WO2020075910A1 - Composite material obtained by surface coating functional material, and method for producing same - Google Patents

Abstract

Provided is a composite powder. The composite powder comprises: a base core; and a coating layer comprising a functional material including carbon layers, and surrounding at least a portion of the base core, wherein the functional material may have a carbon to oxygen ratio of 16 or higher.

Description

Composite material by surface coating of functional material and its manufacturing method

The present invention relates to a composite material by a functional material surface coating and a method for manufacturing the same, more specifically, to a composite material by a functional material surface coating comprising a base core and a carbon coating layer surrounding the base core and a method for manufacturing the same It is related.

Functional material coating technology has been actively researched to overcome the limitations of existing materials across industries such as electronic materials, aviation materials, automotive parts, heat dissipation materials, and thermoelectric materials. Partially specialized coating methods (e.g. spin coating, bar coating, dip coating, spray coating, etc.) are used depending on the shape and characteristics of the material to be coated, but the loss and loss of the functional nanomaterial solution generated in the coating Because of the limitations that can only be applied to specific shapes, research on related technologies is essential.

The existing coating method uses a solution in which functional materials are dispersed, and the viscosity is adjusted according to the method such as spin coating, dip coating, bar coating, and doctor blade coating. Set and use a method of coating on a flat film form or spraying a solution with a spray coating or the like. In addition, a sol-gel coating method and a surface oxidation method of a metal oxide are used to manufacture the nano-unit core-shell composite powder, but the coating method of bulk materials of tens of microns or more has a limited number.

Recently, studies on composite materialization have been actively conducted using two or more materials rather than properties of one material such as polymer-ceramic-metal. The composite material field has the advantage of synergistic effect with complementary properties, and accordingly, the coating technology for giving these properties has been gradually developed.

Industrially used coating technology focuses on film-type materials. For example, conventional techniques such as bar coating, inkjet printing, and spin coating are applicable only on a substrate having a uniform thickness, and a coating method is selected according to the dilution and coating type of the solution to be coated. It is specialized in the production of flat film-oriented products, but has limitations in the field of coating of small parts and coating of raw materials before deviceization.

A representative technique applied to small parts is spray coating. This is a method of adsorbing the solution in which the material to be coated is dispersed through the spraying process, and can be applied to curved small parts, but it has the disadvantage of loss of raw materials generated during the spraying process and difficulty in uniform coating. have. In addition, a solgal coating method and a surface oxidation method of a metal oxide are used to manufacture the core-shell composite powder, but there are disadvantages in that the particle size and material are limited.

Various techniques for easily manufacturing a composite powder coated with a functional material have been continuously researched and developed. For example, in the Republic of Korea Patent Registration No. 10-1457024 (Application No .: 10-2013-0002074, Applicant: Kyungdong Hi-Tech Co., Ltd.), antibacterial, deodorizing water-soluble polymer silicate (water glass) having the structure of SiO2 / M2O, Finely pulverize and mix metal or metal oxide and metal salt powders with complex functions such as far-infrared radiation, anion release, etc. so that a water-soluble polymer silicate is coated on the surface of the powder particles, gel it, filter it, dry it, and then fine it again. Disclosed is a method for producing a composite functional ceramic powder obtained by re-pulverization into a powder. In addition, various technologies related to a composite powder coated with a functional material and a manufacturing method thereof are continuously researched and developed.

One technical problem to be solved by the present invention is to provide a composite material by a functional material surface coating capable of coating on a variety of substrates by a simple method and a method of manufacturing the same.

Another technical problem to be solved by the present invention is to provide a composite material by a functional material surface coating with improved electrical conductivity and thermal conductivity and a method for manufacturing the same.

Another technical problem to be solved by the present invention is to provide a composite powder with improved oxidation resistance and corrosion resistance, a manufacturing method thereof, and a composite material by a functional material surface coating including the same, and a manufacturing method thereof.

The technical problem to be solved by the present invention is not limited to the above.

In order to solve the above technical problems, the present invention provides a composite powder.

According to one embodiment, the composite powder includes a base core, and a functional material including a carbon layer, and includes a coating layer surrounding at least a portion of the base core, wherein the functional material has a ratio of carbon to oxygen of 16 It may include the above.

According to one embodiment, in the Raman spectrum (raman spectroscopy) of the functional material may include that the I _2D / I _G value is greater than 0.4 and less than 0.59.

According to one embodiment, the C 1s content of the functional material may include more than 93 wt%.

According to an embodiment, the functional material may include a carbon layered structure in which a plurality of the carbon layers are stacked.

According to one embodiment, the content of the functional material may include more than 0.49 wt%.

According to an embodiment, the base core may include any one of polymer, ceramic, and metal.

According to one embodiment, the polymer may include HDPE (high-density polyethylene), and the metal may include copper (copper).

According to an embodiment, when the base core includes any one of the ceramic and the metal, a bonding material that bonds the base core and the coating layer may be further included.

According to an embodiment, the binding material may include at least one of a silane coupling agent or a grafted polymer.

In order to solve the above-mentioned technical problems, the present invention provides a method for manufacturing a composite powder.

According to one embodiment, the method of manufacturing the composite powder includes preparing a functional material including a carbon layered structure in which a plurality of carbon layers are stacked, mixing the functional material with a base core, and the base core and the And applying vibration to a functional material to form a composite powder coated with a coating layer containing the functional material on the base core, wherein the carbon of the carbon layered structure included in the functional material before being coated is included. The number of layers may include more than the number of carbon layers of the carbon layered structure included in the functional material after being coated.

According to an embodiment, the preparing of the functional material may include inserting ions between a plurality of the carbon layers to prepare the carbon layered structure, heat-treating the carbon layered structure in which ions are inserted, and It may include the ultrasonic treatment of the heat-treated carbon layered structure.

According to an embodiment, the forming of the coating layer may include exfoliating the carbon layer included in the carbon layered structure by vibration.

According to one embodiment, in the step of mixing the functional material with the base core, by controlling the content of the functional material, it may include controlling the electrical conductivity and thermal conductivity of the composite powder.

In order to solve the above technical problems, the present invention provides a heat dissipation composite material.

According to one embodiment, the heat dissipation composite material, a plurality of base cores, surrounding at least a portion of the plurality of base cores, a coating layer comprising a functional material, and a heat dissipation route provided between the plurality of base cores (route) Including, the heat dissipation route may be disposed within the functional material and the heat dissipation resin included in the coating layer.

According to one embodiment, the base core, polyethylene, SEBS, EVA, PMMA, PDMS, PVDF, PTEF, and includes at least one of PP, the functional material is CNT, graphene, graphite, carbon balck, h-BN , Aluminum nitride, Alumina, Silicon nitride, copper, silver, gold, telilium, platinuim.

A method of manufacturing a composite powder according to an embodiment of the present invention includes preparing a functional material including a carbon layered structure in which a plurality of carbon layers are stacked, mixing the functional material with a base core, and the base core and And applying a vibration on the functional material to form a coating layer comprising the functional material on the base core. Accordingly, the composite powder coated with the functional material on the base core may be provided. That is, the method of manufacturing the composite powder according to the embodiment has an advantage in that the functional material can be coated by a simple method of applying vibration on a substrate having a curved surface such as the base core.

In addition, in the composite powder according to the embodiment, the ratio of carbon to oxygen of the functional material included in the coating layer coated on the base core may be 16 or more. Accordingly, a composite powder having improved oxidation resistance and corrosion resistance can be provided.

In addition, the composite powder according to the embodiment, as a functional material is coated on a polymer, ceramic, metal support, etc., it is possible to impart electrical conductivity, thermal conductivity, and the like to the polymer, ceramic material, which is an insulating material. In addition, the composite powder according to the embodiment may be utilized in various component materials such as thermoelectric materials, heat dissipation materials, and electronic materials.

In addition, the composite powder according to the embodiment can be applied to both a liquid phase process, a solid phase process, and a mass production, and thus can be usefully used in manufacturing various molded products related to coating.

1 is a flowchart illustrating a method of manufacturing a composite powder according to an embodiment of the present invention.

2 is a view showing a manufacturing process of a composite powder according to an embodiment of the present invention.

3 is a view showing a functional material contained in a composite powder according to an embodiment of the present invention.

4 is a view showing a composite powder according to an embodiment of the present invention.

5 is an enlarged view of FIG. 4A.

6 is a view showing the separation of the functional material contained in the composite powder according to an embodiment of the present invention.

7 is a perspective view of a heat dissipation composite material according to an embodiment of the present invention.

8 is a front view of a heat dissipation composite material according to an embodiment of the present invention.

9 to 11 are optical pictures showing before and after the functional material according to an embodiment of the present invention is heat-treated.

12 is a graph showing AFM photographs and thickness information of a functional material manufactured according to an embodiment of the present invention.

13 is a graph showing Raman analysis results of a functional material according to an embodiment of the present invention.

14 is an optical photograph of the base core included in the composite powder according to Example 1 of the present invention.

15 is a photograph taken in general of the composite powder according to Example 1 of the present invention.

16 and 17 are optical photographs of the composite powder according to Example 1 of the present invention.

18 is a graph showing Raman analysis results for FIG. 17.

19 is a graph showing the electrical conductivity and thermal conductivity properties of the composite powder according to Example 1 of the present invention.

20 is a graph showing the resistance properties of the composite powder according to Example 1 of the present invention.

21 and 22 are photographs comparing the content of materials included in the composite powder according to Example 2 according to the number of coating times of the functional material.

23 is a general picture for confirming the chemical resistance of the composite powder according to Example 2 of the present invention.

24 is an optical picture for confirming the chemical resistance of the composite powder according to Example 2 of the present invention.

25 to 27 are graphs comparing component changes according to the heat treatment temperature of the base core included in the composite powder according to Example 2 of the present invention.

28 is a general photograph of a composite powder according to Example 3 of the present invention.

29 is an optical photograph of a composite powder according to Example 3 of the present invention.

30 is an optical photograph of the composite powder according to Example 4 of the present invention.

31 is a graph showing optimization of chemical structure and silane coupling agent binding mechanism and content of a composite powder treated with a silane coupling agent according to Example 4 of the present invention.

32 is an optical photograph of a heat dissipation composite material according to an embodiment of the present invention.

33 is a photograph of a thermal radiation composite material according to an embodiment of the present invention taken with an infrared camera.

34 is a graph showing the thermal conductivity of a heat dissipation composite material according to an embodiment of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the technical spirit of the present invention is not limited to the embodiments described herein and may be embodied in other forms. Rather, the embodiments introduced herein are provided to ensure that the disclosed contents are thorough and complete and that the spirit of the present invention is sufficiently conveyed to those skilled in the art.

In the present specification, when a component is referred to as being on another component, it means that it may be formed directly on another component, or a third component may be interposed between them. In addition, in the drawings, the thickness of the films and regions are exaggerated for effective description of the technical content.

Further, in various embodiments of the present specification, terms such as first, second, and third are used to describe various components, but these components should not be limited by these terms. These terms are only used to distinguish one component from another component. Therefore, what is referred to as the first component in one embodiment may be referred to as the second component in another embodiment. Each embodiment described and illustrated herein also includes its complementary embodiment. Also, in this specification, 'and / or' is used to mean including at least one of the components listed before and after.

In the specification, a singular expression includes a plural expression unless the context clearly indicates otherwise. Also, terms such as “include” or “have” are intended to indicate the presence of features, numbers, steps, elements or combinations thereof described in the specification, and one or more other features, numbers, steps, or configurations. It should not be understood as excluding the possibility of the presence or addition of elements or combinations thereof. In addition, in this specification, "connecting" is used in a sense to include both indirectly connecting a plurality of components, and directly connecting.

In addition, in the following description of the present invention, when it is determined that detailed descriptions of related well-known functions or configurations may unnecessarily obscure the subject matter of the present invention, detailed descriptions thereof will be omitted.

1 is a flow chart illustrating a method of manufacturing a composite powder according to an embodiment of the present invention, Figure 2 is a view showing a manufacturing process of a composite powder according to an embodiment of the present invention, Figure 3 is an embodiment of the present invention 4 is a view showing a functional material included in the composite powder, FIG. 4 is a view showing the composite powder according to an embodiment of the present invention, FIG. 5 is an enlarged view of FIG. 4A, and FIG. 6 is an embodiment of the present invention It is a view showing the separation of the functional material contained in the composite powder.

1 to 5, a functional material (FM) is prepared (S100). According to an embodiment, the functional material FM may include a carbon layered structure 10 in which a plurality of carbon layers 10, 11, 12, 13, 14, 15, 16, 17, 18 are stacked. . For example, the functional material (FM) may be expanded-graphite (EG).

According to one embodiment, the step of preparing the functional material (FM), inserts ions (ion) between the plurality of the carbon layer (10, 11, 12, 13, 14, 15, 16, 17, 18) And manufacturing the carbon layered structure 10, heat-treating the carbon layered structure 10 in which the ions are inserted, and ultrasonicating the heat-treated carbon layered structure 10. . For example, ions inserted between a plurality of the carbon layers (10, 11, 12, 13, 14, 15, 16, 17, 18) are H ₂ SO _4, HNO _3, N ₂ O ₅ , CO _2, SO ₂ ions. Specifically, when the carbon layered structure 10 is heat-treated, graphites forming the carbon layers 10, 11, 12, 13, 14, 15, 16, 17, 18 may be expanded. In addition, when the heat-treated carbon stacked structure 10 is ultrasonicated, expanded graphite may be peeled off.

Accordingly, the functional material (FM) has a small defect compared to rGO formed by a chemical method, and crystallinity can be improved. For example, the functional material (FM) may have a ratio of carbon to oxygen (C / O ratio) of 16 or more. In addition, the C 1s content of the functional material may be 93 wt% or more. Specifically, the ratio of carbon to oxygen (C / O ratio) of the functional material FM may be 16.23, and the C 1s content of the functional material may be 93.19 wt%. As the composite powder described below is manufactured through the functional material FM having a relatively high proportion of carbon, oxidation resistance and chemical resistance of the composite powder described below may be improved.

The functional material FM may be mixed with the base core 100 (S200). According to an embodiment, the base core 100 may include any one of polymer, ceramic, and metal. For example, the polymer may include high-density polyethylene (HDPE). For example, the ceramic may include at least one of h-BN, Aluminum nitride, Alumina, and Silicon nitride. For example, the metal may include copper.

According to an embodiment, the content of the functional material FM mixed with the base core 100 may be controlled. Accordingly, the electrical conductivity and thermal conductivity of the composite powder described later can be controlled. For example, as the content of the functional material (FM) mixed with the base core 100 is controlled to be 0.49 wt% or more, electrical conductivity and thermal conductivity of the composite powder described below may be improved.

Vibration is applied to the mixed base core 100 and the functional material FM, so that a coating layer 200 may be formed on the base core 100 (S300). Accordingly, the composite powder according to the embodiment may be formed. The coating layer 200 may include the functional material (FM). In addition, the coating layer 200 may surround at least a portion of the base core 100. That is, when vibration is applied on the mixed base core 100 and the functional material FM, the functional material FM surrounds at least a portion of the base core 100 to cover the coating layer 200. Can form. According to one embodiment, after the coating layer 200 provides the base core 100 and the functional material FM in a mixing vessel V, the mixing vessel V is subjected to acoustic mixing. It can be formed in a way.

Specifically, when the base core 100 includes a polymer (eg, HDPE), in the process of mixing the functional material (FM) on the base core 100, the carbon layered structure 10 Carbon layer (for example, 11) disposed on one side of the plurality of carbon layers (11, 12, 13, 14, 15, 16, 17, 18) contained in the carbon and the surface of the base core 100 Can be combined. On the other hand, the carbon layer 12 excluding the carbon layer 11 disposed on one side of the plurality of carbon layers 11, 12, 13, 14, 15, 16, 17, 18 included in the carbon layered structure 10 , 13, 14, 15, 16, 17, 18) may each be already coupled through a van der Waals force (Pi-Pi bond). Accordingly, a plurality of the carbon stacked structures 10 are combined on the base core 100, and the plurality of carbon stacked structures 10 form the coating film 200 surrounding the base core 100. can do.

On the other hand, when the base core 100 includes any one of the ceramic and the metal, the composite powder according to the embodiment uses a bonding material that bonds the base core 100 and the coating layer 200. It may further include. For example, the binding material may include any one of siloxane-based coupling agents such as Polysiloxane, Siloxane, Silazane, Silanes, and polymers grafted with Vinyl, Amino, Epoxy, Mercapto, and the like. Specifically, when the base core 100 is copper, the bonding material may be polysiloxane. That is, when the base core 100 includes any one of the ceramic and the metal, the functional material FM may be coupled to the base core 100 by the binding material. According to one embodiment, the coating layer 200 provides the base core 100, the functional material (FM), and the bonding material in the mixing container (V), and then vibrates the mixing container (V) It can be formed by a method of applying.

According to an embodiment, the frequency applied may be controlled according to the type of the base core 100. For example, the frequency applied according to the type of the base core 100 may be controlled to 40g (gravity acceleration), 60g, 80g, and the like. More specifically, when the base core 100 includes a polymer, the applied frequency may be 60 g. On the other hand, when the base core 100 includes any one of ceramic and metal, the applied frequency may be 80 g.

In addition, after the first vibration is applied to the base core 100 and the functional material FM, the second vibration may be sequentially applied. For example, the first vibration may be relatively high vibration, and the second vibration may be relatively low vibration. That is, the composite powder may be formed by a method in which low vibration is applied after high vibration is applied to the base core 100 and the functional material FM. As the first vibration (high vibration) is applied to the base core 100 and the functional material FM, the functional material FM can be easily coated on the base core 100. In addition, as the second vibration (low vibration) is applied to the base core 100 and the functional material FM, the peeling ratio of the functional material FM is reduced, and uniformity of coating can be improved. . In addition, when the first vibration (high vibration) and the second vibration (low vibration) are sequentially applied to the base core 100 and the functional material FM, the above-described effects may be simultaneously implemented.

According to an embodiment, as the coating layer 200 is formed through a method in which vibration is applied on the functional material FM and the base core 100, the functional material FM is included before being coated. The number of carbon layers (11, 12, 13, 14, 15, 16, 17, 18) of the carbon layered structure (10), and the carbon layered structure (F) contained in the functional material (FM) after being coated ( The number of carbon layers 11, 12, 13, 14 possessed by 10) may be different from each other. Specifically, the number of the carbon layers (11, 12, 13, 14, 15, 16, 17, 18) of the carbon layered structure (10) included in the functional material (FM) before being coated, after being coated The number of carbon layers 11, 12, 13, and 14 of the carbon layered structure 10 included in the functional material FM may be greater. That is, by the coating process, at least a part of the carbon layers 11, 12, 13, 14, 15, 16, 17, 18 of the carbon layered structure 10 is peeled off, and the carbon layers 15, 16, 17, 18) may be coated on the base core 100, the carbon layered structure 10 is peeled off.

These results can be confirmed by the I _2D / I _G value of Raman spectrum (raman sepectroscopyh). For example, the I _2D / I _G value in the Raman spectroscopy of the functional material (FM) before coating is less than 0.4, and the I _2D / I _G in the Raman spectrum of the functional material (FM) after coating The value can be greater than 0.4 and less than 0.59. This, in the step of forming the coating layer 200, a plurality of the carbon layer (11, 12, 13, 14, 15, 16, 17) of the carbon layered structure (10) included in the functional material (FM) , 18) It can be determined that any one of the carbon layers (for example, 15, 16, 17, 18) is peeled by vibration.

The method of manufacturing a composite powder according to an embodiment of the present invention includes the carbon layered structure 10 in which a plurality of the carbon layers 11, 12, 13, 14, 15, 16, 17, 18 are stacked. Preparing a functional material (FM), mixing the functional material (FM) with the base core (100), and applying vibration on the base core (100) and the functional material (FM), the And forming the coating layer 200 including the functional material FM on the base core 100. Accordingly, the composite powder coated with the functional material FM on the base core 100 may be provided. That is, in the method of manufacturing the composite powder according to the embodiment, the functional material (FM) may be coated on a substrate having a curved surface such as the base core 100 by a simple method of applying vibration. There is an advantage.

In addition, in the composite powder according to the embodiment, the ratio of carbon to carbon (C / O ratio) of the functional material (FM) included in the coating layer 200 coated on the base core 100 is 16 or more. You can. Accordingly, a composite powder having improved oxidation resistance and corrosion resistance can be provided.

In the above, the composite powder according to the embodiment of the present invention and a method of manufacturing the same have been described. Hereinafter, a heat dissipation composite material according to an embodiment of the present invention will be described with reference to FIGS. 7 and 8.

7 is a perspective view of a heat dissipation composite material according to an embodiment of the present invention, and FIG. 8 is a front view of the heat dissipation composite material according to an embodiment of the present invention.

7 and 8, the heat dissipation composite material according to the embodiment may include a plurality of base cores 100, a coating layer 200, and a heat dissipation route (route, 300). According to one embodiment, the base core 100 may include at least one of polyethylene, SEBS, EVA, PMMA, PDMS, PVDF, PTEF, PP.

The coating layer 200 may surround at least a portion of the plurality of base cores 100. According to one embodiment, the coating layer 200 may include a functional material (FM). For example, the functional material (FM) may include at least one of CNT, graphene, graphite, carbon balck, h-BN, Aluminum nitride, Alumina, Silicon nitride, copper, silver, gold, telilium, platinuim . The heat dissipation route 300 may be provided between the plurality of base cores 100. According to an embodiment, the functional material FM included in the coating layer 200 and the heat dissipation resin R may be disposed in the heat dissipation route 300. The heat dissipation route 300 may provide a space in which heat is moved.

That is, the plurality of base cores 100 are respectively surrounded by the coating layer 200 including the functional material FM, and the plurality of coating layers 200 surrounding each base core 100 are connected. Thus, the heat dissipation route 300 may be formed.

According to one embodiment, the composite powder comprising the base core 100 and the coating layer 200 surrounding it is the same as the method for manufacturing the composite powder according to the embodiment described with reference to FIGS. 1 to 6. It can be prepared by a method. That is, after mixing the base core 100 and the functional material FM, the composite powder may be formed through a method of applying vibration. According to one embodiment, a plurality of the composite powder may be prepared. Thereafter, a plurality of the composite powder is agglomerated, and the agglomerated plurality of the composite powder is compressed, so that the heat dissipation composite material according to the embodiment includes a plurality of the base core 100 and the plurality of base cores 100 ), The coating layer 200 surrounding at least a portion, and the heat dissipation route 300 provided between the plurality of base cores 100 may be formed. Thereafter, the heat dissipation material R is provided in the heat dissipation route 300, so that the heat dissipation composite material according to the embodiment may be manufactured.

The heat dissipation composite material according to an embodiment of the present invention surrounds at least a portion of the plurality of base cores 100 and the plurality of base cores 100, and the coating layer 200 including the functional material FM. And the heat dissipation route 300 provided between the plurality of base cores 100, wherein the functional material FM contained in the coating layer 200 in the heat dissipation route 300 and the heat dissipation resin (R) may be disposed. Accordingly, a plurality of the heat dissipation routes 300 are provided inside the heat dissipation composite material according to the embodiment, so that heat dissipation efficiency can be improved.

In the above, the heat dissipation composite material according to the embodiment of the present invention has been described. Hereinafter, specific experimental examples and property evaluation results of the composite powder according to the embodiment of the present invention will be described.

Preparation of functional materials according to embodiments

Expanded Graphite (EG) is prepared. After inserting ions into the prepared EG, heat treatment and ultrasonic treatment were performed to prepare a functional material according to the embodiment.

9 to 11 are optical pictures showing before and after the functional material according to an embodiment of the present invention is heat-treated.

Referring to (a) to (c) of FIG. 9, a functional material according to the above embodiment is prepared, and a functional material in a state before heat treatment is prepared to obtain SEM (magnification at 100 μm, 5 μm, and 500 nm, respectively). scanning electron microscope), and referring to FIGS. 10 (a) to 10 (c), a functional material according to the above example was prepared and SEM photographed at magnifications of 100 μm, 5 μm, and 500 nm, respectively. 9 and 10, it can be seen that the functional material according to the embodiment expands as it is heat-treated.

Referring to (a) to (c) of FIG. 11, the functional material, which has been expanded by heat treatment and peeled by post-treatment, is photographed by TEM (transmission electron microscope) at different magnifications. FIG. 11 (a) shows a segment of graphene constituting the functional material, FIG. 11 (b) is a photograph of the functional material at high magnification, and FIG. 11 (c) shows the SAED of the functional material (selected area electron diffraction) pattern image. As shown in FIG. 11 (b), it was confirmed that the functional material exhibited a lattice structure, and as shown in FIG. 11 (c), the graphene constituting the functional material exhibited a single crystal.

12 is a graph showing AFM photographs and thickness information of a functional material manufactured according to an embodiment of the present invention.

Referring to (a) of FIG. 12, an atomic force microscopy (AFM) photograph of the functional material was taken and illustrated. Referring to (b) of FIG. 12, the thickness of the functional material was measured and graphed. As can be seen through (a) and (b) of FIG. 12, it was confirmed that the functional material according to the embodiment was made of carbon layers having a thin thickness.

13 is a graph showing Raman analysis results of a functional material according to an embodiment of the present invention.

Referring to (a) to (c) of FIG. 13, a functional material according to the above embodiment is prepared, but before the heat treatment, after the heat treatment, and after the ultrasonic treatment, a Raman spectroscopy is shown for each of the states. Did.

As can be seen from FIG. 13 (a), the functional material according to the embodiment before heat treatment is shown as an I _2D / I _G value of 0.34, and the functional material according to the embodiment after heat treatment is an I _2D / I _G value It appeared as 0.40, it was confirmed that the I _2D / I _G value is 0.38 for the functional material according to the embodiment after ultrasonic treatment. That is, it can be seen that the functional material according to the embodiment has a multi-layer regardless of heat treatment or ultrasonic treatment.

In addition, the specific contents and proportions of the components included in the functional material according to the embodiment are summarized through <Table 1> below.

Atomic conc.	C 1s (wt%)	O 1s (wt%)	S 2p (wt%)	N 1s (wt%)	C / O ratio
EX-G	93.19	5.74	0.38	0.68	16.23

Composite powder preparation according to Example 1

Prepare 4 g of high-density polyethylene (HDPE) with a reduced particle diameter through a ball milling process. In addition, after preparing a functional material according to the above embodiment having a concentration of 0.5 wt%, 1 wt%, 3 wt%, 5 wt%, 10 wt%, 20 wt%, and 30 wt%, each functional material and 4 g HDPE was mixed and acoustic mixing was performed for a time of 15 minutes for each. Accordingly, the functional material (EG) is coated on the base core (HDPE), according to Examples 1-1, 1-2, 1-3, 1-4, 1-5, 1-6, and 1-7 Composite powders were prepared.

14 is an optical photograph of the base core included in the composite powder according to the first embodiment of the present invention, and FIG. 15 is a general photograph of the composite powder according to the first embodiment of the present invention.

14 (a) and (b), the base core prepared for the preparation of the composite powder according to Example 1 was shown by SEM imaging at 100 μm and 10 μm magnification. As can be seen from (a) and (b) of FIG. 14, it can be seen that the base core prepared for the production of the composite powder according to Example 1 is a powder in a conical shape with an upper surface curved.

15 (a), before the composite powders according to Examples 1-1, 1-2, 1-3, 1-4, 1-5, 1-6, and 1-7 were prepared, The state in which each base core and the functional material are mixed is shown by taking a general picture, and referring to FIG. 15 (b), the above Examples 1-1, 1-2, 1-3, 1-4, 1- Composite powders according to 5, and 1-6 are shown by general photographing. As can be seen from (a) and (b) of FIG. 15, it was confirmed that the functional material can be easily coated on the base core through the method of manufacturing the composite powder according to Example 1 above.

16 and 17 are optical photographs of the composite powder according to Example 1 of the present invention.

Referring to (a) and (b) of FIG. 16, the composite powder according to Example 1-4 was shown by SEM photographing at a magnification of 500 μm and 250 μm. Referring to FIG. 16 (c), the The composite powder according to Example 1 was shown by TEM imaging at a magnification of 10 nm.

As can be seen from (a) and (b) of Figure 16, it can be seen that the composite powder according to Example 1-4 has a form in which the functional material (EG) surrounds the base powder (HDPE). In addition, as can be seen in Figure 16 (c), the composite powder according to Example 1-4 was formed with a thickness of 8 nm, the functional layer (EG) constituting the coating layer is a plurality of carbon layers are laminated It can be seen that it appears in the old form.

17 (a) and (b), the composite powder according to Example 1-4 was SEM photographed at a different magnification from FIGS. 16 (a) and (b). 17 (a) and (b), it can be seen that the composite powder according to Example 1-4 has a core-shell structure as a whole.

18 is a graph showing Raman analysis results for FIG. 17.

Referring to FIG. 18, a Raman spectroscopy is shown for a functional material of a coating layer included in the composite powder according to Examples 1-4. As can be seen in FIG. 18, it was found that the functional material of the coating layer included in the composite powder according to Example 1-4 has an I _2D / I _G value of 0.59.

That is, as can be seen through comparison of FIGS. 13 and 18, it was found that the I _2D / I _G value increases in the process of coating the functional material according to the embodiment on the base core. This is considered to be a phenomenon that occurs as part of the carbon layer laminated by vibration during the process of coating the functional material on the base core is peeled off. As a result, it can be seen that the functional material of the coating layer included in the composite powder according to Examples 1-4 has an I _2D / I _G value of more than 0.4 and 0.59 or less in a Raman spectroscopy.

19 is a graph showing the electrical conductivity and thermal conductivity properties of the composite powder according to Example 1 of the present invention.

Referring to (a) of Figure 19, to measure the electrical conductivity properties of the composite powder according to the first embodiment, to compare the correlation according to the content of the functional material contained in the composite powder, according to the first embodiment In the process of preparing the composite powder, the content of the functional material mixed with the base core (EG content, wt%) is controlled to 0 to 30 wt%, and the electrical conductivity (S / m) of the composite powder prepared with each content is controlled. ). As can be seen from Figure 19 (a), it can be seen that the composite powder according to Example 1 increases the electrical conductivity as the content of the functional material increases. In particular, it can be seen that the electrical conductivity of the composite powder containing 0.49 wt% of the functional material is significantly improved compared to the previous.

Referring to (b) of Figure 19, to measure the thermal conductivity properties of the composite powder according to Example 1, to compare the correlation according to the content of the functional material contained in the composite powder, according to Example 1 In the process of preparing the composite powder, the content of the functional material mixed with the base core (EG content, wt%) is controlled to 0 to 30 wt%, and the thermal conductivity (W / mK) of the composite powder prepared with each content is controlled. ). As can be seen in Figure 19 (b), it can be seen that the composite powder according to Example 1, the thermal conductivity also increases as the content of the functional material increases.

20 is a graph showing the resistance properties of the composite powder according to Example 1 of the present invention.

Referring to Figure 20, to measure the resistance properties of the composite powder according to Example 1, to compare the correlation according to the content of the functional material contained in the composite powder, the preparation process of the composite powder according to Example 1 In the content of the functional material to be mixed with the base core (EG content, wt%) is controlled to 0 to 30 wt%, it is shown by measuring the resistance (Resistivity) of the composite powder prepared with each content. As can be seen in Figure 20, the composite powder according to Example 1, it was found that the resistance decreases as the content of the functional material increases.

Preparation of composite powder according to Example 2

As the base core, a copper ball with an average diameter of 1 mm and a capacity of 20 g is prepared. After the prepared base core was mixed with 20 ml of the binding material, polysiloxane, and 1 wt% of the functional material (EG) according to the above embodiment, acoustic mixing was performed for a time of 3 minutes. Subsequently, the primary heat treatment was performed at a temperature of 300 ° C. for 1 hour, and a secondary heat treatment was performed at a temperature of 400 ° C. for 5 hours to prepare a composite powder according to Example 2.

21 and 22 are photographs comparing the content of materials included in the composite powder according to Example 2 according to the number of coating times of the functional material.

Referring to FIG. 21, SEM-EDX of the composite powder according to Example 2, wherein the functional material was coated once, and FIG. 22, SEM- of the composite powder according to Example 2, wherein the functional material was coated twice. EDX.

The SEM-EDX results of FIG. 21 are summarized through <Table 2> below, and the SEM-EDX results of FIG. 22 are summarized through <Table 3> below.

Element	Weight%	Atomic%
C K	75.62	85.08
O K	11.78	9.95
Si K	8.53	4.10
Cu L	4.07	0.87

Element	Weight%	Atomic%
C K	48.68	63.09
O K	24.11	23.46
Si K	21.97	12.17
Cu L	5.24	1.28

As can be seen in Figure 21 and <Table 1>, the composite powder according to Example 2, wherein the functional material was coated once, was surrounded by about 75% C, and it was confirmed that the surface of Cu was slightly exposed. In addition, it was confirmed that the peaks of Si and O also appear by the binding material.

As can be seen in Figure 22 and <Table 2>, the composite powder according to Example 2, in which the functional material was coated twice, shows little Cu shape, and the EG particles are uniformly coated with a size of 5 to 15 microns. I could confirm that. In addition, it was confirmed that the proportion of Si and O increased as the amount of the binding material increased to coat the functional material twice.

23 are general pictures for confirming chemical resistance of the composite powder according to Example 2 of the present invention, and FIG. 24 are optical pictures for confirming chemical resistance of the composite powder according to Example 2 of the present invention.

Referring to (a) and (b) of Figure 23, a general copper powder is prepared. After dropping NaCl at a concentration of 3.5 wt% on the prepared copper powder, changes occurring on the copper powder for 72 hours were observed. FIG. 23 (a) is a photograph of a state before dropping NaCl in a normal copper powder, and FIG. 23 (b) is a photograph of 72 hours after dropping NaCl in a normal copper powder. As can be seen from (a) and (b) of FIG. 23, in the case of the general copper powder, it was confirmed that corrosion occurred after a certain time after contact with NaCl.

Referring to (c) and (d) of FIG. 23, after dropping NaCl at a concentration of 3.5 wt% on the composite powder according to Example 2, a change occurring on the copper powder was observed for 72 hours. Figure 23 (c) is a photograph of the state before dropping NaCl on the composite powder according to Example 2, Figure 23 (d) is dropped NaCl on the composite powder according to Example 2 This is a picture taken 72 hours later. As can be seen from (c) and (d) of FIG. 23, it was confirmed that the composite powder according to Example 2 was protected from NaCl by a coated functional material (FM).

Referring to (a) and (b) of FIG. 24, SEM images of the general copper powder in the state (b) and (d) of FIG. 23 and the composite powder according to Example 2 were taken by SEM. As can be seen from (a) and (b) of FIG. 24, it was confirmed that the composite powder according to Example 2 was uniformly preserved in the state of the surface by the coated functional material (FM).

25 to 27 are graphs comparing component changes according to the heat treatment temperature of the base core included in the composite powder according to Example 2 of the present invention.

Referring to FIG. 25, a general copper powder (Cu), a composite powder (Single) coated with a functional material (FM) once, and a composite powder (Double) coated with a functional material (FM) twice at a temperature of 300 ° C. After heat treatment for 1 hour (1h), 3 hours (3h), and 5 hours (5h), XRD results for each were illustrated. As can be seen in FIG. 25, it was confirmed that CuO was formed and exhibited a high peak in the case of general copper powder (Cu) being heat-treated.

Referring to FIG. 26, the general copper powder (Cu), the composite powder (Single) coated with the functional material (FM) once, and the composite powder (Double) coated with the functional material (FM) twice at a temperature of 400 ° C. After heat treatment for 1 hour (1h), 3 hours (3h), and 5 hours (5h), XRD results for each were illustrated. As can be seen in FIG. 26, it was confirmed that CuO and Cu2O were formed as the general copper powder (Cu) was heat-treated. However, in the case of the composite powder according to Example 2, in which the functional material (FM) was coated on the copper powder, it was confirmed that CuO and Cu2O appeared less.

Referring to FIG. 27, a general copper powder (Cu), a composite powder (Single) coated with a functional material (FM) once, and a composite powder (Double) coated with a functional material (FM) twice at a temperature of 500 ° C. After heat treatment for 1 hour (1h), 3 hours (3h), and 5 hours (5h), XRD results for each were illustrated. As can be seen in FIG. 26, it was confirmed that CuO and Cu2O were formed as the general copper powder (Cu) was heat-treated. However, in the case of the composite powder according to Example 2, in which the functional material (FM) was coated on the copper powder, it was confirmed that CuO and Cu2O appeared less.

As can be seen in Figures 25 to 27, it can be seen that the composite powder according to Example 2, as the functional material (FM) is coated on the copper powder, the oxidation resistance of the copper powder is improved.

Composite powder preparation according to Example 3

Prepare 7 g of high-density polyethylene (HDPE) with a reduced particle size through a ball milling process. In addition, after preparing h-BN functionality having a concentration of 1 wt%, the functional substance and 7 g HDPE were mixed, and acoustic mixing was performed for a time of 15 minutes. Accordingly, a composite powder according to Example 3 was prepared in which a functional material (h-BN) was coated on a base core (HDPE).

28 is a general photograph of a composite powder according to Example 3 of the present invention, and FIG. 29 is an optical photograph of the composite powder according to Example 3 of the present invention.

Referring to (a) and (b) of FIG. 28, the base core (HDPE) and the functional material (h-BN) used in the production of the composite powder according to Example 3 were photographed in general and FIG. 28 (a) ), And the composite powder according to Example 3 formed of a base core (HDPE) and a functional material (h-BN) was photographed in general and shown in FIG. 28 (b). Referring to (a) to (d) of FIG. 29, the composite powders according to Example 3 were shown by SEM photographing at different magnifications and different angles, respectively. 28 and 29, it was confirmed that the composite powder according to Example 3 had a functional material (h-BN) formed around the base core (HDPE).

Preparation of composite powder according to Example 4

PMMA is prepared as a base core. After mixing the prepared PMMA with a silane coupling agent, which is a binding material, and a functional material (h-BN), acoustic mixing was performed to prepare a composite powder according to Example 4.

30 is an optical photograph of the composite powder according to Example 4 of the present invention.

Referring to (a) to (e) of FIG. 30, a functional material (h-BN) shows an image of a case in which a silane coupling agent is not added to and a case in which a silane coupling agent is added to the uncoated polymer material, and the binding is performed. When a material (silane coupling agent) was added, it was confirmed that a uniform coating was achieved, and when the images of each coated composite powder were made of a composite material were confirmed, a coupling material (silane coupling agent) was added. In this case, it was confirmed that uniform dispersion was achieved throughout the composite material.

As can be seen from (d) and (e) of FIG. 30, in the process of manufacturing the composite powder according to Example 4, as the silane couping agent is used, the base core (PMMA) and the functional material (h-BN) are It was confirmed that it was easily combined.

31 is a graph showing optimization of the chemical structure and silane coupling agent binding mechanism and content of the composite powder according to Example 4 of the present invention.

Referring to (a) of Figure 31, for the preparation of the composite powder according to Example 4, the base core (PMMA), a coupling material (silane coupling agent), and a functional material (h-BN) is combined with the chemical formula Shown. As can be seen from FIG. 31 (a), the base core (PMMA) and the functional material (h-BN) are easily combined by a silane coupling agent in the process of enhancing the composite powder according to Example 4 above. I could confirm that it was done.

Referring to (b) and (c) of FIG. 31, it can be confirmed that the silane coupling agent is chemically bound to the functional material (h-BN), and the content of the optimized silane coupling agent is It was confirmed that the mass ratio was 3% compared to the functional substance (h-BN).

Preparation of heat dissipation composite material according to the embodiment

After preparing a plurality of composite powders according to Example 4, a plurality of composite powders were agglomerated and compressed. In addition, by injecting PMMA resin into the heat dissipation route formed in the pressing process, a heat dissipation composite material according to the above embodiment was prepared.

The composite powder and the heat dissipation composite material according to the above embodiments are summarized through <Table 4> below.

division	Configuration
Example 1 Composite powder	HDPE + EG
Example 2 Composite Powder	Cu ball + EG
Example 3 Composite Powder	HDPE + h-BN
Example 4 Composite Powder	PMMA + h-BN
Example heat dissipation composite material	Example 4 Compression after agglomeration

32 is an optical photograph of a heat dissipation composite material according to an embodiment of the present invention.

Referring to (a) to (c) of FIG. 32, the composite powder according to Example 4 is agglomerated, the agglomerated composite powder is compressed to form a heat dissipation route, and the PMMA resin is injected into the heat dissipation route. The heat dissipation composite material according to the embodiment is shown by SEM photographing. As can be seen from (a) to (c) of FIG. 32, it was confirmed that the heat dissipation composite material according to the above embodiment forms a heat dissipation route in the process of agglomeration of a plurality of the composite powders according to Example 4.

33 is a photograph of a thermal radiation composite material according to an embodiment of the present invention taken with an infrared camera.

Referring to Figure 33, the composite material according to the above embodiment, the functional material (right) is a polymer material (left) and the functional material is a randomly dispersed composite material (middle) three types of material in the vertical direction, Shown is a picture observed with an infrared camera that heat transfer occurs as heat is applied in the horizontal direction. As can be seen in Figure 33, it was confirmed that the composite material according to the embodiment is easily made to heat dissipation.

34 is a graph showing the thermal conductivity of a heat dissipation composite material according to an embodiment of the present invention.

Referring to (a) and (b) of FIG. 34, a composite material according to the embodiment (Double filler-to-polymer percolation), a composite material manufactured by the method according to the embodiment but not filling the voids of the composite material ( Single filler percolation), and the thermal conductivity of the vertical and horizontal directions of the composite material according to the embodiment in which the functional material is randomly dispersed (Randomly dispersed) are shown in a graph. As can be seen from (a) and (b) of FIG. 34, it was confirmed that the composite material according to the embodiment has excellent heat dissipation characteristics.

As described above, the present invention has been described in detail using preferred embodiments, but the scope of the present invention is not limited to specific embodiments, and should be interpreted by the appended claims. In addition, those skilled in the art should understand that many modifications and variations are possible without departing from the scope of the present invention.

The composite material according to the embodiment of the present invention can be used in various industrial fields, such as parts materials for automobiles and spacecraft that require wear resistance, corrosion resistance, and oxidation resistance, electronic materials, electric vehicles, heat dissipation materials, and thermoelectric materials.

Claims (15)

1. Base core; And

   It comprises a functional material comprising a carbon layer, and includes a coating layer surrounding at least a portion of the base core,

   The functional material is a composite powder comprising a carbon to oxygen ratio of 16 or more.
2. According to claim 1,

   A composite powder comprising an I _2D / I _G value of greater than 0.4 and less than 0.59 in a Raman spectroscopy of the functional material.
3. According to claim 1,

   C 1s content of the functional material is a composite powder comprising at least 93 wt%.
4. According to claim 1,

   The functional material is a composite powder comprising a carbon layered structure in which a plurality of the carbon layers are stacked.
5. According to claim 1,

   The content of the functional substance is a composite powder comprising 0.49 wt% or more.
6. According to claim 1,

   The base core is a composite powder comprising any one of polymer, ceramic, and metal.
7. The method of claim 6,

   The polymer includes HDPE (high-density polyethylene), and the metal is copper (copper).
8. The method of claim 6,

   When the base core includes any one of the ceramic and the metal,

   A composite powder further comprising a bonding material bonding the base core and the coating layer.
9. The method of claim 8,

   The binding material is a composite powder comprising at least one of a silane coupling agent or a grafted polymer.
10. Preparing a functional material including a carbon layered structure in which a plurality of carbon layers are stacked;

    Mixing the functional material with a base core; And

    Comprising the steps of applying a vibration to the base core and the functional material, forming a composite powder coated with a coating layer containing the functional material on the base core,

    The number of the carbon layers of the carbon layered structure included in the functional material before coating is greater than the number of carbon layers of the carbon layered structure included in the functional material after being coated. Manufacturing method.
11. The method of claim 10,

    The step of preparing the functional material,

    Inserting ions between the stacked plurality of carbon layers to produce the carbon stack structure;

    Heat-treating the carbon layered structure in which ions are inserted; And

    Method of manufacturing a composite powder comprising the step of ultrasonically treating the heat-treated carbon layered structure.
12. The method of claim 10,

    The step of forming the coating layer,

    Method for producing a composite powder comprising the carbon layer contained in the carbon layered structure is peeled off by vibration.
13. The method of claim 10,

    In the step of mixing the functional material with the base core,

    A method of manufacturing a composite powder, comprising controlling the content of the functional material to control the electrical conductivity and thermal conductivity of the composite powder.
14. A plurality of base cores;

    A coating layer surrounding at least a portion of the plurality of base cores and including a functional material; And

    It includes a heat dissipation route (route) provided between the plurality of base cores,

    The heat dissipation route is a heat dissipation composite material in which the functional material and heat dissipation resin included in the coating layer are disposed.
15. The method of claim 14,

    The base core includes at least one of polyethylene, SEBS, EVA, PMMA, PDMS, PVDF, PTEF, PP,

    The functional material is CNT, graphene, graphite, carbon balck, h-BN, Aluminum nitride, Alumina, Silicon nitride, copper, silver, gold, telilium, platinuim at least one of the heat-resistant composite material.

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