KR20200015343A - Mold for growing carbon materials having various shapes and method for growing carbon materials using the same - Google Patents

Abstract

The present invention relates to a mold for growth of carbon bodies of various shapes and a carbon body growth method using the same. The present invention provides the mold for growth of the carbon body which includes a mold (M) for growing the carbon body, the mold (M) made of iron-copper alloy; and the carbon body growth method using the same. According to one embodiment, the mold (M) comprises: a mold main body (10); a cavity (20) formed in the mold main body (10) and having a three-dimensional space; and a carbon source inlet/outlet (30) for injecting and discharging a carbon source into the cavity (20). According to the present invention, the carbon body such as graphene can be stably grown (generated) to have high efficiency and various shapes.

Description

Mold for carbon body growth of various shapes and carbon body growth method using the same {MOLD FOR GROWING CARBON MATERIALS HAVING VARIOUS SHAPES AND METHOD FOR GROWING CARBON MATERIALS USING THE SAME}

The present invention relates to a carbon body growth mold capable of growing carbon bodies, such as graphene, and a carbon body growth method using the same. According to one embodiment, a carbon body such as graphene is highly efficient and various. It relates to a carbon body growth mold capable of growing (producing) to have a shape and a carbon body growth method using the same.

Carbon bodies such as graphene and graphite are used in various industries. Graphene has a plate-shaped two-dimensional crystal structure in which carbon atoms are connected in a hexagonal shape, and graphite has a structure in which graphene of the two-dimensional crystal structure is stacked. These carbon bodies have excellent electrical, thermal, and optical properties, and thus their application ranges are widening.

For example, graphene is attracting attention as a semiconductor material that can replace silicon in the future because it is structurally and chemically stable and its carrier mobility is higher than that of silicon. In addition, graphene is very useful for electric devices such as electrodes for display elements and electrodes for solar cells because of excellent transparency and conductivity.

In general, graphene is manufactured by a method such as mechanical peeling, chemical separation, epitaxy synthesis, and chemical vapor deposition (CVD).

The mechanical peeling method is obtained by attaching scotch tape to graphite to remove the graphene and then separating the graphene stuck to the scotch tape. This mechanical exfoliation served to rapidly disperse early graphene research. However, the mechanical exfoliation method is difficult to break the graphene and graphite pieces together with the graphene in the process of separating the graphene from the Scotch tape, and use analytical equipment such as a microscope and a Raman spectrometer to separate and recover only the graphene. There is this.

Chemical separation is a method of chemically treating graphite to separate graphene. In other words, in the chemical separation method, the graphene is oxidized and then crushed through ultrasonic waves to obtain graphene oxide dispersed in an aqueous solution, and then the graphene is separated by returning it back to graphene using a reducing agent such as hydrazine. Way. This chemical separation method has the advantage of producing a large amount of graphene. However, in the chemical separation method, since graphene oxide is not completely reduced, physical properties such as electrical properties are inferior to those of other methods, which is also complicated by chemical processes of various processes. There is a problem that the crystal structure and properties may be damaged.

The epitaxy synthesis method heat-treats a polar material such as silicon carbide (SiC) at high temperature to selectively evaporate the silicon on the surface, and the carbon component remains on the surface to crystallize the surface of the silicon carbide. Therefore, it is a method of growing graphene. This epitaxy synthesis method has a monotonous advantage compared to the chemical separation method. However, graphene produced through epitaxy synthesis has low electrical properties, and silicon carbide (SiC) itself is expensive, and thus economical.

Chemical vapor deposition is a method of growing (synthesizing) graphene using a metal that adsorbs carbon at a high temperature as a catalyst layer, which is also called a catalytic method. That is, the chemical vapor deposition method forms a metal catalyst layer on a substrate, and then reacts graphene generating gas (carbon-containing gas such as C ₂ H ₄ ) at a high temperature of about 1,000 ° C. or higher to allow carbon to be adsorbed onto the catalyst layer and then cooled To crystallize carbon atoms adsorbed on the metal catalyst layer to grow (synthesize) graphene. Thereafter, the graphene grown on the metal catalyst layer is obtained by separating the graphene through release separation or etching removal of the metal catalyst layer.

At this time, the metal catalyst layer is mainly used copper (Cu) or nickel (Ni) metal in consideration of the adsorption of carbon atoms. The chemical vapor deposition method has an advantage in that it is possible to produce graphene having significantly improved electrical and optical properties (such as sheet resistance and transmittance) compared to other methods. Therefore, in recent years, such a chemical vapor deposition method is preferred for graphene growth (manufacturing), has been proposed in several prior documents.

For example, Korean Patent Registration No. 10-1451139, Korean Patent Publication No. 10-2016-0134669, Korean Patent Publication No. 10-2018-0039156, Japanese Patent Application Publication No. JP2017-095327 and Japanese Patent Application Publication No. JP2017-171570 et al. Present a related technique.

However, the prior art has the following problems, for example.

First, the metal catalyst layer that provides the surface on which graphene is grown, that is, the metal catalyst layer of copper (Cu) or nickel (Ni), is weak to heat or low in thermal conductivity. For example, in the case of copper (Cu), it deteriorates in a high temperature gas atmosphere, and durability is inferior. In addition, in the case of nickel (Ni), the growth rate and crystallization rate of the graphene is low, and thus the graphene production efficiency is low and it is difficult to stably produce a large area graphene.

In addition, graphene is limited to a planar shape. That is, graphene grown on the conventional metal catalyst layer has a two-dimensional planar shape. Accordingly, the graphene produced according to the prior art can be limited to only flat elements such as display elements in most cases, the application range is narrow.

Korea Patent Registration No. 10-1451139 Korean Laid-Open Patent No. 10-2016-0134669 Korean Laid-Open Patent No. 10-2018-0039156 Japanese Laid-Open Patent No. JP2017-095327 Japanese Laid-Open Patent No. JP2017-171570

Accordingly, the present invention is a mold for growing carbon bodies such as graphene, and can grow carbon bodies such as graphene with high quality and high efficiency, and a carbon body growth mold having excellent durability and a carbon body growth method using the same. The purpose is to provide.

In addition, the present invention is not limited to a planar shape, the carbon body, such as graphene having a variety of shapes, for example, a 3D mold for carbon body growth capable of growing a carbon material having a three-dimensional (3-Dimensions) three-dimensional shape And it is an object to provide a carbon body growth method using the same.

The present invention to achieve the above object,

A mold for growing a carbon body;

The mold provides a mold for growing carbon bodies, which is an iron-copper alloy.

According to an embodiment of the invention, the iron-copper alloy is 55 to 95 atomic percent iron; And 5 to 45 atomic percent copper.

In addition, the present invention,

A mold for growing a carbon body;

The mold is

With the mold body,

It is formed in the mold body, the cavity of the three-dimensional space (cavity),

And a carbon source inlet and outlet for injecting and discharging a carbon source into the cavity.

In this case, the mold may further include a cooling passage formed in the mold body and through which the cooling medium passes.

In addition, the present invention,

A first step of preparing a mold including an mold body of an iron-copper alloy and a cavity formed in the mold body and having a cavity of a three-dimensional space;

A second step of heating the mold;

A third step of growing a carbon body by supplying a carbon source to a cavity of the heated mold; And

It provides a carbon body growth method comprising a fourth step of cooling the mold.

The present invention also provides a carbon body produced by vapor deposition of a carbon source and having a three-dimensional solid shape. The carbon body may be, for example, graphene.

According to the present invention, it is possible to grow carbon bodies such as graphene with high quality and high efficiency. Moreover, it is excellent in durability at least, and has long life characteristic.

Further, according to the present invention, it has the effect of growing (manufacturing) carbon bodies having various shapes such as three-dimensional solid shapes as well as two-dimensional planar shapes. Accordingly, the carbon body can be used not only in flat devices such as display devices, but also in various industrial fields in which three-dimensional shapes are required, and its application range is wide.

In addition, according to the present invention, the cooling efficiency is improved by having an optimal cooling flow path, and with this, the design of various cooling flow paths is possible.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing of the carbon body growth metal mold which concerns on 1st Embodiment of this invention.
2 is a cross-sectional configuration diagram of a carbon body growth die according to a second embodiment of the present invention.
3 is a BH curve of the Fe-Cu alloy prepared according to the embodiment of the present invention.
Figure 4 is a SEM photograph of the magnification of the Fe-Cu alloy particles prepared according to the embodiment of the present invention.
5 is an EDS analysis result of the Fe—Cu alloy particles prepared according to the embodiment of the present invention.
6 is an EDS analysis result of the Fe—Cu alloy particles prepared according to the embodiment of the present invention.
7 is an EDS analysis result of the Fe—Cu alloy particles prepared according to the embodiment of the present invention.
8 is an SEM photograph of a particle specimen according to a comparative example.

As used herein, the term "and / or" is used in a sense including at least one or more of the components listed before and after. As used herein, the term "one or more" means one or more than one. In addition, the terms "first", "second", "one side" and "other side" used in the present invention are used to distinguish one component from another component, and each component is used as the term. It is not limited by them.

According to a first aspect, the present invention provides a die for growing carbon body for growing a carbon body. This invention provides the carbon body growth method (manufacturing method) which grows a carbon body using the metal mold | die which concerns on said 1st form according to 2nd aspect. The present invention also provides a carbon body grown in accordance with the first aspect and / or the second aspect in accordance with the third aspect.

In the present invention, the "carbon body" is included in the present invention as long as it has a crystal structure of carbon (C) atoms. The carbon body may be selected from, for example, graphene, graphite, fullerene, carbon nanotubes and / or carbon nanofibers. That is, the carbon body grown according to the present invention may be one or two or more composites selected from graphene, graphite, fullerene, carbon nanotubes and carbon nanofibers. In one example, the carbon body may include at least graphene. In another example, the carbon body may include a composite of graphene and graphite.

The carbon bodies are as well known. For example, the graphene has a plate-shaped two-dimensional crystal structure in which carbon atoms are connected in a hexagonal shape, which may include a single layer or ten or less layers of graphene. The graphite has a structure in which graphene of a two-dimensional crystal structure is stacked. In addition, the fullerene includes carbon rings in which carbon atoms are arranged in a pentagon, hexagon, or the like, and the carbon rings are bonded to each other to form a hollow hollow shape (eg, a soccer ball).

1 and 2 show a carbon body growth mold according to an embodiment of the present invention. The accompanying drawings show exemplary embodiments of the invention, which are provided merely to assist in understanding the invention. In the accompanying drawings, in order to clearly express each component and region, the thickness may be enlarged, and the scope of the present invention is not limited by the thickness, size, and ratio shown in the drawings. Hereinafter, in describing the present invention, detailed descriptions of related well-known general functions and / or configurations will be omitted.

1 and 2, the mold for growing carbon body according to the present invention includes a mold M for growing the carbon body. According to an embodiment of the present invention, the mold M is composed of an iron-copper alloy. That is, the material of the mold M is an alloy of iron (Fe) and copper (Cu), which is preferably an iron-copper alloy having a specific composition. The specific configuration for this iron-copper alloy will be described later.

In the present invention, the shape and size of the mold (M) is not limited. The mold M may have, for example, a flat plate or a three-dimensional shape. The mold M may have, for example, an outer shape selected from a square plate shape, a disc shape, a hexahedron, a cylinder shape, and the like, but is not limited thereto.

On the surface S of the mold M, a carbon skin layer C is formed. The carbon skin layer (C) is formed by growing a carbon body, which may be selected from graphene, graphite, fullerene, carbon nanotubes and carbon nanofibers as mentioned above, and includes graphene in one example. do. That is, the carbon skin layer C is a graphene skin formed by growing graphene in one example.

The carbon skin layer C may have various shapes such as a planar shape of 2-Dimensions or a 3-Dimensional three-dimensional shape. According to one embodiment, in the case where the mold M has a flat surface S (for example, a flat plate), a carbon body is grown on the surface S of such a mold M so that a two-dimensional plane is formed. A carbon skin layer C having a shape may be formed. According to another embodiment, when the surface S of the mold M has a shape other than the plane, the carbon skin layer C may have various shapes other than the plane, for example, three-dimensional (3D) three-dimensional shape. Can be. This will be described with reference to FIGS. 1 and 2 as follows.

1 is a cross-sectional configuration diagram of a mold M according to the first embodiment of the present invention. The mold M may have a rectangular parallelepiped shape having a predetermined size (width x length) and thickness in one example. However, the shape of the mold M is not limited to the rectangular parallelepiped, and it may be any one that can provide the surface S on which the carbon skin layer C of various shapes (such as three-dimensional solid shape) can be grown.

According to a preferred embodiment, the mold M includes a mold main body 10, a cavity 20 formed inside the mold main body 10, and a carbon source to be injected and discharged into the cavity 20. It includes a carbon source inlet and outlet 30 for.

The mold main body 10 has an external shape of a rectangular parallelepiped, for example. 1 illustrates a state in which the mold body 10 is cut in the horizontal direction. The mold body 10 may have a structure divided into two or more pieces, and the plurality of divided parts may be joined by high frequency welding to form the mold body 10. In addition, for example, the mold M may further include a cover (not shown), and the cover may be hermetically coupled to an upper portion and / or a lower portion of the mold body 10.

One or two or more cavity 20 may be formed in the mold body 10, which is a three-dimensional space. That is, the cavity 20 is a hollow formed in the mold body 10, which is a three-dimensional space. As shown in FIG. 1, the cavity 20 has a surface S. FIG. The carbon body is grown on the surface S of the cavity 20 to form the carbon skin layer C. At this time, the cavity 20 has various spatial shapes, which have a three-dimensional three-dimensional spatial shape according to the purpose of use and application of the carbon body (graphene, etc.). 1 illustrates a cavity 20 having a “♡” space shape as a heart shape. When the carbon body is grown on the surface S of the cavity 20, a carbon skin layer C having a “♡” shape may be formed. For reference, FIG. 2 shows a cavity 20 in which a carbon skin layer C having a tube shape may be formed.

The mold body 10 as described above implements a carbon body of various shapes. That is, the carbon body of various shapes is realized by the cavity 20 of the three-dimensional space. For example, a carbon body having a three-dimensional three-dimensional shape is grown. At this time, the mold main body 10 in which the cavity 20 of the three-dimensional space is formed is selected from, for example, a metal material, which may be one in which carbon bodies can be grown. The metal body 10 may be composed of a single metal selected from copper (Cu), nickel (Ni), iron (Fe), or the like, or an alloy including one or more metals selected therefrom. Specific examples of the metal body 10 include copper (Cu), nickel (Ni), copper-nickel (Cu-Ni) alloys, copper-aluminum (Cu-Al) alloys, and iron-copper (Fe-Cu). Alloys and the like, and preferably, iron-copper (Fe-Cu) alloys.

The carbon source inlet and outlet 30 is for injecting and discharging the carbon source, which specifically includes an inlet 32 through which the carbon source is injected and an outlet 34 through which the carbon source is discharged. As illustrated in FIG. 1, the entrances and exits 30, 32, and 34 are formed to penetrate from one side of the mold body 10 to the cavity 20.

The carbon source is a raw material for producing a carbon body, which is not particularly limited as long as it contains at least one carbon (C) in the molecule. The carbon source may be selected from, for example, hydrocarbon type or the like. The carbon source may be, for example, at least one hydrocarbon gas selected from acetylene (C ₂ H ₂ ), ethylene (C ₂ H ₄ ), methane (CH ₄ ), carbon dioxide (CO ₂ ), and / or carbon monoxide (CO). It may include, but is not limited to these. In addition, a gas such as hydrogen (H ₂ ) and / or argon (Ar) may be injected and discharged into the carbon source inlet and outlet 30 together with the carbon source.

According to an embodiment of the present invention, the mold M may further include cooling means for cooling the mold body 10. The cooling means may be formed, for example, on the outer surface of the mold body 10. According to a preferred embodiment, the cooling means preferably includes a cooling passage 40 formed inside the mold body 10. Cooling medium is introduced and discharged through the cooling passage 40. The cooling medium may be any one capable of cooling the mold body 10. The cooling medium includes a cooling fluid such as liquid and / or gaseous phase, which may be selected from, for example, cooling water, liquefied nitrogen and / or nitrogen gas.

The cooling passage 40 may be formed to penetrate from one side surface to the other side surface of the mold body 10. In addition, the cooling passage 40 includes a cooling medium inlet 42 formed at one side of the mold body 10 and a cooling medium outlet 44 formed at the other side of the mold body 10. The cooling efficiency is improved by the cooling passage 40. That is, a cooling passage 40 is formed in the mold body 10, and the cooling medium passes directly through the inside of the mold body 10 through the cooling passage 40, so that the mold body 10 may be efficiently cooled. Can be.

The cooling passage 40 may be formed in the mold body 10, and may be formed in the same shape at a position close to the surface S of the cavity 20. Specifically, as shown in FIG. 1, the cooling passage 40 is continuously formed along the circumference of the surface S at a position proximate to the surface S of the cavity 20, and the cavity 20. It is preferable to be formed in the same shape, for example, "♡" shape. As such, when the cooling passage 40 is formed in the same shape near the surface S of the cavity 20, the cooling efficiency may be further improved to generate the carbon skin layer C having a stable crystal structure.

2 is a cross-sectional configuration diagram of the mold M according to the second embodiment of the present invention. Referring to FIG. 2, the mold M includes a mold main body 10, a cavity 20 formed inside the mold main body 10, and a carbon source inlet / out port for injecting and ejecting a carbon source into the cavity 20. 30), wherein the mold body 10 may include a first mold body 10A and a second mold body 10B as a divided structure. At this time, the first mold body 10A and the second mold body 10 are made of an iron-copper alloy, which may be joined by a method such as high frequency welding.

In FIG. 2, the mold body 10 may have a cylindrical outer shape. The cavity 20 formed in the mold body 10 may have a three-dimensional three-dimensional space shape of a tube shape. Accordingly, when the carbon body is grown on the surface S of the cavity 20, the tubular carbon skin layer C may be three-dimensionally formed.

2, when the mold body 10 includes the first mold body 10A and the second mold body 10B, the cooling passage 40 for cooling the first mold passage 10 may include a first cooling passage ( 40A) and the second cooling passage 40B. That is, the cooling passage 40 may include a first cooling passage 40A formed inside the first mold body 10A and a second cooling passage 40B formed inside the second mold body 10B. Can be. In addition, as shown in FIG. 2, the first cooling passage 40A and the second cooling passage 40B are formed along the circumference of the surface S at a position close to the surface S of the cavity 20. The cavity 20 may be formed in the same shape as, for example, a substantially tube shape.

On the other hand, the growth method of the carbon body according to the present invention is included in the present invention as long as the carbon body growth die according to the present invention is used to grow (generate) the carbon body.

According to a specific embodiment, the growth method of the carbon body according to the present invention comprises the first step of preparing a mold (M); A second step of heating the mold (M); A third step of growing a carbon body by supplying a carbon source to the heated mold (M); And a fourth step of cooling the mold (M). In this case, the mold M includes a mold body 10 and a cavity 20 of a three-dimensional space formed inside the mold body 10. A carbon source is supplied to the cavity 20 to grow (generate) the carbon body.

In addition, the second step of heating, for example, can heat the mold (M) at a temperature of 700 ℃ to 1,200 ℃. Specific process conditions of the second step (heating), the third step (growth) and the fourth step (cooling), for example, the heating rate, the injection flow rate of the carbon source, the injection time of the carbon source, the cooling rate and the cooling time The condition may proceed as usual. Among these process conditions, for example, the thickness of the carbon skin layer (C) and / or the number of layers of the carbon body may be controlled by adjusting the injection flow rate of the carbon source and / or the injection time of the carbon source. In addition, the third step (growth) and the fourth step (cooling) as a cycle (cycle), it can be repeated two or more times.

Therefore, according to the present invention, the cavity 20 of the three-dimensional space is formed in the mold body 10, the carbon body is grown by chemical vapor deposition on the surface (S) of the cavity 20 to the carbon skin Layer (C) is formed. In this case, the carbon skin layer C may have various shapes as shapes corresponding to the cavity 20. That is, the cavity 20 inside the mold body 10 may be designed in a desired shape according to the purpose of use and application of the carbon body, and the carbon body may be grown (generated) in various shapes through the cavity 20. Can be. Preferably, as a three-dimensional three-dimensional shape, it can be grown (created) to have various three-dimensional three-dimensional shapes, such as a tube, a hemispherical shape, and a robot joint. Accordingly, the present invention can be widely applied to a planar element such as a display element as well as a medical field and a wastewater treatment field requiring a three-dimensional shape.

In addition, according to the present invention, the cooling efficiency is improved by having the optimum cooling passage 40. Specifically, as mentioned above, the cooling medium 40 passes directly through the inside of the mold body 10 through the cooling passage 40 formed in the mold body 10 can be efficiently cooled the mold body 10. . By such efficient cooling, carbon body generation in the mold main body 10 is controlled, stable crystallization of the carbon body can be achieved, and high quality and high efficiency carbon body can be produced. In addition, various cooling passages 40 can be designed by the three-dimensional shape of the mold body 10.

In addition, the carbon body according to the present invention is included in the present invention as long as it is formed (generated) through the carbon body growth mold of the present invention and / or the growth method of the present invention as described above. According to one embodiment, the carbon body according to the present invention is produced by vapor deposition of a carbon source, and at least the appearance may have a three-dimensional solid shape. In the present invention, the "three-dimensional solid shape" is a shape other than a plane, which means that it has a horizontal-vertical-height (x-y-z) in three-dimensional space, such as a tube or hemispherical shape.

On the other hand, as described above, the mold M, that is, the mold body 10 is composed of an iron-copper alloy. The iron-copper alloy preferably has a specific alloy composition. According to the present invention, it is composed of an iron-copper alloy having a specific alloy composition, so that carbon bodies (graphene and the like) can be produced at least in high quality and high efficiency. In addition, deterioration of the mold main body 10 is prevented and at least durability and the like are improved. Hereinafter, the iron-copper alloy specified in the present invention will be described. The present inventor has presented in Korean Patent Application No. 10-2017-0015982 (Registration No. 10-1910015) for the iron-copper alloy.

The iron-copper alloy constituting the mold body 10 includes iron (Fe) and copper (Cu), and is an iron-based copper alloy having a higher content of iron (Fe) than copper (Cu). The total standard of copper (Cu) includes 55 to 95 atomic percent iron (Fe) and 5 to 45 atomic percent copper (Cu).

The content unit "atomic%" used in the present invention is based on the entire atomic (a sum of Fe and Cu) of iron (Fe) and copper (Cu), which is also known in the metal field as Volume% ”. That is, in the present invention, it may be expressed as atomic% = volume%.

According to a preferred embodiment, the iron-copper alloy does not contain metal elements other than iron and copper. In addition, the iron-copper alloy may include impurities such as carbon (C) and oxygen (O) as unavoidable impurities, but such impurities are very small. Impurities may be inevitably included, for example, at most 0.1 atomic% (0.1 vol%), or at most 0.01 atomic%.

The iron-copper alloy includes an appropriate amount of copper in iron, so that the advantages of iron and copper are well coordinated and have improved properties. The iron-copper alloy has excellent adsorption to carbon atoms upon growth of the carbon body, which also has excellent heat resistance, thermal conductivity and mechanical properties. Specifically, the iron-copper alloy composition specified in the present invention has excellent heat resistance, thermal conductivity, mechanical properties, and the like, compared to copper (Cu) or nickel (Ni) used as a metal catalyst layer in conventional chemical vapor deposition. It has carbon adsorption equivalent or more. For example, it has excellent heat resistance, hardness, wear resistance, and the like compared to copper (Cu) and copper (Cu) alloys, and has higher thermal conductivity and elasticity than nickel (Ni) and nickel (Ni) alloys. In addition, the iron-copper alloy can be welded, and has a high economical efficiency based on inexpensive iron as a base (main component).

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of an iron-copper alloy is demonstrated together, demonstrating the manufacturing method of the said iron-copper alloy. The manufacturing method described below easily implements the production of the iron-copper alloy having the specific composition. However, the iron-copper alloy is not limited to that produced by the manufacturing method described below.

The manufacturing method of the iron-copper alloy (hereinafter, abbreviated as "manufacturing method") is a first step of preparing a melting furnace, a second step of adding iron and copper to the melting furnace to melt to form a molten metal, the molten metal The third step of stabilizing the step and the fourth step of casting by casting the stabilized molten metal in the casting mold. In addition, the manufacturing method may further include a fifth step of obtaining powdery iron-copper alloy particles from the casting obtained through the fourth step as an optional step. Embodiments are described for each process as follows.

[1] melting furnace preparation (first step)

As described above, the iron-copper alloy specified in the present invention contains 55 to 95 atomic% iron and 5 to 45 atomic% copper. The alloy composition specified in the present invention is not a theoretical molten alloy composition. That is, the proportion of iron in excess of the amount that can theoretically be alloyed. This alloy composition is difficult to be made into an amorphous complete alloy through a melting method by melting (molten metal). In general, the molten alloy may be made of iron and copper when the iron content is lower than that of copper (eg, less than 2.5% by volume of Fe content). However, in the case of the alloy composition specified in the present invention, two-phase separation of the Fe-rich phase and the Cu-rich phase occurs in the molten metal, and segregation (which one metal is biased in one place) occurs, resulting in a complete molten alloy having a uniform distribution. It is difficult to make.

As a result of numerous studies to achieve a complete molten alloy with a high iron content, the present inventors have found that without proper segregation (biasing) when the copper content is titrated, the impurities are minimized, and / or the dissolution process is improved. It can be seen that a complete molten alloy is achieved. According to the present inventors, it can be seen that a complete molten alloy is achieved in the case of improving the melting furnace and / or the raw material input method in the melting process according to one embodiment.

In this first step, one embodiment for solving the above problems is provided. According to the first step, a melting furnace for forming a molten iron and copper molten metal is prepared, but the melting furnace uses a melting furnace of high frequency induction heat capable of rapid melting through rapid temperature rise. In addition, it is preferable to use a ceramic melting furnace containing magnesium as a main component. As the ceramic melting furnace, for example, one manufactured by heating a ceramic containing magnesium oxide as a main component at high temperature and firing can be used. Such furnaces readily implement alloys of iron-copper.

According to a preferred embodiment, the melting furnace is used by forming a porous impurity absorbing layer on the inner surface. Specifically, the first process includes preparing a ceramic melting furnace of high frequency induction heat, and forming a porous impurity absorbing layer on the inner surface of the ceramic melting furnace. In this case, the impurity absorbing layer may be formed on the whole or part of the inner surface of the melting furnace, and specifically, may be formed on at least an inner bottom surface and / or a wall inner surface of the melting furnace as a surface in contact with the molten metal.

In addition, the impurity absorbing layer contains at least an impurity absorbent. Specifically, in the surface treatment step, an absorbing layer composition including an impurity absorbent, a resin, and a solvent may be applied to the inner surface of the melting furnace, and then calcined to form a porous impurity absorbing layer. According to the present invention, the porous impurity absorbing layer absorbs and removes impurities (for example, C, O, etc.) contained in the molten iron-copper molten metal and segregates even in the non-theoretical alloy composition. Without complete alloying is achieved. The porous impurity absorbing layer may have a thickness of, for example, 0.5 mm to 2 mm, but is not limited thereto.

The impurity absorbent is not particularly limited as long as it can absorb and remove impurities (for example, C, O, etc.) contained in the molten iron-copper. The impurity absorbent may be in the form of a powder, for example, having a size of 50 to 500 μm. The impurity absorbent may be selected from metal oxides and / or metals, preferably including at least one selected from zirconium silicate and aluminum (Al). The impurity absorbent is more preferably both zirconium silicate and aluminum (Al). At this time, the aluminum (Al) may be used having a high purity of 99.8% by weight or more. The above zirconium silicate and aluminum (Al) as the impurity absorber can remove impurities in the molten metal more effectively than other metal oxides or metals, and are preferable in the present invention. Specifically, the zirconium silicate and aluminum (Al) may completely remove impurities in the molten metal to form a high purity alloy molten metal including only iron and copper. This can also be confirmed by the following examples.

In addition, the resin is not particularly limited as long as it has an adhesive property, and this resin may be any material capable of providing initial adhesion between the inner surface of the melting furnace and the impurity absorbing layer while aggregating the powdery impurity absorbents with each other. In addition, the resin is removed by high temperature heat by sintering to impart porosity to the impurity absorbing layer. The resin may be selected from synthetic resins and / or natural resins. The resin may be solid and / or liquid, which may be, for example, one or more polymers and / or copolymers thereof selected from acrylic, vinyl, epoxy, urethane, silicone, olefin, ester, rubber and the like. Can be selected.

The resin may preferably be a butadiene-styrene-alkyl methacrylate copolymer (Butadiene-Styrene-Alkyl Methacrylate copolymer). The butadiene-styrene-alkyl methacrylate copolymer is, for example, butadiene-styrene-methyl methacrylate copolymer, butadiene-styrene-ethyl methacrylate copolymer and / or butadiene-styrene-butyl methacrylate air Coalescing and the like. In one example, the butadiene-styrene-alkyl methacrylate copolymer may be used having a particle size of 50nm to 500nm. As such, when the butadiene-styrene-alkyl methacrylate copolymer is selected as the resin and one having a nano size is used, it can be quickly removed through calcination and is evenly dispersed between the powdery impurity absorbents. As a result, the cohesion between the impurity absorbents is improved, and a homogeneous and fine porous structure is formed in the impurity absorber layer, thereby improving the absorption and removal capability of the impurity.

The solvent is for dispersibility and applicability, which may be selected from hydrocarbon systems. The solvent may be selected from, for example, alcohols and / or ketones.

In addition, the absorbent layer composition may include 50 to 80% by weight of impurity absorbent, 5 to 20% by weight of resin, and 15 to 40% by weight of solvent in one example. In this case, when the content of the impurity absorbent is less than 50% by weight, the absorption and removal ability of the impurity may be insignificant, and when the content of the impurity absorber exceeds 80% by weight, porosity and applicability may be deteriorated. In addition, when the content of the resin is less than 5% by weight, porosity and adhesion may be lowered, and when the content of more than 20% by weight, the content of the impurity absorbent is relatively low, so that the absorption and removal capability of the impurities may be insignificant. And a solvent is good in the said range in consideration of dispersibility and applicability | paintability.

As described above, when the porous impurity absorbing layer is formed on the inner surface of the melting furnace through the first process, impurities contained in the molten metal are absorbed and removed during the dissolution process to form a homogeneous complete iron-copper alloy, and together with the impurities It is possible to effectively obtain a high-purity iron-copper alloy containing almost no.

[2] dissolution (second process)

An alloy raw material of iron and copper is introduced into the melting furnace. In this case, iron may use high purity pure iron, and the copper may use high purity electrolytic copper. The furnace may be heated by high frequency induction heat by power application. The melting furnace may be maintained at a temperature at which iron and copper can be dissolved. For example, it is preferable to dissolve iron and copper by rapidly heating the melting furnace through high frequency induction heat and maintaining the temperature at about 1,520 ° C to 1,650 ° C. In this dissolution process, stirring may proceed.

In the second process, the iron and the iron in the melting furnace to include 55 to 95 atomic% (or volume%) and 5 to 45 atomic% (or volume%) of iron as the total basis of the iron-copper alloy finally produced. Copper is added and dissolved to form a molten metal. Specifically, the alloy composition is obtained when the total input of iron and copper to the furnace is 55 to 95% by volume of iron and 5 to 45% by volume of copper (that is, volume ratio of iron: copper = 55 to 95: 5 to 45). can do. At this time, when the content of copper is less than 5 atomic% (5 vol%), for example, carbon adsorption, thermal conductivity and / or corrosion resistance may be insignificant. And when the content of copper exceeds 45 atomic% (45% by volume), the iron content is relatively low, for example, the thermal / mechanical properties such as heat resistance, hardness and wear resistance can be lowered.

In accordance with a preferred embodiment of the present invention, in view of the above, in the second step, the melting furnace includes 80 to 95 atomic% iron and 5 to 20 atomic% copper based on the total amount of the iron-copper alloy finally produced. Iron and copper are added and dissolved to form a molten metal. That is, when the total amount of iron and copper input to the furnace is 80 to 95% by volume of iron and 5 to 20% by volume of copper (that is, iron: copper = 80 to 95: 5 to 20 by volume) It is preferable. More specifically, for example, iron and copper may be added to and dissolved in the melting furnace so as to include 80.5 to 95 atomic% iron and 5 to 19.5 atomic% copper. In the case of having such a preferred alloy composition, it has very good carbon adsorption, thermal conductivity, heat resistance, mechanical properties, and the like, and is very useful as a material of the mold M.

According to one embodiment, in introducing iron and copper into the melting furnace, iron and copper are initially added in a volume ratio of 1: 1, rapidly dissolved while stirring, and then iron is further added to the alloy. It can be made to have a composition. In other words, rather than having the alloy composition through a single input, it is initially added in a volume ratio of 1: 1 iron and copper, and then an additional iron is added to the alloy composition of the homogeneous iron-copper. desirable. In addition, it is more preferable to intermittently add little by little at the time of addition of iron. In other words, the addition of iron in small quantities over several times is advantageous for the homogeneous alloy composition.

In addition, in this 2nd process (dissolution process), it can advance, adding a deoxidizer to a melting furnace as usual, deoxidizing (oxidation prevention). In addition, in this 2nd process (melting process), flux can be further added as usual. At this time, the deoxidizer and flux may be used that is commonly used. The deoxidizer may be, for example, 99.8% by weight or more of high purity Al and / or high purity Ti, and the flux may be Al ₂ O ₃ , CaO and / or SiO ₂ , or the like.

[3] stabilization (third step)

The melt formed through the dissolution is stabilized. Stabilization may be performed by interrupting the power supply to the furnace and leaving the molten metal in the furnace for a predetermined time. At this time, the stabilization may proceed by maintaining the molten metal temperature, for example, 1,450 ℃ to 1,520 ℃. By this stabilization, homogenization of iron and copper can be achieved.

[4] foundry (fourth process)

The stabilized molten metal is injected into a casting mold and cast into an alloy casting of a certain form. This 4th process (casting) is based on a normal metal casting process. The casting mold is not particularly limited, and may have a shape of an ingot and a casting piece, or in some cases, a shape of a mold M. In addition, the casting mold may have a cooling function as usual.

In addition, the casting obtained through the fourth process may be post-processed through a process such as conventional heat treatment and / or cooling. The casting may be post-processed through, for example, a process such as annealing, normalizing, quenching and / or tempering. Such post-treatment can improve mechanical strength (tensile strength and hardness, etc.). The casting thus obtained can be used for the manufacture of the mold (M).

[5] granulation (fifth step)

This fifth process is an optional process, through which a powdered iron-copper alloy can be obtained. According to this fifth step, the casting obtained in the fourth step (casting) is redissolved and then sprayed to obtain powdered iron-copper alloy particles. Specifically, the fifth process may include a re-dissolving step of re-dissolving the casting, and a granulation step of spraying the re-dissolved melt to obtain powdered iron-copper alloy particles.

In this case, the remelting step may use the same melting furnace as in the first step. In the re-dissolving step of the fifth process, in order to prevent oxidation of the iron-copper alloy, it is preferable to re-dissolve in a melting furnace of a vacuum. That is, a melting furnace can use a vacuum furnace. In such a vacuum furnace, the casting may be re-dissolved at 1,600 ° C to 1,700 ° C. In the granulation step, the re-dissolved melt may be sprayed at 1,400 ° C. to 1,500 ° C. to granulate the powder. In this case, the granulated powder may have a size of, for example, 0.1 μm to 150 μm. The powdered iron-copper alloy particles thus obtained may preferably have a spherical particulate form.

According to the above manufacturing method, iron-copper alloy containing 55 to 95 atomic% iron and 5 to 45 atomic% copper, which is a non-theoretical alloy composition, but complete alloying without segregation (biasing). In addition, the iron-copper alloy is well coordinated with the advantages of iron and copper, as described above excellent carbon adsorption, thermal conductivity, heat resistance and mechanical properties (tensile strength, hardness and wear resistance, etc.) for the carbon body growth Very useful as a material for the mold (M).

In addition, as described above, according to a preferred embodiment, the iron-copper alloy includes 800 to 95 atomic percent iron and 5 to 20 atomic percent copper. Specifically, it may include 80.5 to 95 atomic% iron and 5 to 19.5 atomic% copper, and more specifically, 82.5 to 90.5 atomic% iron and 9.5 to 17.5 atomic% copper. In the case of such an alloy composition, properties such as thermal conductivity, heat resistance, and mechanical properties are effectively improved.

According to one embodiment, the iron-copper alloy has the same composition as above, but preferably has a thermal conductivity of 70 W / m · K or more. In the case of having such thermal conductivity, the carbon body can be grown with high quality and high efficiency in favor of the growth of the carbon body. According to a specific embodiment, it is preferable that the iron-copper alloy has physical properties of the following (a) to (c). In the case of having the physical properties of the following (a) to (c), it is preferable not only for the growth of the carbon body but also for durability.

(a) Thermal conductivity 70 W / mK or more

(b) tensile strength over 300 N / mm2

(c) hardness of 100 HB or more

The thermal conductivity, tensile strength and hardness are in accordance with conventional measuring methods. The thermal conductivity may be, for example, a value measured at room temperature (20 ° C. to 25 ° C.) according to ASTM E1461 (Laser flash: Thru-plane). And tensile strength is measured according to KS B 0801, hardness may be measured according to KS B 0805.

The thermal conductivity may specifically have 70 to 150 W / m · K, for example, preferably 72 W / m · K or more, and more preferably 75 W / m · K or more. In addition, the tensile strength may have, for example, 300 to 1,350 N / mm 2. And the hardness is Brinell Hardness (Brinell Hardness), which may have a specific H 100 ~ 400 HB, for example. Each of these properties can be optimized according to the application. For example, in the case of the tensile strength and hardness, it can be increased through the post-treatment (such as soaking, quenching and tempering, etc.) as described above, by such a post-treatment tensile strength is 500 N / ㎜ or more, hardness is 200 HB It can have more than.

In addition, the iron-copper alloy preferably has a spherical particulate form. The spherical particulate phase may be implemented through the fifth process. At this time, the iron-copper alloy has a spherical particulate form, for example, may have a size of 0.1㎛ ~ 150㎛. As such, in the case of spherical particles, it can be produced in a mold (M) through a 3D printer. Here, "spherical" does not mean only a perfect sphere, which includes a quasi-spherical as well as a complete spherical.

In addition, in the present invention, the "spherical particles", even though the iron-copper alloy is a non-theoretical alloy composition, iron and copper are uniformly distributed in the alloy and a complete molten alloy is formed without segregation (declination). Means. In this sense, "spherical particles" have a technical significance. In other words, when a complete molten alloy is not achieved, it is difficult to have spherical particulates through spraying. In addition, in the present invention, the "spherical particles" has a technical significance in that the iron-copper alloy molding having a uniform composition can be processed through re-dissolution.

The iron-copper alloy described above is used as a raw material for manufacturing the mold M according to the present invention, that is, the mold body 10. The iron-copper alloy provides a surface S having high carbon adsorption and excellent growth rate. At this time, the mold main body 10 uses an iron-copper alloy casting (an ingot or a cast piece) obtained in the fourth step (casting), or the powdered iron-copper alloy particles obtained in the fifth step (granulation). It can be molded using.

According to one embodiment, the mold body 10 may be manufactured by melting an iron-copper alloy casting (an ingot or cast piece) or an iron-copper alloy particle, and then, for example, injection molding or the like. Through such injection molding, the mold main body 10 having the cavity 20 may be molded.

According to another embodiment, the mold body 10 may be manufactured through 3D printing. Copper (Cu), which is mainly used as a conventional metal catalyst layer, is difficult to 3D printing and welding. However, the iron-copper alloy of the composition specified in the present invention can be 3D printing and welding. For example, when manufacturing the three-dimensional metal mold | die main body 10 shown in FIG. 1, first, a plurality of metal mold pieces are obtained using an iron-copper alloy using a 3D printer. That is, using a 3D printer, the individual mold pieces in which the mold main body 10 shown in FIG. 1 was divided into several pieces are obtained. At this time, the plurality of mold pieces are bonded to each other to have a shape of the mold body 10 shown in FIG. 1. When using such 3D printing, the mold main body 10 which has the cavity 20 of the precise and various shape can be obtained. This is realized because the iron-copper alloy is capable of 3D printing and welding.

For example, when the medical robot joint is manufactured with graphene, first, the scanned robot joint is printed by a 3D printer to obtain a plurality of mold pieces. Then, a plurality of mold pieces are joined to obtain a robot joint mold body 10. At this time, the cavity 20 of the mold body 10 has a robot joint-shaped 3D space. Thereafter, when graphene is grown from the surface S of the cavity 20, a robot joint composed of graphene may be obtained.

Hereinafter, the Example and comparative example of this invention are illustrated. The following examples are provided by way of example only to help understanding of the present invention, whereby the technical scope of the present invention is not limited. In addition, the following comparative examples do not imply prior art, they are provided only for comparison with the examples.

1. Alloy Manufacturing

Example 1

<Melting Furnace>

As a high frequency induction heat melting furnace, a ceramic melting furnace mainly composed of magnesium was prepared. Thereafter, a porous impurity absorbing layer was formed on the inner wall and bottom of the prepared melting furnace. The porous impurity absorbing layer is coated with an absorbent layer composition containing 65% by weight of impurity absorbent, 15% by weight of resin, and 30% by weight of solvent, based on the total weight of the composition, and then heated to a temperature of about 1,150 ° C., It calcined and formed. In this case, zirconium silicate (ZrSiO ₄ ) and Al powder were used as the impurity absorbent, butadiene-styrene-methyl methacrylate copolymer was used as the resin, and isopropyl alcohol was used as the solvent.

<Molten / Stabilized / Foundry>

Iron (purity of about 99.9 wt% pure iron) and copper (electrolytic copper of about 99.9 wt% purity) were initially added to the melting furnace at a volume ratio of 1: 1, and the output was rapidly dissolved while stirring while increasing the output. At this time, in the dissolution process, deoxidizing agent (Al) was added intermittently while deoxidizing. In addition, after confirming the complete dissolution of the added iron and copper through visual observation, in order to increase the iron content of iron was added little by little and completely dissolved at about 1,550 ℃ melt temperature. Thereafter, the power of the melting furnace was cut off and allowed to stand until the molten metal temperature became about 1,500 ° C. Next, the stabilized molten metal was poured into a casting mold, and then cooled to obtain a Fe—Cu alloy ingot.

EXAMPLE 2 AND 3

Compared to Example 1, in order to change the final alloy composition (atomic% of Fe and Cu), the same as in Example 1 except that the addition amount of iron in the melting process was changed to Fe-Cu alloy ingots were obtained.

Comparative Example 1

In forming the porous impurity absorbing layer on the inner surface of the melting furnace, it was carried out in the same manner as in Example 1 except that the type of impurity absorbent was changed. Specifically, it was carried out in the same manner as in Example 1 except that zirconium oxide (ZrO ₂ ) was used instead of zirconium silicate (ZrSiO ₄ ) and Al as the impurity absorber.

Comparative Example 2

Compared to Example 1, the iron and copper in the melting furnace at a 9: 1 by volume ratio, and the inner surface of the furnace was prepared by melting without forming a porous impurity absorbing layer in this Comparative Example 2 Was used as a specimen.

For the Fe-Cu alloy specimens obtained as above, the components were analyzed as follows, and the results are shown in the following [Table 1]. In addition, the thermal conductivity, tensile strength, hardness and permeability of each alloy specimen were evaluated, and the results are shown together in the following [Table 1]. Thermal conductivity is a method of measuring the thermal conductivity of a metal sample, and the density, specific heat, and thermal diffusivity of each alloy specimen were measured, and then evaluated according to ASTM E1461 (Laser flash: Thru-plane). At this time, all the tests were carried out at a temperature of 25 ℃. In addition, tensile strength was evaluated according to KS B 0801, and hardness was evaluated by Brinell Hardness according to KS B 0805. The permeability was evaluated at a frequency of 50 Hz using a permeability measuring instrument (product of Japan, Lee Yeon Electronics Co., Ltd., model name BHU-60).

<Component Analysis>

The weighed alloy specimen was placed in a glass beaker and 10 mL of aqua regia (hydrochloric acid + aqueous sulfuric acid solution) was added to dissolve it. In addition, Fe and Cu were quantified by high frequency inductively coupled plasma emission spectrometry (ICP-AES) according to the following measurement conditions, and converted into concentrations in the sample for analysis.

* Measurement condition of ICP-AES

Measuring device: PerkinElmer Optima 5300DV

Measurement wavelength: 238.204nm (Fe), 327.393nm (Cu)

-Quantitative method: Internal standard method

                 <Component Analysis and Property Evaluation Results of Fe-Cu Alloy>
Remarks
impurities
Absorbent Ingredient composition
(atom%)
Thermal conductivity
[W / mK]
The tensile strength
[N / mm2]
Brinell hardness
[HB]
Permeability
[m _m ] Fe
Cu Example 1
ZrSiO ₄ + Al 89.58 10.42 74.3 327 154 630 Example 2
ZrSiO ₄ + Al 88.32 11.68 76.6 323 143 613 Example 3
ZrSiO ₄ + Al 90.07 9.93 70.5 342 161 637 Comparative Example 1
ZrO ₂ Segregation 56.1 crack - - Comparative Example 2
- Segregation 47.3 crack - -

As shown in Table 1, in the case of the Fe-Cu alloy according to the embodiments, it can be seen that it has a high thermal conductivity of 70 W / m · K or more than the comparative examples. In addition, it can be seen that the Fe-Cu alloys according to the embodiments have a tensile strength of 320 N / mm 2 or more and a hardness of 140 HB or more. In this case, a high tensile strength of 320 N / mm 2 or more means that a complete alloy was formed while the Fe and Cu had a uniform distribution without segregation (declination). In addition, approximately 600 m _m It can be seen that the level of permeability is shown, which means that it has electromagnetic shielding ability. The attached Figure 3 shows the BH curve (magnetization curve) of the alloy according to Example 1, which means that it has a soft magnetic properties.

On the contrary, in the comparative examples, it was found that segregation occurred without a complete alloy. In addition, the crack was generated due to segregation during the measurement of the tensile strength, it was impossible to measure the tensile strength. In addition, in the case of the comparative examples, because the components are non-uniform due to segregation, it can not be accurately evaluated, it is not shown in Table 1. Hardness and permeability are not shown for the same reason.

Table 2 shows the results of evaluation of physical properties according to the post-treatment, which shows the results before and after treatment for the same alloy specimen as in Example 2. Post-treatment was performed by annealing, normalizing, quenching and tempering in a conventional manner.

         <Result of Property Change by Post-treatment of Fe-Cu Alloy>
Remarks
Before treatment
(Example 2) After Treatment (Example 2) Annealed calling out Quenching (900 ℃)
+ Tempering Quenching (1,050 ℃)
+ Tempering The tensile strength
[N / mm2] 323 301 604 1,016 1,311 Elongation
[%] 10 30 15 3 One Brinell hardness
[HB] 143 100 207 282 374

As shown in [Table 2], the Fe-Cu alloy was found to change the physical properties by the post-treatment. For example, when quenching (and tempering) at a temperature of 1,050 ° C., the tensile strength of 1,300 N / mm 2 or more and the hardness of 370 HB or more were found, and the mechanical strength was improved. As such, when the mechanical strength is improved by heat treatment like ordinary pure single metal (such as pure iron), this means that a complete alloy has been achieved.

[Examples 4 to 6]

Compared to Example 1, in order to change the final alloy composition (atomic% of Fe and Cu), except that the addition amount of iron in the dissolution process was carried out in the same manner as in Example 1 each Example Fe-Cu alloy ingot according to (4-6) was obtained. In addition, in the present embodiments, the Fe-Cu alloy ingot obtained through casting was granulated as follows to prepare powdery Fe-Cu alloy particles.

First, the Fe-Cu alloy ingots according to the respective examples (4 to 6) obtained through casting were put in a melting furnace of high frequency induction heat, and the maximum output was applied to redissolve at a temperature of about 1,650 ° C. At this time, the furnace was maintained in a vacuum to prevent oxidation. Next, the redissolved melt was sprayed using an injector to granulate. At this time, the injection chamber was maintained in an argon (Ar) gas atmosphere to prevent oxidation, and the melt was prepared by spraying at a temperature of 1,450 ℃.

4 to 7 show SEM photographs and EDS analysis results of the powdery Fe—Cu alloy particles prepared according to the examples (4 to 6). Figure 4 is a SEM picture of the magnification of the Fe-Cu alloy particles according to Example 4, Figure 5 shows the results of EDS analysis of the Fe-Cu alloy particles according to Example 4. And Figure 6 shows the results of EDS analysis of Fe-Cu alloy particles according to Example 5, Figure 7 shows the results of EDS analysis of Fe-Cu alloy particles according to Example 6.

As shown in Figures 4 to 7, it can be seen that the Fe-Cu alloy particles produced according to each of the embodiments (4 to 6) has a nearly full spherical shape as fine particles of 30㎛ or less. In addition, the three pictures shown at the bottom of Figure 5 shows the distribution of Fe and Cu (Fe: red, Cu: green), it can be seen that the Fe and Cu are uniformly distributed without segregation (biased) have. At this time, among the three pictures shown at the bottom of FIG. 5, the middle picture shows the distribution of Fe (red), the rightmost picture shows the distribution of Cu (green), and the leftmost picture shows the distribution of Fe and Cu. It is seen. As such, the Fe-Cu alloy particles having a perfect spherical shape and showing a uniform distribution mean that Fe and Cu are completely alloys.

On the other hand, Figure 8 attached is a SEM photograph of the particle specimen sprayed using an ingot according to Comparative Example 2. As shown in FIG. 8, in Comparative Example 2, the particles had a non-uniform piece shape due to segregation. This means that no complete alloy has been achieved.

2. Graphene Synthesis

[Examples 7 to 13]

A plate-like graphene growth substrate was manufactured using the Fe—Cu alloy ingot according to Example 2 showing the best thermal conductivity among the examples of Fe-Cu alloy manufacturing. The substrate was washed, and then graphene was grown on the Fe-Cu substrate by CVD.

First, the Fe—Cu substrate was placed in a quartz reaction chamber, and the reaction chamber was heated and annealed. Thereafter, hydrogen (H ₂ ) and ethylene (C ₂ H ₄ ) gas were injected while maintaining the temperature of about 1,000 ° C. to synthesize graphene. At this time, the injection flow rate (sccm) of hydrogen (H ₂ ), the injection flow rate (sccm) of ethylene (C ₂ H ₄ ) and the synthesis time were different according to each embodiment (7 ~ 13). Then, the growth state and thickness of the graphene according to each test specimen were measured using a microscope, a spectrometer, and an image analysis. The above results are shown in the following [Table 3].

[Comparative Examples 3 to 5]

In contrast to Example 7, the graphene growth substrate was made of Ni-Cu alloy. All conditions except the substrate were the same as in Example 7. In addition, the injection flow rate (sccm) of hydrogen (H ₂ ), the injection flow rate (sccm) of ethylene (C ₂ H ₄ ), and the synthesis time were different according to each comparative example (3 to 5). The thickness of the graphene according to each comparative specimen was measured and the results are shown together in the following [Table 3].

 <Graphene thickness measurement results according to the alloy composition and processing conditions of the substrate> Remarks Growth substrate Process conditions
result H ₂
[Cm 3 / min] C ₂ H ₄
[Cm 3 / min] Synthesis time Example 7
Fe-Cu alloy 30 60 30 minutes >> 3 μm Example 8
Fe-Cu alloy 30 60 5 minutes > 3 μm Example 9
Fe-Cu alloy 30 30 1 minute > 2 μm Example 10
Fe-Cu alloy 30 30 30 seconds > 1 μm Example 11
Fe-Cu alloy 30 30 10 sec > 100 nm Example 12
Fe-Cu alloy 30 60 5 sec About 100 nm Example 13
Fe-Cu alloy 30 30 5 sec Not Full Growth Comparative Example 3
Ni-Cu Alloy 30 60 30 minutes <2 μm Comparative Example 4
Ni-Cu Alloy 30 60 5 minutes About 100 nm Comparative Example 5
Ni-Cu Alloy 30 30 30 seconds Not Full Growth

As shown in Table 3, it was found that the use of the Fe-Cu alloy as the substrate (Example) shows a much improved graphene growth rate (thickness) compared to the case of using the Ni-Cu alloy (Comparative Example). Could. As a specimen proceeded under the same process conditions, for example, in comparison with Example 7 and Comparative Example 3, and Example 11 and Comparative Example 5, the Fe-Cu alloy (Example) has a fast growth rate It was found that the large area of graphene grows to a good full growth.

In addition, as shown in [Table 3], it can be seen that the production thickness of graphene varies depending on the C ₂ H ₄ injection flow rate (sccm, cm 3 / min) and the synthesis time as the graphene generation gas. Through these results, at least C ₂ H ₄ It was found that the thickness of the graphene can be controlled by adjusting process conditions such as injection flow rate and synthesis time.

10: mold body 20: cavity
30: carbon source inlet and outlet 40: cooling passage
C: carbon skin layer M: mold
S: surface

Claims (12)

Including a mold (M) for growing a carbon body,
The mold (M) is a carbon-die growth mold, characterized in that the iron-copper alloy.
The method of claim 1,
The iron-copper alloy,
Iron 55-95 atomic%; And
Carbon body growth mold, characterized in that containing 5 to 45 atomic% copper.
The method of claim 1,
The iron-copper alloy,
80 to 95 atomic percent iron; And
5 to 20 atomic percent copper,
A die for carbon body growth, wherein the thermal conductivity is 70 W / m · K or more.
The method of claim 1,
The mold (M),
A mold body 10 of an iron-copper alloy,
It is formed in the mold body 10, the cavity 20 of the three-dimensional space,
And a carbon source inlet and outlet (30) for injecting and ejecting a carbon source into the cavity (20).
The method of claim 4, wherein
The mold (M) is formed in the mold body 10, the carbon body growth mold, characterized in that it further comprises a cooling passage 40 through which the cooling medium passes.
Including a mold (M) for growing a carbon body,
The mold (M),
The mold body 10,
It is formed in the mold body 10, the cavity 20 of the three-dimensional space,
And a carbon source inlet and outlet (30) for injecting and ejecting a carbon source into the cavity (20).
The method of claim 6,
The mold body 10 is a carbon body growth mold, characterized in that composed of at least one metal selected from copper, nickel and iron.
A carbon body growth method comprising using the carbon body growth die according to any one of claims 1 to 7.
A first step of preparing a mold (M) including a mold body (10) and a cavity (20) formed in the mold body (10) in a three-dimensional space;
A second step of heating the mold (M);
A third step of growing a carbon body by supplying a carbon source to the cavity 20 of the heated mold M; And
And a fourth step of cooling the mold (M).
A carbon body produced by vapor deposition of a carbon source and having a three-dimensional solid shape.
Carbon body produced according to the carbon body growth method according to claim 8, having a three-dimensional solid shape.
The method according to claim 10 or 11,
The carbon body is characterized in that it comprises graphene.

Images