CN114717442A

CN114717442A - Graphene metal-based composite material and efficient preparation method thereof

Info

Publication number: CN114717442A
Application number: CN202010520699.XA
Authority: CN
Inventors: 姜春辉
Original assignee: Individual
Current assignee: Individual
Priority date: 2020-06-09
Filing date: 2020-06-09
Publication date: 2022-07-08

Abstract

The invention provides a graphene metal-based composite material and an efficient preparation method thereof, wherein graphene and a swelling agent are uniformly mixed, added into an organic solvent, mixed and ultrasonically dispersed to obtain a dispersion, the dispersion is filled in a cavity of a metal piece or an alloy piece and is filled with inert gas for sealing, then the filled metal piece or alloy piece is put into molten metal or alloy, and the inert gas in the metal piece or alloy piece is rapidly swelled under the action of high temperature, so that the graphene is effectively introduced into a metal-based material, the dispersion effect of the graphene can be greatly improved, the graphene and the metal or alloy composite material are in good contact, the characteristics of the graphene material are fully exerted, the electric conductivity, the heat conductivity, the toughness and the strength of the graphene metal-based composite material are effectively improved, and the high-performance graphene metal-based composite material is obtained.

Description

Graphene metal-based composite material and efficient preparation method thereof

Technical Field

The invention relates to the technical field of preparation methods of composite materials, in particular to a graphene metal-based composite material and an efficient preparation method thereof.

Background

The graphene is a novel two-dimensional nano material, the strength of the graphene is as high as 1.01Tpa, which is 100 times that of structural steel, and the density of the graphene is 1/5 of the structural steel. Due to the fact that the graphene is low in density, the density of the material can be reduced while the strength of the metal material is improved. The graphene also has excellent physical properties such as ultrahigh electron mobility, electric conductivity, Young modulus, low thermal expansion coefficient, high thermal conductivity and the like. Therefore, the graphene metal-based composite material prepared by compounding the graphene and the metal or the alloy has the advantages of light weight, high strength, low thermal expansion, high thermal conductivity and the like, can improve the electrical conductivity of the graphene metal-based composite material, and has important application in the fields of electrical conductivity, thermal conductivity, microelectronics, aerospace and the like. However, since the graphene materials have very large specific surface areas, the graphene fillers tend to overlap each other to reduce their surface energy, thereby causing easy agglomeration during the preparation and application of the nanocomposite and adversely affecting the mechanical properties of the composite. In addition, the density difference between the metal or alloy matrix and the graphene nanofiller is large, which brings great difficulty to the uniform dispersion of the graphene nanoplatelets in the metal or alloy matrix.

How to achieve effective dispersion of graphene in a metal or alloy matrix; how to obtain good interface bonding between the graphene nanofiller and the metal or alloy material; how to ensure that the structure of the graphene filler is not damaged at the heat treatment process temperature. These three aspects are the main scientific and engineering issues for graphene metal-based composites. The effective dispersion of graphene in a metal matrix is the first difficult problem to be solved for preparing the graphene metal matrix composite. The simple mechanical mixing of graphene and other metal and alloy powder cannot completely and uniformly disperse the graphene and other metal and alloy powder, and in order to reduce the phenomenon of graphene agglomeration, ultrasonic dispersion, wet mechanical stirring and mixing, ball milling, planetary high-energy ball milling, surface modification, electrostatic adsorption and the like of powder are difficult to solve.

Disclosure of Invention

The invention aims to provide a graphene metal-based composite material and an efficient preparation method thereof, so as to solve the problem that the existing graphene is effectively dispersed in a metal matrix and effectively improve the electrical, mechanical and thermal properties of the composite material.

The efficient preparation method of the graphene metal matrix composite material comprises the following steps:

(1) adding graphene and a swelling agent into an organic solvent, mixing and carrying out ultrasonic treatment to obtain a dispersion;

(2) filling the obtained dispersion into a cavity of a metal piece or an alloy piece;

(3) filling inert gas into a cavity of the metal piece or the alloy piece and sealing the cavity of the metal piece or the alloy piece;

(4) melting at least one metal or alloy, stirring, adding the closed metal piece or alloy piece, and continuing stirring;

(5) and cooling and forming to obtain the composite material.

According to the efficient preparation method of the graphene metal matrix composite, the obtained dispersion is dried and then filled into the cavity of the metal piece or the alloy piece, or the obtained dispersion is filled into the cavity of the metal piece or the alloy piece and then dried.

According to the efficient preparation method of the graphene metal matrix composite material, the metal piece or the alloy piece is tubular or spherical.

According to the efficient preparation method of the graphene metal matrix composite, the tubular metal piece or the alloy piece is 250mm-2500mm in length and 2.5mm-250mm in diameter; the diameter of the spherical metal piece or the alloy piece is 2.5mm-250 mm.

According to the efficient preparation method of the graphene metal matrix composite, graphene, metal powder/particles and a swelling agent are added into an organic solvent to be mixed, and ultrasonic treatment is carried out to obtain a dispersion.

In the efficient preparation method of the graphene metal matrix composite material, the metal powder/particles are at least one of aluminum, copper, gold, silver, tin, zinc, vanadium, titanium, iron, steel, nickel, cobalt, manganese, molybdenum, neodymium, chromium, tantalum, indium, lead, tungsten, magnesium, ruthenium, palladium, osmium, niobium, rhenium, lanthanum, cerium, europium, gadolinium, terbium, holmium, erbium, yttrium and rhenium.

According to the efficient preparation method of the graphene metal matrix composite material, the swelling agent is at least one of sodium tetraborate, rosin, potassium chloride, sodium carbonate, silicon dioxide and calcium fluoride.

According to the efficient preparation method of the graphene metal matrix composite material, the organic solvent is at least one of methanol, ethanol, isopropanol, acetone and an isopropanol solution.

The efficient preparation method of the graphene metal matrix composite material is characterized in that in the step (1), 0.01-4.2 parts of graphene, 0.02-1.3 parts of swelling agent and 0.5-1.4 parts of organic solvent are used.

According to the efficient preparation method of the graphene metal-based composite material, 0.01-4.2 parts of graphene, 0.02-1.3 parts of swelling agent, 0.5-1.4 parts of organic solvent and 0.01-0.0218 part of metal powder/particle are used.

According to the efficient preparation method of the graphene metal matrix composite material, the ratio of the dispersion to the molten metal or alloy in the step (4) is 0.0001-0.003: 1.

In the efficient preparation method of the graphene metal matrix composite material, in the step (4), the metal or the alloy is melted in the furnace at 550-4000 degrees, and the anti-oxidation gas is filled.

The graphene metal-based composite material is prepared by the method.

The invention has the beneficial effects that: the graphene metal-based composite material and the efficient preparation method thereof are characterized in that graphene and a swelling agent are uniformly mixed, added into an organic solvent, mixed and ultrasonically dispersed to obtain a dispersion, the dispersion is filled into a cavity of a metal piece or an alloy piece and is filled with inert gas to be sealed, then the filled metal piece or alloy piece is put into molten metal or alloy, and the inert gas in the metal piece or alloy piece is rapidly swelled under the action of high temperature, so that the graphene is effectively introduced into a metal-based material, more importantly, the dispersion effect of the graphene is greatly improved, and the graphene and the metal or alloy composite material are in good contact with each other, so that the characteristics of the graphene material are fully exerted, the electric conductivity, the heat conduction, the toughness and the strength of the graphene metal-based composite material are effectively improved, and the high-performance graphene metal-based composite material is obtained. Compared with the prior art, the preparation method of the graphene metal composite material can realize excellent dispersion and combination of metal and graphene, so that the electric conductivity, the heat conductivity and the strength of the pure metal-based material are greatly improved, and the preparation method of the graphene metal composite material has the advantages of low cost, simple process, better material quality and contribution to large-scale production.

The composite material prepared by the efficient preparation method of the graphene metal-based composite material can be applied to the fields of military industry, aviation, power cables, automobile industry, electrical appliance industry and semiconductors.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.

FIG. 1 is a photograph of a tubular metal or alloy article according to an embodiment of the present invention.

FIG. 2 is a photograph of a tubular metal or alloy member according to another embodiment of the present invention.

Fig. 3 is a cross-sectional SEM image of the graphene aluminum composite according to the embodiment of the present invention.

Fig. 4 is a raman spectrum of a cross section of the graphene-aluminum composite material according to the embodiment of the present invention.

Fig. 5 is SEM and EDS images of a cross section of the graphene aluminum composite according to an embodiment of the present invention.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example one

The embodiment provides an efficient preparation method of a graphene stainless steel composite material, which comprises the following steps:

(1) graphene and a swelling agent were added to an organic solvent, mixed and sonicated for 1 hour to obtain a dispersion. Wherein, the graphene accounts for 1.2 parts, the swelling agent accounts for 0.02 part, the methanol accounts for 0.9 part, and the sodium tetraborate accounts for 0.1 part.

(2) The resulting dispersion was filled into the cavity of a stainless steel piece. The stainless steel member in this embodiment is tubular. The tubular stainless steel part has a length of 250mm-2500mm and a diameter of 2.5mm-250 mm.

(3) The dispersion was dried and then charged with inert gas and the stainless steel part was closed.

Of course, the dispersion can also be dried before filling into the cavity of the stainless steel part.

For the stainless steel pipe, one end of the stainless steel pipe is extruded and sealed before filling, the other end of the stainless steel pipe is sealed after filling, air holes are reserved, protective gas is filled after drying, and then the air holes are sealed by an extrusion method.

(4) Melting stainless steel in a smelting furnace at 1800 ℃, stirring, filling anti-oxidation gas into the smelting furnace, adding a sealed stainless steel piece, rapidly expanding the stainless steel piece in the molten stainless steel, rapidly and uniformly dispersing graphene into the stainless steel, and continuously stirring.

Wherein the ratio of the dried dispersion to the molten stainless steel is 0.001: 1.

(5) And cooling and forming to obtain the composite material.

The embodiment also provides a graphene stainless steel composite material prepared by the method.

The following table shows the performance indexes of the composite material of the embodiment:

detecting items	Detection unit	The result of the detection	Detection method
				Coefficient of thermal conductivity	W/(m·k)	248	GB/T 36133-2018
Yield strength	Mpa	176	GB/T 228.1-2010
				Tensile strength	Mpa	229	GB/T 228.1-2010
Elongation after fracture	％	87	GB/T 228.1-2010

Example two

The embodiment provides an efficient preparation method of a graphene metal matrix composite, which comprises the following steps:

(1) graphene, metal powder/particles and a swelling agent are added to an organic solvent to be mixed and ultrasonically treated for 10 hours to obtain a dispersion.

Wherein, the graphene accounts for 1.5 parts, the swelling agent accounts for 0.03 part, and the organic solvent accounts for 1.2 parts.

The metal powder/particles include: 0.01 part of nickel, 0.008 part of vanadium, 0.0003 part of manganese and 0.0002 part of molybdenum.

Of course, the metal powder/particles may be at least one of aluminum, copper, gold, silver, tin, zinc, vanadium, titanium, iron, steel, nickel, cobalt, manganese, molybdenum, neodymium, chromium, tantalum, indium, lead, tungsten, magnesium, ruthenium, palladium, osmium, niobium, rhenium, lanthanum, cerium, europium, gadolinium, terbium, holmium, erbium, yttrium, and rhenium, and may be configured according to actual needs. But to ensure that the temperature of the furnace is above the melting point of all metals.

Wherein, the metal powder/particle can be metal powder or metal particle or metal powder and metal particle.

The swelling agent is sodium tetraborate.

Of course, the swelling agent may be at least one of sodium tetraborate, rosin, potassium chloride, sodium carbonate, silica, and calcium fluoride.

The organic solvent is methanol and acetone, and the volume ratio of the methanol to the acetone is 1: 1.

Of course, the organic solvent may be at least one of methanol, ethanol, isopropanol, acetone, and an isopropanol solution.

(2) The resulting dispersion was filled into the cavity of a stainless steel piece.

Wherein, the stainless steel part is tubular. The tubular stainless steel part has a length of 250mm-2500mm and a diameter of 2.5mm-250 mm. Of course, the stainless steel member may be spherical, and the diameter of the spherical stainless steel member is 2.5mm to 250 mm.

(4) And (2) melting the stainless steel in a smelting furnace at 3000 ℃, stirring, filling the smelting furnace with anti-oxidation gas, adding a sealed stainless steel piece, rapidly puffing the stainless steel piece in the molten stainless steel, rapidly and uniformly dispersing the graphene into the stainless steel, and continuously stirring.

Wherein the ratio of the dried dispersion to stainless steel is 0.002: 1.

(5) Cooling and forming to obtain the composite material.

The embodiment also provides a graphene metal matrix composite material prepared by the method.

detecting items	Detection unit	The result of the detection	Detection method
				Coefficient of thermal conductivity	W/(m·k)	252	GB/T 36133-2018
Yield strength	Mpa	182	GB/T 228.1-2010
				Tensile strength	Mpa	256	GB/T 228.1-2010
Elongation after fracture	％	68	GB/T 228.1-2010

EXAMPLE III

The embodiment provides an efficient preparation method of a graphene metal aluminum composite material, which comprises the following steps:

(1) graphene and a swelling agent were added to an organic solvent, mixed and sonicated for 1 hour to obtain a dispersion.

Wherein, the graphene accounts for 3 parts, the swelling agent accounts for 1.1 parts, and the organic solvent accounts for 1.2 parts.

The swelling agent is sodium tetraborate.

(2) The resulting dispersion was poured into a metallic aluminum chamber.

As shown in fig. 1, the aluminum metal is tubular. The tubular metal aluminum has a length of 250mm-2500mm and a diameter of 2.5mm-250 mm.

Of course, as shown in fig. 2, the aluminum metal may further include a main pipe body and a pipe cap, and the main pipe body and the pipe cap are combined together in an interference fit manner to form a closed cavity.

Of course, the metal aluminum can also be two hemispheres, the two hemispheres are combined together by interference fit to form a sphere, and the diameter of the spherical metal aluminum is 2.5mm-250 mm.

(3) And (4) drying the dispersion, filling inert gas into the dispersion and sealing the cavity of the metal aluminum.

(4) Melting and stirring metal aluminum in a melting furnace at 900 ℃, filling anti-oxidation gas into the melting furnace, adding a sealed metal aluminum piece, rapidly expanding the metal aluminum piece in molten metal aluminum water, rapidly and uniformly dispersing graphene into the aluminum water, and continuously stirring.

Wherein the ratio of dried dispersion to aluminum is 0.0024: 1.

(5) And cooling and forming to obtain the composite material.

The embodiment also provides a graphene metal aluminum composite material prepared by the method.

FIG. 3 is a SEM image of a cross-section of a sample of the composite material of this example. FIG. 4 shows a Raman spectrum of a fresh section of the composite material of this example. The metal does not generate a Raman signal, the graphene has an obvious Raman signal, the embodiment has an obvious graphene Raman signal, and the G peak is obviously enhanced compared with the D peak, which indicates that the graphene is successfully introduced into the composite material.

FIG. 5 is a fresh cross-sectional view of the sample of this example and its corresponding EDS energy spectrum. It can be seen that the carbon content of the composite material of this example is significantly increased, indicating that graphene was successfully mixed with aluminum.

The following table shows the properties of the composite material of this example:

detecting items	Detection unit	The result of the detection	Detection method
				Conductivity (20 ℃ C.)	％IACS	78	GB/T351-1995
Yield strength	Mpa	76	GB/T 228.1-2010
				Tensile strength	Mpa	133	GB/T 228.1-2010
Elongation after fracture	％	56	GB/T 228.1-2010

Example four

The embodiment provides an efficient preparation method of a graphene metal aluminum alloy composite material, which comprises the following steps:

(1) graphene, metal powder/particles and a swelling agent are added to an organic solvent to be mixed and subjected to ultrasonic treatment for 1 hour to obtain a dispersion.

Wherein, the graphene accounts for 4 parts, the swelling agent accounts for 1.2 parts, and the organic solvent accounts for 1.3 parts.

The metal powder includes: 0.0095 part of copper, 0.008 part of cobalt, 0.0003 part of manganese and 0.0002 part of titanium.

Of course, the metal powder/particles may be at least one of aluminum, copper, gold, silver, tin, zinc, vanadium, titanium, iron, steel, nickel, cobalt, manganese, molybdenum, neodymium, chromium, tantalum, indium, lead, tungsten, magnesium, ruthenium, palladium, osmium, niobium, rhenium, lanthanum, cerium, europium, gadolinium, terbium, holmium, erbium, yttrium, and rhenium, and may be configured according to actual requirements. But to ensure that the temperature of the furnace is above the melting point of all metals.

The metal powder/particles may be metal powder or metal particles or metal powder and metal particles.

The swelling agent is sodium tetraborate.

(2) The resulting dispersion was poured into a metallic aluminum chamber.

As shown in fig. 2, the aluminum metal is tubular. The tubular metal aluminum has a length of 250mm-2500mm and a diameter of 2.5mm-250 mm.

The metallic aluminum of this embodiment is including being responsible for body and pipe cap, is responsible for body and pipe cap interference fit and combines to form the cavity together.

Of course, the metal aluminum can also be spherical, and the diameter of the spherical metal aluminum is 2.5mm-250 mm.

(4) Melting and stirring the metal aluminum in a 2000-DEG furnace, filling the furnace with anti-oxidation gas, adding a closed metal aluminum piece, and continuing stirring.

Wherein the ratio of dried dispersion to aluminum is 0.0022: 1.

(5) And cooling and forming to obtain the graphene-aluminum alloy composite material.

The embodiment also provides a graphene-aluminum alloy composite material prepared by the method.

detecting items	Detection unit	The result of the detection	Detection method
				Conductivity (20 ℃ C.)	％IACS	73	GB/T351-1995
Yield strength	Mpa	90	GB/T 228.1-2010
				Tensile strength	Mpa	150	GB/T 228.1-2010
Elongation after fracture	％	45	GB/T 228.1-2010

Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims

1. The efficient preparation method of the graphene metal-based composite material is characterized by comprising the following steps:

(3) filling inert gas into the cavity of the metal piece or the alloy piece and sealing the cavity of the metal piece or the alloy piece;

(5) and cooling and forming to obtain the composite material.

2. The method for efficiently preparing the graphene metal matrix composite according to claim 1, wherein the obtained dispersion is dried and then filled into a cavity of a metal or alloy part, or the obtained dispersion is filled into a cavity of a metal or alloy part and then dried.

3. The method for efficiently preparing the graphene metal matrix composite according to claim 1, wherein the metal or alloy member is tubular or spherical.

4. The efficient preparation method of the graphene metal matrix composite according to claim 2, wherein the tubular metal or alloy piece has a length of 250mm to 2500mm and a diameter of 2.5mm to 250 mm; the diameter of the spherical metal piece or the alloy piece is 2.5mm-250 mm.

5. The efficient preparation method of the graphene metal matrix composite material according to claim 1, wherein graphene, metal powder/particles and a swelling agent are added into an organic solvent to be mixed and subjected to ultrasonic treatment to obtain a dispersion.

6. The method for efficiently preparing a graphene metal-based composite material according to claim 4, wherein the metal powder/particles is at least one of aluminum, copper, gold, silver, tin, zinc, vanadium, titanium, iron, steel, nickel, cobalt, manganese, molybdenum, neodymium, chromium, tantalum, indium, lead, tungsten, magnesium, ruthenium, palladium, osmium, niobium, rhenium, lanthanum, cerium, europium, gadolinium, terbium, holmium, erbium, yttrium, and rhenium.

7. The method for efficiently preparing the graphene metal-based composite material according to any one of claims 1 to 6, wherein the swelling agent is at least one of sodium tetraborate, rosin, potassium chloride, sodium carbonate, silicon dioxide and calcium fluoride.

8. The method for efficiently preparing the graphene metal matrix composite according to any one of claims 1 to 6, wherein the organic solvent is at least one of methanol, ethanol, isopropanol, acetone, and an isopropanol solution.

9. The efficient preparation method of the graphene metal matrix composite material according to any one of claims 1 to 6, wherein the graphene in the step (1) is 0.01 to 4.2 parts, the swelling agent is 0.02 to 1.3 parts, and the organic solvent is 0.5 to 1.4 parts.

10. The efficient preparation method of the graphene metal-based composite material according to claim 5 or 6, wherein the graphene is 0.01-4.2 parts, the swelling agent is 0.02-1.3 parts, the organic solvent is 0.5-1.4 parts, and the metal powder/particle is 0.01-0.0218 parts.

11. The efficient preparation method of the graphene metal-based composite material according to any one of claims 1 to 6, wherein the ratio of the dispersion to the molten metal or alloy in the step (4) is 0.0001-0.003: 1.

12. The method for efficiently preparing the graphene metal-matrix composite according to any one of claims 1 to 6, wherein in the step (4), the metal or the alloy is melted in a furnace at 550-4000 degrees, and an anti-oxidation gas is introduced.

13. A graphene metal matrix composite material, characterized in that the graphene metal matrix composite material is prepared by the method of any one of claims 1 to 12.