the properties of metal materials have been improved up to now by various alloy designs, improvement of solidification methods, and subsequent heat treatment, and the materials developed through such efforts are usefully used in actual industrial sites. However, the modern industry wants materials that exhibit excellent properties even under more extreme conditions, and the existing crystalline metal materials and composite materials using the same have been limited in this demand.

On the other hand, the amorphous alloy is an alloy having a disordered and irregular atomic arrangement state that does not form a crystal, due to such a structural feature, in the various physical properties such as strength, hardness, stiffness and corrosion resistance limit the limitations of the existing metal material It is a high-tech new material that can get the characteristics over.

In manufacturing such an amorphous alloy (or amorphous composite material) into a plate used as a base material of various products, a pair of rapid cooling of molten amorphous alloy composition disclosed in Korean Patent Laid-Open Publication No. 2006-73358 As a strip casting method of passing through a casting roll, a method of making a molten alloy of an amorphous alloy composition and then rapidly cooling the molten metal through a casting apparatus has been mainly used.

However, when the plate is manufactured through rapid cooling at a melting point (Tm, melting temperature) or more, as disclosed in the above-mentioned patent, due to the effects of too low melt viscosity, turbulence and peroxidation of alloying components due to high temperature work, etc. Not only is it difficult to manufacture a beautiful sheet material in appearance, it is easy to produce casting defects, and it is not suitable for commercial use in a state of being cast without post-treatment.

The present invention was developed to solve the above-mentioned problems of the prior art, and provides a method of manufacturing an amorphous alloy or amorphous composite material into a plate-like product that can be visually beautiful and minimize casting defects for commercialization. To solve the problem.

In addition, another object of the present invention is to provide a method for producing an amorphous alloy or amorphous composite material in the shape of the final product.

In addition, another object of the present invention is to provide a method for producing a composite material that can composite different materials in the process of manufacturing an amorphous alloy into a plate-like product.

The first aspect of the present invention for solving the problems of the present invention is a method for producing a plate-shaped product made of an amorphous alloy, (a) casting the molten metal to prepare an amorphous alloy input material, and (b) the glass of the input material It is to provide a method comprising the step of heating the input material in the transition temperature (Tg) ~ crystallization temperature (Tx) range, and (c) forming and cooling the heated input material in the form of a plate.

In the present invention, the term 'amorphous alloy' refers to an alloy having an atomic structure of 95% or more in an amorphous state, and may include some impurities or crystallized structure.

The most distinctive difference between amorphous materials over crystalline materials is the glass transition temperature (Tg) and crystallization temperature (Tx), which are not found in crystalline materials. In these two temperature ranges, ΔT (Tg-Tx), the amorphous material changes into a sticky high viscosity state such as crude texture or honey, and in this state, the external applied force can be easily weakened even at room temperature. It can be shaped into a shape.

Method for producing a plate-like product of the amorphous alloy according to the present invention, unlike the prior art to make a plate by passing the molten metal heated above the melting point between the rotating rolls, first to prepare a feed stock of the amorphous alloy of a predetermined shape (feed stock) Then, through the method of heating the input material in the ΔT section and press-molded at this temperature, there is the biggest difference in making a plate-like product having a complicated shape as well as a plate.

A second aspect of the present invention for solving the other problem of the present invention is a method for producing a plate-shaped product made of an amorphous composite material, (a) casting the molten metal to prepare the input material of the amorphous composite material, and (b) It is to provide a method comprising the step of heating to the nucleation temperature (Tn) ~ melting point (Tm) of the crystalline structure of the input material, and (c) forming and cooling the heated input material in the form of a plate.

In the present invention, 'amorphous composite material' refers to a material in which an amorphous structure and a crystalline structure are combined, of which the amorphous structure is 25 to 85 vol.%, And the rest is a material composed of a crystalline structure such as a dendrite phase. .

Because amorphous composites coexist amorphous and crystalline and have a higher melting point and higher viscosity at the same heating temperature than full amorphous alloy materials, it is not only difficult to produce an apparently beautiful plate-shaped product when molded in the same temperature range as an amorphous alloy. It is also difficult for the crystalline structure to be uniformly redistributed within the amorphous matrix after molding. In view of this point, in the case of the amorphous composite material, the heating temperature during molding is in the range of nucleation temperature (Tn) to melting point (Tm) of the crystalline structure. This temperature range is a solid / liquid coexistence area between the liquidus and the solidus, and not only can be superplasticized, but also obtain a crystalline structure that is uniformly redistributed within the amorphous liquid matrix after molding.

In addition, in the first and second aspects of the present invention, in the step (a) is characterized in that the input material is produced in the shape of a rod or plate. Although the shape of the input material may be variously manufactured, it is because the shape of the rod or plate is advantageous to the molding of the step (c). In addition, in the present invention, the 'rod' refers to a form extending in the longitudinal direction and its cross-sectional shape may form a variety of forms, such as circular, oval, polygonal. In addition, in the present invention, the 'plate-like' refers to a form having a wider width than the thickness, the surface structure may include a flat or full or partial uneven structure.

In addition, in the first aspect of the present invention, the viscosity of the input material in the step (b) is characterized in that it is maintained at 1 × 10 ⁵ ~ 1 × 10 ¹⁰ PaS. If the viscosity of the input material is less than 1 × 10 ⁵ PaS, the viscosity is low, which is advantageous for molding, but in order to maintain this viscosity, it may be close to or above the crystallization temperature, and the crystallization may have a viscosity of 1 × 10 ⁵ PaS. This is because molding is difficult when it exceeds ¹⁰ PaS.

In addition, in the first or second aspect of the present invention, the forming of the step (c) is characterized by one or more rotating roll pairs consisting of two rotating rolls rotating in opposite directions. That is, the molding of the step (c) may be molded directly into the final product through a pair of rotary rolls, but may be a method of gradually forming the final product through two or more pairs of rotary rolls. In addition, the first pair of rotary rolls can perform molding in various forms, such as performing only molding, and the rotary rolls arranged at the rear end thereof perform cooling.

Further, in the first or second aspect of the present invention, the rotating rolls are characterized in that they are maintained at or below the Tg of the amorphous alloy or the Tn of the amorphous composite material.

Further, in the first or second aspect of the present invention, the rotary roll pair is characterized in that the first rotary roll pair is wider than the thickness of the final plate and then adjusted to the final thickness before the feed is passed through the roll. It is done.

In addition, in the first or second aspect of the present invention, the final thickness is characterized in that 0.1 ~ 1.0mm.

Moreover, in the 1st or 2nd side surface of this invention, the predetermined shape or pattern is processed so that the predetermined shape or pattern can be transferred to the input material to be shape | molded by a plate on the surface of the said rotary roll. The pattern of the desired shape is formed on the surface of the rotating roll so that the pattern formed on the surface of the rotating pole is transferred when the input material passes through the rotating roll to transfer various patterns to the surface of the plate-shaped product to be formed. It may be. Since the molding according to the invention is carried out in a region capable of superplastic processing of the amorphous material, it is possible to transfer micro- or nano-sized patterns, for example to form holograms on the surface of the final plate-shaped product.

Further, in the first or second aspect of the present invention, at least one of the rotary roll pairs is embossed with a predetermined shape on the surface of one side, and intaglio processing corresponding to the embossing is performed on the surface of the other side. It is characterized by being. When using the rotary rolls embossed and engraved in this way, it is possible to make an egg plate-shaped or honeycomb-shaped plate material, it is possible to make an excellent energy absorber by pasting the plate material thus prepared.

In addition, in the first or second aspect of the present invention, the rotational speed of the rotary roll pair is preferably 1 ~ 10 cm / sec, which is when the feed material exits the rotary roll when the rotational speed is less than 1 cm / sec There is a risk of solidification on the roll and solidification, and when the rotational speed exceeds 10 cm / sec, the rotation of the rotational roll is too fast to give a sufficient cooling effect.

In addition, according to the first or second aspect of the present invention, the steps (a) to (c) is characterized in that it is carried out in a vacuum or inert atmosphere, which is characterized in that the alloy component in the manufacturing process of the amorphous alloy or amorphous composite material It is to prevent oxidation. In the present invention, the 'vacuum' means a vacuum state of 1x10 ^-1 torr or less. In addition, the term "inert atmosphere" refers to maintaining an atmospheric pressure of 300 torr or more in an inert gas atmosphere such as Ar, He, or N.

In addition, a third aspect of the present invention for solving another object of the present invention is a method of manufacturing a composite material of an amorphous alloy and a dissimilar material, (a) casting the molten metal to prepare an amorphous alloy input material, ( b) heating the feed material between Tg and Tx, and (c) forming the heated feed material by placing the heated feed material in a pair of rolls arranged opposite to each other and rotating in opposite directions, between the pair roll and the feed material. By introducing together, it provides a method comprising the step of combining the dissimilar material and the input material.

The method for producing a plate-shaped product of an amorphous alloy or an amorphous composite material according to the present invention can be expected the following effects.

First, compared with the conventional method of manufacturing a plate directly from the molten metal, the amorphous alloy is formed into the final product in the ΔT section, which is considerably lower than the melting point, and can be forged in the forming process. It is possible to manufacture a product having a minimal appearance and a beautiful appearance, which enables direct commercialization.

Second, since molding is performed in the ΔT section where superplasticity is possible, not only the thickness of the plate can be easily adjusted, but also the various 2D / 3D shapes are pre-processed on the rotating rolls, so that the complexities of the macro patterns in the fine patterns such as holograms are complicated. Plate-shaped products of various shapes up to the shape can be manufactured through one process.

Third, when different types of materials are clad together when the amorphous alloy is passed through a rotating roll, a separate composite can be easily produced.

1 is a manufacturing process chart according to the present invention.
2 is a schematic view of a molding apparatus used in the present invention.
3 is a view showing a relationship between a rolling temperature and time and a time nose in the manufacturing method according to the present invention.
4 is a photograph of an amorphous alloy input material prepared according to Example 1 of the present invention.
5 is a photograph of an amorphous alloy plate prepared according to Example 1 of the present invention.
FIG. 6 is a diagram illustrating an XRD analysis result of an amorphous alloy input material and an amorphous alloy plate material prepared according to Example 1 of the present invention. FIG.
7 is a photograph of an amorphous composite plate prepared according to Example 2 of the present invention.
8 is a schematic diagram of a rolling roll used in an amorphous alloy or an amorphous composite plate-shaped product according to an embodiment of the present invention.
9 is a photograph of an amorphous alloy plate-shaped product prepared according to Example 3 of the present invention.

Hereinafter, the present invention will be described in detail with reference to exemplary embodiments of the present invention. However, the technical spirit of the present invention is not limited thereto, but may be variously modified and modified by those skilled in the art.

Example 1

1 is a plate manufacturing process according to the first embodiment of the present invention. As shown in Figure 1, the plate material production according to the first embodiment is made through the input material production, input material heating, plate-forming and cooling process.

The melting of the amorphous alloy for preparing the amorphous alloy input material is mainly performed by vacuum induction melting (VIM) or arc melting (Arc Melting) method.

In the embodiment of the present invention, the VIM method was used. The weighed amorphous raw material was placed in a graphite crucible, charged in a chamber capable of vacuum heating, and then vacuum and Ar purging was performed two or three times, thereby arranging Ar gas at about 350 torr. After filling to an inert gas atmosphere, the temperature of the vacuum chamber is raised to melt the raw materials. At this time, the heating temperature is raised to about 1000 ℃ higher than the liquidus temperature (about 750 ℃) of the amorphous alloy in order to obtain a uniform liquid composition, and after a total of 1 hour of alloying work, Zr: 42.1 atomic%, Ti: 13.8 About 10 Kg of molten metal having a composition of atomic%, Cu: 12.5 atomic%, Ni: 10 atomic% and Be: 22.5 atomic% was prepared.

In the present invention, the amorphous alloy is not limited to the above embodiments, and Zr-based, Ti-based, Ni-based, Fe-based, Mg-based, Cu-based, Al-based, etc. as long as the alloy exhibits Tg and Tx, which are the characteristics of the amorphous alloy. Either can be a subject of the present invention.

In addition, although the graphite crucible was used in the preparation of the amorphous alloy molten metal in the embodiment of the present invention, various types of crucibles such as alumina, magnesia, silica, and zirconia may be used.

The molten metal prepared as described above was injected into a water-cooled copper mold, thereby forming a plate-shaped amorphous input material as shown in FIG. 4. The alloy composition used in the embodiment of the present invention was excellent in amorphous forming ability, and even when injected into a water-cooled mold, a plate-shaped amorphous alloy input material having a thickness of about 2 cm or more could be produced. On the other hand, in the case of using an amorphous alloy having a low amorphous forming ability, it is also possible to use a method such as die casting for melting an amorphous alloy molten metal by induction heating and then preparing an input material having a rod or plate shape through an injection system.

XRD analysis was performed to confirm the amorphous state of the plate-shaped amorphous alloy input material prepared as described above. As shown in FIG. 6, the XRD analysis result was prepared according to the embodiment of the present invention as confirmed by the broad peak. The plate-like input material is in an amorphous state.

2 is a schematic diagram of a molding apparatus 10 used to produce a plate-shaped product using the amorphous alloy input material described above in an embodiment of the present invention. As shown in FIG. 2, the molding apparatus 10 is largely provided with a chamber 100, an input means 200 for introducing an amorphous alloy input material F into the chamber 100, and an amorphous alloy input material F. Heating means 300 for heating), rolling means 400 for rolling and cooling means 500 for cooling the rolled sheet.

The chamber 100 is formed in a substantially rectangular parallelepiped, and a window 110 for identifying the inside of the chamber is formed at one side thereof, and a blowout port (not shown) for taking out the prepared amorphous alloy plate P is formed at the lower side thereof. It is.

The feeding means 200 is disposed on the upper portion of the heating means 300, a fixed portion for fixing the input material (F) is formed at the lower end and the transfer rod 210 to move up and down, and the transfer rod 210 Two slide rods 220 disposed between the slide rods 220 and the slide rods 220 and slidably fixed to the slide rods 220 and connected to the transfer shafts 210 and disposed inside the transfer rods 210. It comprises a drive motor 223 for driving the drive shaft 222. When the driving motor 223 rotates the drive shaft 222, the transfer rod 210 engaged with the drive shaft 222 is vertically moved, and thus the input material F fixed to the lower end of the transfer rod 210 is It is fed at the feed rate of the feed rod (210). At this time, it is possible to adjust the heating temperature of the input material (F) through the transfer speed of the transfer rod (210).

The heating means 300 has the same structure as a general heating chamber, the resistance coil 310 for heating the input material (F) is arranged in the upper portion of the chamber 100 in the vertical direction the rolling means 400 Is disposed directly above.

The rolling means 400 is located above the chamber 100 and consists of a pair of rotary rolls 410a and 410b. The interval between the rotary rolls (410a, 410b) can be adjusted in consideration of the thickness of the final plate.

The cooling means 500 is disposed below the pair of rotary rolls to blow gas such as argon to the plate discharged from the rotary rolls 410a and 410b. On the other hand, in the embodiment of the present invention to use a gas for cooling, it is also possible to use a variety of known cooling methods such as using a rotary roll or oil cooling.

By using the heating means 200 of the molding apparatus 10 having the above structure, the amorphous input material F was first heated to about 400 ° C. This temperature corresponds to a high portion of the ΔT section. Subsequently, an amorphous alloy plate P having a thickness of 0.1 mm as shown in FIG. 5 was prepared by passing through the rotating rolls 410a and 410b at a roll speed of 2 cm / sec and then cooling through an argon gas.

At this time, the surface temperature of the rotary rolls (410a, 410b) may be a method of maintaining the room temperature or heating up to a constant temperature without heating, it is easier to heat to a temperature of less than Tg than room temperature. In addition, an important point in rolling is that the area of the contact area between the rotary roll 410a and the rotary roll 410b via the input material F is very small, so that the temperature of the input material must be a ΔT section to obtain an amorphous surface of the beautiful surface. You can get it. In addition, since the crystallization may proceed if the time for reaching the desired temperature is too long when the input material F is heated, it must be added to the roll at a high speed before the crystallization proceeds. That is, as shown in Figure 3, the rolling process should not pass the time nose (Time nose) to form a crystallization, the amorphous alloy composition used in the embodiment of the present invention is a time nose is about 100 seconds is enough heating time However, in the case of an alloy with a short time-nose, the crystallization can be prevented only after the rapid heating is performed immediately on the rotary roll through a method such as induction heating.

Through this method, it was possible to produce a thin plate as shown in Figure 5, as shown in Figure 6, the XRD measurement result of the amorphous alloy plate produced as a result of the crystallization in the manufacturing process was maintained in an amorphous state .

[Example 2]

In the same manner as in Example 1, a molten metal for preparing an amorphous composite material input material was prepared.

Through the above process, the composition of the molten metal prepared in Example 2 of the present invention is Zr: 56.25 atomic%, Ti: 11.25 atomic%, Cu: 6.88 atomic%, Ni: 5.63 atomic%, Be: 12.5 atomic%, Nb : 7.5 atomic%. On the other hand, any composition can be used as long as it is a composition capable of producing an amorphous and crystalline mixed state in addition to the Ti-based, Fe-based, and Mg-based compounds.

However, in the case of the composition, considering the high melting point and viscosity, unlike the amorphous alloy composition of Example 1, the temperature of the molten metal was maintained at 1200 ℃. The molten metal thus prepared was injected into a copper mold to be cooled in the same manner as in Example 1 to prepare a plate-shaped amorphous input material. Through this process, an input material of a composite tissue in which crystalline and amorphous tissues composed of a dendrite phase is combined in-situ can be obtained.

The amorphous composite material input material thus obtained was manufactured in the same manner using the same plate-forming apparatus 10 as in Example 1, except that the input material before rolling was heated to 880 ° C higher than the Tn (about 850 ° C) of the input material. As a result, as shown in Figure 7 it was possible to manufacture a plate thickness of less than 1mm, even after this process, the structure of the amorphous composite material was maintained.

Example 3

Example 3 of the present invention is an example showing that through the method of manufacturing a plate-shaped product of the present invention, the final shape of the product can be produced immediately.

8 is a schematic diagram of a rolling roll used in an amorphous alloy or an amorphous composite plate-shaped product according to an embodiment of the present invention. As shown in Figure 8, the surface of the rolling roll may be processed in a variety of shapes or patterns.

9 is alternately processed into pyramidal protrusions and grooves on the surfaces of the rotary rolls 410a and 410b of the molding apparatus 10 using the amorphous alloy input material of Example 1, and then the same process as in Example 1 It is a photograph of the product molded under conditions. As can be seen from Figure 9, according to the embodiment of the present invention, it is possible to obtain a product of the final shape that does not require further processing, it is possible to obtain a final shape while producing a sheet material in this way, the surface unique to amorphous This is because replication characteristics can be used in the present invention.

Claims (16)

In the manufacturing method of the plate-shaped product consisting of an amorphous alloy,
(a) casting the molten metal to prepare an amorphous alloy input material;
(b) heating the input material within a glass transition temperature (Tg) to a crystallization temperature (Tx) of the input material; And
(c) forming and cooling the heated input material into a plate shape. In the manufacturing method of the plate-shaped product consisting of amorphous composite material,
(a) casting a molten metal to prepare an input of an amorphous composite material;
(b) heating the nucleation temperature (Tn) to melting point (Tm) of the crystalline structure of the input material; And
(c) forming and cooling the heated input material into a plate shape. The method according to claim 1 or 2,
In the step (a), the input material is characterized in that the rod or plate manufactured. The method of claim 1,
In the step (b), characterized in that the viscosity of the input material is maintained at 1 × 10 ⁵ ~ 1 × 10 ¹⁰ PaS. The method according to claim 1 or 2,
Forming into the plate shape of step (c) is characterized by one or more rotary roll pairs consisting of two rotary rolls rotating in opposite directions to each other. The method of claim 5, wherein
And the temperature of the rotating roll pair is maintained below the Tg of the amorphous alloy. The method of claim 5, wherein
And the temperature of the rotary roll pair is maintained below the Tn of the amorphous composite material. The method of claim 5, wherein
The rotating roll pair wherein the first rotating roll pair is wider than the thickness of the final plate and then adjusted to the final thickness before the feed passes through the roll . The method of claim 8,
The final thickness is 0.1 to 1.0 mm. The method of claim 5, wherein
And a predetermined shape or pattern is processed on the surface of the rotating roll so as to transfer the predetermined shape or pattern to the input material to be molded into the sheet material. The method of claim 5, wherein
The surface of one side of the said rotary roll pair is embossed of a predetermined shape, The surface of the other side is embossed corresponding to the said embossing. The method of claim 5, wherein
And a predetermined shape or pattern is processed on the surface of the rotary roll pair added in addition to the first rotary roll pair so that a predetermined shape or pattern can be transferred to an input material formed of a sheet material. The method of claim 12,
The surface of one side is embossed of a predetermined shape among the said additional pairs of rotary rolls, and the surface of the other side is embossed corresponding to the said embossing process. The method of claim 5, wherein
The rotational speed of the rotary roll pair is 1-10 cm / sec . The method according to claim 1 or 2,
Step (a) ~ (c) is characterized in that it is carried out in a vacuum or inert gas atmosphere. As a method of manufacturing a composite material of an amorphous alloy and a different material,
(a) casting the molten metal to prepare an amorphous alloy input material;
(b) heating the input material between Tg and Tx; And
(c) combining the dissimilar material and the input material by injecting the dissimilar material together between the pair roll and the input material when the heated input materials are disposed to face each other and are formed by inputting to the pair rolls rotating in opposite directions. ;, Including.

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