CN115679303A - Graphene surface metallization method, graphene metal matrix composite material and application thereof - Google Patents
Graphene surface metallization method, graphene metal matrix composite material and application thereof Download PDFInfo
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
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Abstract
The invention discloses a graphene surface metallization method, which comprises the following steps: s1, uniformly dispersing graphene oxide into a metal salt solution with a metallized surface under continuous stirring; and S2, adding a reducing agent, fully stirring, separating, washing with water, and drying to obtain the graphene powder with the metallized surface. The graphene powder with the metallized surface prepared by the method is more uniform in graphene and better in dispersity. The graphene powder with the metallized surface and the graphene metal matrix composite material prepared by the metal matrix are prepared by the preparation method, and the metallization layer which is the same as the matrix metal is coated on the surface of the graphene, so that the dispersity and wettability of the graphene in the metal matrix and the bonding strength of the graphene and the metal matrix can be obviously improved under the condition of not introducing other impurity elements. The method has wide application prospect in the fields of aerospace, equipment, nuclear power, automobiles, rail transit and the like.
Description
Technical Field
The invention relates to the technical field of additive manufacturing, in particular to a graphene surface metallization method and application thereof in additive manufacturing.
Background
The metal matrix composite material is a composite material consisting of a metal matrix and a heterogeneous reinforcing phase, wherein the matrix phase is continuous and can play a role in supporting the reinforcing phase so as to provide stability for the composite material; while the reinforcing phase may be continuous or discontinuous, when the material is subjected to a load, part of the stress will be transferred to the reinforcing phase, thereby altering the mechanical strength of the composite. The metal matrix composite material has designability, and can be used for designing the components, types and forms of a matrix and a reinforcing phase according to the service environment to obtain the performances of fatigue resistance, wear resistance, heat resistance, corrosion resistance, high heat conduction, low thermal expansion, radiation shielding and the like which are superior to those of a simple substance material. Therefore, the metal matrix composite material is widely applied to the fields of national important requirements of aerospace, equipment, nuclear power, automobiles, rail transit and the like and national economic equipment manufacturing.
The graphene has high damping, elastic modulus, electric conductivity, heat conductivity, mechanical strength and good self-lubricating property, and has wide application prospect in the field of metal matrix composite materials as an ideal novel reinforcing phase. Compared with the traditional reinforcing phase, the high specific surface area of the reinforcing phase has obvious advantages in the aspect of reinforcing efficiency, and can obviously improve the mechanical, physical and chemical properties of the metal material. At present, the problems restricting the development of graphene metal matrix composite materials mainly lie in: (1) the dispersibility of graphene in a metal matrix is poor; (2) the wettability of graphene and a metal matrix is poor; (3) the interfacial bonding of graphene to metal matrices is a problem. To this end, researchers have attempted to solve the above problems by introducing an amphiphilic metallic interfacial layer between the substrate and the graphene by surface modification of the graphene. The graphene surface modification technologies developed at present mainly include: chemical plating, vacuum evaporation, magnetron sputtering, physical/chemical vapor deposition, conductive adhesive coating and other methods, wherein the vacuum evaporation, magnetron sputtering and physical/chemical vapor deposition technologies need inert gas protection or harsh conditions such as high temperature, high pressure and the like, have higher cost and are not easy to prepare on a large scale; the coating of the conductive adhesive needs the use of an organic binder, has the problems of insufficient thermal shock resistance, impurity residues and the like, and does not obviously improve the bonding strength of the graphene and the metal interface. In contrast, the chemical plating technology has mild conditions and is easy for large-scale production, but has the defects of single plating layer (chemical copper or nickel plating), complex process (coarsening-sensitization-activation-chemical plating) and need of using a noble metal catalyst (palladium or silver), thereby limiting the large-scale popularization of the chemical plating technology.
Therefore, if a novel graphene surface modification technology which is low in cost, simple in process, mild in condition, suitable for large-scale preparation and customizable in plating layer can be developed, the method has important significance for the preparation, application and industrialization process of the graphene metal matrix composite material.
Disclosure of Invention
The invention mainly aims to solve the technical problems that graphene is not uniformly dispersed in a metal matrix, the wettability is poor, the bonding strength with the metal matrix is not enough, and the structure and the performance of a composite material are influenced by introducing impurity metal into the metal matrix.
In a second object of the present invention, a surface-metallized graphene powder prepared by the above preparation method is provided.
The third objective of the present invention is to provide a graphene metal matrix composite material including the above surface-metallized graphene powder, wherein the graphene metal matrix composite material is formed by coating a metallization layer on the surface of graphene, wherein the metallization layer is the same as the matrix metal, so that the dispersibility and wettability of graphene in the metal matrix and the bonding strength with the metal matrix can be significantly improved without introducing other impurity elements.
The fourth purpose of the invention is to provide the application of the graphene metal matrix composite material in the fields of aerospace, equipment, nuclear power, automobiles and rail transit.
In order to achieve the purpose, the invention provides the following technical scheme:
a graphene surface metallization method comprises the following steps:
s1, uniformly dispersing graphene oxide into a metal salt solution with a metallized surface under continuous stirring;
and S2, adding a reducing agent, fully stirring, separating, washing with water, and drying to obtain the graphene powder with the metallized surface.
In some embodiments of the invention, the reaction mechanism of the invention is as follows:
1. and (3) carrying out coordination reaction of graphene oxide and metal ions: hydroxyl (-OH) and epoxy (-C (O) C-) on surface of graphene oxide]Active groups such as carbonyl (-C = O), carboxyl (-COOH), and ester (-COO-) can be combined with metal ion (M) x+ And x is the number of electrons) as shown in the following equation:
M x+ +C-OH→C-OH-M (x-1)+
2. reduction reaction of graphene oxide and metal ion complex: the hydrogen radical (. H) or metal-hydrogen bond (M-H) reduces the complex of graphene oxide and metal ions to the graphene composite material with metallized surface, and the typical reaction is shown in the following equation:
C-OH-M+·H→C+M+H 2 O。
in some embodiments of the present invention, in step S1, the concentration of the metal salt solution for surface metallization is 10 to 300g/L, and the uniform dispersion time is 50 to 70min of ultrasonic dispersion.
In some embodiments of the present invention, in step S1, the graphene oxide has a diameter of 5 to 10 μm and a lamella thickness of 3 to 10nm.
In some embodiments of the present invention, in step S1, the metal salt in the metal salt solution is selected from at least one of chromium salt, manganese salt, iron salt, cobalt salt, nickel salt, copper salt, zinc salt, molybdenum salt, ruthenium salt, rhodium salt, palladium salt, silver salt, cadmium salt, tin salt, tantalum salt, tungsten salt, platinum salt, gold salt, lead salt, and a mixed salt thereof.
In some embodiments of the present invention, in step S1, the mass ratio of the graphene oxide to the metal salt in the metal salt solution is 1: (1-100).
In some embodiments of the present invention, in step S2, the reducing agent is selected from hydrogen, hydrazine hydrate, formaldehyde, metal hydride, metal borohydride, and at least one of lithium powder, sodium powder, potassium powder, rubidium powder, cesium powder, aluminum powder, magnesium powder, titanium powder, or zinc powder.
In some embodiments of the invention, in step S2, the concentration of the reducing agent is 0.1 to 100g L -1 。
In addition, the invention also provides graphene powder with a metallized surface, which is prepared by the graphene surface metallization method. The graphene powder with the metallized surface is uniformly dispersed in the metal matrix, has good wettability and high bonding strength with the metal matrix, effectively avoids introducing other metal elements into the metal matrix to influence the structure and the performance of the composite material, and has comprehensive performance superior to that of graphene.
In addition, the invention also provides a graphene metal matrix composite material, which is prepared from the graphene powder with the metallized surface and a metal matrix; the preparation method comprises the following steps: the graphene powder with the metalized surface is dispersed in a metal liquid, or the graphene powder with the metalized surface is uniformly mixed with the metal powder and then prepared in a powder metallurgy, 3D printing, spraying or accumulative rolling mode.
In addition, the invention also provides application of the graphene metal matrix composite material in the fields of aerospace, equipment, nuclear power, automobiles and rail transit.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the preparation method, the metal salt solution with the required surface metallization and the graphene oxide with low cost and stronger water solubility are directly adopted as main raw materials, and a specific reducing agent is added to carry out synchronous in-situ reduction reaction to prepare the graphene powder with the surface metallization, so that compared with the preparation conditions of vacuum evaporation, magnetron sputtering and physical/chemical vapor deposition technologies, the preparation method is mild, economic and easy for large-scale preparation; compared with the conductive adhesive coated with the conductive adhesive, the conductive adhesive has stronger thermal shock resistance, is more beneficial to improving the bonding strength of graphene and a metal interface, and does not introduce any impurity; compared with the chemical plating technology, the method is simpler and more efficient, has more various types of metallization layers, and does not need any catalyst.
(2) The graphene in the graphene powder with the metallized surface prepared by the preparation method is more uniform and has better dispersibility.
(3) The graphene powder with the metallized surface and the graphene metal matrix composite material prepared by the metal matrix are prepared by the preparation method, and the metallized layer which is the same as the matrix metal is coated on the surface of the graphene, so that the dispersity and wettability of the graphene in the metal matrix and the bonding strength of the graphene and the metal matrix can be obviously improved under the condition of not introducing other impurity elements. The method has wide application prospect in the fields of aerospace, equipment, nuclear power, automobiles, rail transit and the like.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) photograph of modified graphene of example 1 of the present invention;
fig. 2 is an energy spectrum (EDS) diagram of modified graphene of example 1 of the present invention;
fig. 3 is an SEM photograph and EDS picture of modified graphene of example 2 of the present invention;
fig. 4 is an EDS photograph of a modified graphene of example 4 of the present invention;
fig. 5 is a digital photograph of the graphene mixed with the metal powder (a) and the modified graphene mixed with the metal powder (b) according to example 8 of the present invention;
fig. 6 is an SEM photograph of the graphene metal matrix composite of example 8 of the present invention;
fig. 7 is an SEM photograph of the graphene metal matrix composite material according to example 10 of the present invention.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
Example 1: preparation of surface-metallized graphene
S1, under the condition of continuous stirring, 1g of graphene oxide (with the diameter of 10 mu m and the lamella thickness of 5 nm) is added into 1L of nickel sulfate (with the concentration of 50g L) -1 ) Performing ultrasonic dispersion in the aqueous solution for 60min to realize coordination of the two;
s2, adding 1g of sodium borohydride into the coordination solution obtained in the step S1, and then separating, washing and drying to obtain graphene with the surface coated with nickel;
the SEM photograph and the EDS spectrum of the modified graphene prepared in this example are respectively shown in fig. 1 and 2, and it can be seen that the composite powder obtained after the complex of nickel and graphene oxide is reduced by sodium borohydride is uniformly dispersed, which indicates that the surface of graphene is successfully coated with nickel.
Example 2: preparation of surface-metallized graphene
The ratio of graphene oxide to nickel sulfate used in step S1 of example 1 was changed to 1:100 (1 g L) -1 Graphene oxide, 100g L -1 Nickel sulfate), and other steps and condition parameters are the same as those of the embodiment 1, so that the graphene with the nickel-coated surface is prepared;
as shown in fig. 3, an SEM photograph and an EDS spectrum of the nickel-modified graphene prepared in this example show that as the concentration of the nickel salt increases, the content of nickel in the prepared nickel-coated graphene composite powder significantly increases, which indicates that the adjustment of the coating degree of graphene by metal can be achieved by changing the ratio of graphene oxide to the metal salt.
Example 3: preparation of surface-metallized graphene
The ratio of graphene oxide to nickel sulfate used in step S1 of example 1 was changed to 1:1, preparing graphene with the surface coated with nickel by using the same steps and condition parameters as those of the embodiment 1;
SEM photographs and EDS spectra of the nickel-modified graphene prepared in this example are similar to those of fig. 1 and 2, except that the nickel content of the prepared nickel-coated graphene composite powder is lower.
Example 4: preparation of surface-metallized graphene
Changing the nickel sulfate used in the step S1 of the embodiment 1 into copper sulfate, and preparing the graphene with the copper-coated surface by using other steps and condition parameters which are the same as those of the embodiment 1;
the SEM photograph and EDS spectrum of the copper-modified graphene prepared in this example are shown in fig. 4, which illustrates that other metal salts can be used as the metal salt for synthesizing the surface-metallized graphene according to the present invention.
Example 5: preparation of surface-metallized graphene
The concentration of sodium borohydride in step S1 of example 1 was changed to 0.1g L -1 Other steps and condition parameters are the same as those in the embodiment 1, and graphene with the surface coated with nickel is prepared;
the morphology and the elemental composition of the nickel-modified graphene prepared in this example are similar to those of fig. 1 and 2, respectively, except that the required reaction time is longer, which indicates that the nickel-coated graphene can also be prepared by reducing the content of the reducing agent, and the reaction rate of the surface metallization of the graphene can be controlled by adjusting the content of the catalyst.
Example 6: preparation of surface-metallized graphene
The concentration of sodium borohydride in step S2 of example 1 was changed to 100g L -1 Other steps and condition parameters are the same as those in the embodiment 1, and the graphene with the nickel-coated surface is prepared;
the morphology and the elemental composition of the nickel-modified graphene prepared in this embodiment are similar to those of fig. 1 and 2, respectively, but the reaction rate is significantly increased, and it should be noted that sodium borohydride reacts violently with water, and needs to be added a small amount of times to avoid explosion.
Example 7: preparation of surface-metallized graphene
Changing the metal borohydride in the step S2 of the embodiment 1 into hydrogen, hydrazine hydrate, formaldehyde, metal hydride, lithium powder, sodium powder, potassium powder, rubidium powder, cesium powder, aluminum powder, magnesium powder, titanium powder or zinc powder, and preparing the graphene with the nickel-coated surface by using the same steps and condition parameters as those in the embodiment 1;
the morphology and elemental composition of all the nickel-modified graphene prepared in this example are similar to those of fig. 1 and 2, respectively, which illustrates that other catalysts can also be used to achieve surface metallization of graphene.
Example 8: application examples
Ball milling the graphene coated with nickel on the surface prepared in example 1 and nickel powder (the mass percentage of the graphene is 0.6%), drying, and obtaining composite powder, as shown in fig. 5, it can be seen that the dispersion performance of the nickel-modified graphene (fig. 5 b) prepared by the invention in the nickel powder is obviously better than that of the unmodified graphene (fig. 5 a); then, laser additive manufacturing is carried out to obtain the graphene metal matrix composite, and then the obtained composite is observed through SEM (scanning electron microscope), as shown in figure 6, the modified graphene can be seen to be uniformly distributed in the composite, which shows that the surface metallization graphene prepared by the invention has excellent dispersibility and metal wettability; similarly, the surface-metallized graphene prepared in examples 2 to 7 also has excellent dispersibility and metal wettability, as measured by the same method.
Example 9: application examples
Ball-milling and mixing the graphene coated with nickel on the surface and prepared in the example 1 with nickel powder, drying to obtain composite powder, then putting the mixed powder into a die for cold press molding, and preparing a graphene metal matrix composite material by using a hot-pressing sintering technology, wherein the microstructure of the graphene metal matrix composite material is similar to that of figure 6, and the graphene is uniformly distributed in a matrix;
similarly, as can be seen from the same method test, the SEM images of the graphene metal matrix composites prepared by surface-metallizing the graphene prepared in examples 2 to 7 are similar to fig. 6, and have excellent dispersibility and metal wettability;
similarly, an SEM image of the graphene metal matrix composite material prepared by directly dispersing in the molten metal rock, spraying and accumulative rolling is similar to that of the SEM image shown in the figure 6, and the graphene metal matrix composite material also has excellent dispersibility and metal wettability;
the above results show that: by carrying out customized surface modification on graphene, a surface metallized graphene modified reinforcing phase which is the same as that of a metal matrix used by the metal matrix composite can be obtained, so that the problems of uneven dispersion and poor wettability of graphene in the metal matrix and insufficient bonding strength with the metal matrix are solved, and the introduction of impurity metal is effectively avoided, thereby improving the comprehensive performance of the graphene metal matrix composite; the graphene surface modification method is low in cost, simple to operate, mild in condition, free of any catalyst, capable of realizing personalized customization of multiple metallization layers on the surface of graphene, and particularly suitable for high-performance manufacturing of graphene metal matrix composite integral components with complex shapes.
Example 10: application examples
Ball-milling, mixing and drying the powder of the graphene coated with nickel and nickel-based high-temperature alloy (the component is 63.59Ni-22.54Cr-18.15Fe-9.41Mo-1.57Co-0.51W-0.03Mn-0.03Si-0.02Ti-0.03Al-0.07C by mass percent) prepared in the example 1 to obtain composite powder, wherein other steps and condition parameters are the same as those in the example 9 to prepare a graphene metal-based composite material, and as shown in fig. 7, the graphene is uniformly distributed in a metal matrix;
similarly, the SEM images of the graphene metal matrix composite materials prepared by the surface-metallized graphene prepared in examples 2 to 7 are similar to fig. 7 and have excellent dispersibility and metal wettability;
the above results show that: on the premise of ensuring that the graphene surface is coated with metal without influencing or improving the performance of the graphene metal matrix composite material, the composition of the graphene surface metallization layer can be different from that of the metal matrix.
The above examples of the present invention are merely illustrative and not restrictive of the specific embodiments of the present invention. Other variations and modifications in light of the above examples may be apparent to those skilled in the art. Not all embodiments are exemplified in detail herein. Obvious changes and modifications of the present invention are also within the scope of the present invention.
Claims (10)
1. A graphene surface metallization method is characterized by comprising the following steps:
s1, uniformly dispersing graphene oxide into a metal salt solution with a metallized surface under continuous stirring;
and S2, adding a reducing agent, fully stirring, separating, washing with water, and drying to obtain the graphene powder with the metallized surface.
2. The graphene surface metallization method according to claim 1, wherein in the step S1, the concentration of the metal salt solution to be subjected to surface metallization is 10-300 g/L, and the uniform dispersion time is 50-70min of ultrasonic dispersion.
3. The graphene surface metallization method according to claim 1, wherein in step S1, the graphene oxide has a diameter of 5 to 10 μm and a lamella thickness of 3 to 10nm.
4. The method according to claim 1 or 2, wherein in step S1, the metal salt in the metal salt solution is at least one selected from a group consisting of chromium salt, manganese salt, iron salt, cobalt salt, nickel salt, copper salt, zinc salt, molybdenum salt, ruthenium salt, rhodium salt, palladium salt, silver salt, cadmium salt, tin salt, tantalum salt, tungsten salt, platinum salt, gold salt, lead salt, and a mixed salt thereof.
5. The graphene surface metallization method according to claim 1 or 2, wherein in step S1, the mass ratio of the graphene oxide to the metal salt in the metal salt solution is 1: (1-100).
6. The graphene surface metallization method according to claim 1, wherein in step S2, the reducing agent is selected from hydrogen, hydrazine hydrate, formaldehyde, metal hydrides, metal borohydrides, and at least one of lithium powder, sodium powder, potassium powder, rubidium powder, cesium powder, aluminum powder, magnesium powder, titanium powder, or zinc powder.
7. The method for metallizing a surface of graphene according to claim 1 or 6, wherein in step S2, the concentration of the reducing agent is 0.1 to 100g L -1 。
8. The graphene surface metallization method according to any one of claims 1 to 7, so as to prepare the surface-metallized graphene powder.
9. A graphene metal matrix composite prepared from the surface-metallized graphene powder of claim 8 and a metal matrix; the preparation method comprises the following steps: the graphene powder with the metalized surface is dispersed into a metal liquid to prepare the graphene powder, or the graphene powder with the metalized surface and the metal powder are uniformly mixed and then prepared in a powder metallurgy, 3D printing, spraying or accumulative rolling mode.
10. The graphene metal matrix composite material according to claim 9, for use in the fields of aerospace, equipment, nuclear power, automobiles, and rail transit.
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| CN103157809A (en) * | 2013-02-05 | 2013-06-19 | 西南科技大学 | Preparation method of graphene/metal nanoparticle composite material with sandwich structure |
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