CN110280773B - Preparation method of low-temperature self-propagating composite material - Google Patents
Preparation method of low-temperature self-propagating composite material Download PDFInfo
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- CN110280773B CN110280773B CN201910660766.5A CN201910660766A CN110280773B CN 110280773 B CN110280773 B CN 110280773B CN 201910660766 A CN201910660766 A CN 201910660766A CN 110280773 B CN110280773 B CN 110280773B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
- B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
- B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
Abstract
The invention relates to a preparation method of a low-temperature self-propagating composite material. The method mainly comprises the following steps: graphene powder with nano-sheet structure and micron-sized structureOther Al powder, Fe2O3Powder, ZnO powder, SiO2Powder B2O3Powder and Cu-Ti alloy powder, and the preparation method comprises spray granulation and vacuum sintering. The invention has the advantages that the material components are compounded with a certain amount of lubricant, cooling agent, heat dissipating agent and wetting agent, so that the melting temperature of a reaction system can be reduced, and the fluidity and the spreading wettability of the material on the interface of an aluminum alloy matrix are improved. And materials that can alter the amount of heat released from the thermite reaction system. The method is suitable for preparing the self-lubricating wear-resistant coating on the inner wall of the aluminum alloy cylinder part with the diameter smaller than 50 mm.
Description
Technical Field
The invention belongs to the technical field of low-temperature self-propagating composite powder materials for preparing graphene self-lubricating wear-resistant coatings, and particularly relates to a preparation method of a low-temperature self-propagating composite material.
Background
The aluminum alloy has the advantages of small density, high strength, good forming and processing performance and the like, and is widely applied to manufacturing various cylinder parts. But the hardness is lower, the wear resistance is poor, and the application is limited due to the poor corrosion resistance. These disadvantages of aluminium alloys are improved by different methods of surface modification. The prior domestic and overseas modified aluminum alloy surface treatment method mainly comprises the following steps: electroplating, anodizing, thermal spraying, laser cladding, micro-arc oxidation and the like. The electroplating, anodizing and micro-arc oxidation are suitable technologies for protecting the wear-resistant coating on the inner wall of the cylinder part, and the preparation of the wear-resistant coating on the inner wall of the aluminum alloy cylinder by thermal spraying, laser cladding and the like is limited by the inner diameter size (the diameter is 35-100 mm) and the mechanical property and the strength of an aluminum alloy matrix (the temperature bearing capacity of the aluminum alloy is less than 660 ℃) due to thermal damage and heat influence.
The self-propagating high-temperature synthesis coating technology is a technology for synthesizing materials by utilizing the self-heating of a reaction system and the self-conduction effect in the system through the exothermic reaction of the reaction system. Once the reactant in the reaction system is ignited by the external heat source, the reactant in the reaction system can rapidly spread from the reaction area to the unreacted area in the mode of combustion wave. Compared with the conventional spraying preparation technology, the self-propagating high-temperature synthetic coating technology has the characteristics of fast heat dissipation of the coating prepared on the inner wall of the small-size cylinder part, no need of spray particle acceleration, simple structure of the ignition device, less smoke dust generation and the like.
The high-temperature self-propagating technology can be used for preparing wear-resistant coatings for barrel parts with different inner diameter sizes, but the limitation is that the temperature of a reflecting system is too high, Al and Fe2O3 are basic components of a high-temperature self-propagating synthetic coating, the wettability of Fe and Al2O3 generated by the reaction of the Al and the Fe2O3 is poor, the highest adiabatic temperature of the reaction can reach 3509K, the highest adiabatic temperature is higher than the melting point (2313K) of an aluminum alloy oxide or Al2O3 and is far higher than the boiling point (2723K) of Al, and the Al can be greatly evaporated in the reaction process, so that a large number of air holes are formed in the coating, and the proportion of reaction products is unbalanced. Aiming at the problems that the melting point of the aluminum alloy cylinder substrate is low, and the mechanical property of the aluminum alloy is seriously reduced at the temperature higher than 660 ℃, the existing high-temperature self-propagating coating forming technology needs to be improved.
Disclosure of Invention
The purpose of the invention is: the preparation method of the low-temperature self-propagating composite material is provided for protection of the wear-resistant coating on the inner wall of the small-size (35-100 mm in diameter) aluminum alloy cylinder part.
The technical scheme of the invention is as follows:
the preparation method of the low-temperature self-propagating composite material comprises the following steps:
step 1, uniformly mixing graphene powder and Al powder, wherein the graphene is of a lamellar structure, and the mass percentage of the graphene to the Al is (0.1-0.5): (99.5 to 99.9);
adding Fe2O3Powder, ZnO powder, SiO2Powder B2O3Uniformly mixing the powder and Cu-Ti alloy powder to obtain mixed powder; preferably, the mass percentages of Cu and Ti are (92-98): (8-2); most preferably 95: 5;
the mass percentage of each component in the mixed powder is (12-18) graphene and Al: (62-65) Fe2O3: (7-9) ZnO: (1-3) SiO2: (1-3) B2O3: (2-17) Cu-Ti;
and 2, uniformly mixing the mixed powder and polyvinyl alcohol, heating at 82-85 ℃, performing spray granulation, and performing vacuum sintering to obtain the low-temperature self-propagating composite material.
Preferably, the thickness of the lamella structure is 1-5 nm.
Further, in the step 1, the granularity of the Al powder is 10-15 nm, the graphene and the Al powder are mixed in a liquid medium (such as alcohol) through ball milling, the ball milling speed is 5-9 rpm/s, and the ball milling mixing time is 7-10 hours; performing ultrasonic dispersion treatment for 2-3 hours after ball milling, wherein the ultrasonic dispersion frequency is 20-25 Hz; and drying for 2-3 hours at 60-90 ℃ after ultrasonic dispersion treatment to obtain mixed powder with the particle size of 1-3 mu m.
Further, Fe in step 12O3Powder particle size of 1-3 μm, ZnO powder particle size of 1 μm, SiO2The particle size of the powder is 1-2 μm, B2O3The particle size of the powder is 1-2 μm, and the particle size of the Cu-Ti powder is 1 μm.
Further, in the step 2, the mass ratio of the polyvinyl alcohol to the mixed powder after being uniformly mixed is 5-8%, and the stirring speed is 330-380 rpm/min.
Further, the low-temperature self-propagating composite material is a powder material, and the particle size is 15-20 microns.
Further, the time for heating and stirring the mixed powder and polyvinyl alcohol after mixing is 30-60 min, and the stirring speed is 300-500 rpm/min.
Further, in step 2, the vacuum degree of the vacuum sintering reaction is 1X 10-3Pa, the sintering temperature is 810-830 ℃, the temperature rise rate of the sintering temperature is 10-15 ℃/min, high-purity argon is used as shielding gas in the sintering process, and the sintering time is 1-2 hours.
The invention has the advantages that:
1) the invention provides a material which is compounded with a certain cooling agent, a certain heat radiating agent and can change the heat release amount of an aluminothermic reaction system. The method is suitable for preparing the inner wall wear-resistant coating of the aluminum alloy cylinder part with the diameter less than 50 mm. Compared with the high-temperature self-propagating synthetic coating technology, the invention provides the method for adding Cu, 5 percent of Ti and Al2O3Can be wetted, and the compactness and bonding strength of the coating are improved. SiO 22、B2O3The melting point is low, and silicate structures are generated with other oxides in the melting and condensing processes of the coating, and the coating is in a glass or enamel state, so that the porosity of the coating is reduced. ZnO is a fluxing agent, can reduce the melting temperature of a reaction system, and can improve the fluidity and spreading wettability of the ZnO on the interface of an aluminum alloy matrix.
2) Graphene is used as a novel carbon solid lubricating material of a nano thin layer, and is used for modifying nano aluminum powder, so that the nano aluminum powder and Fe can be improved2O3The reaction contact area and the reaction heat release energy of the graphene can also play the characteristic that the graphene forms a carbonaceous self-lubricating film in the coating in the dispersion distribution friction process, so that the friction coefficient of the coating is reduced, and the wear rate is reduced.
Drawings
FIG. 1 is a schematic view of the micro-topography of a low temperature self-propagating composite;
Detailed Description
The present invention is described in further detail below.
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood 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 1:
the preparation method of the low-temperature self-propagating composite material comprises the following steps:
step 1, uniformly mixing graphene powder and Al powder, wherein the graphene is of a lamellar structure, and the mass percentage of the graphene to the Al is 0.1: 99.9;
adding Fe2O3Powder, ZnO powder, SiO2Powder B2O3Uniformly mixing the powder and Cu-Ti alloy powder to obtain mixed powder, wherein the mass percentage of Cu to Ti is 95: 5;
the mass percentage of each component in the mixed powder is 12 of graphene and Al: 62 of Fe2O3: ZnO of 7: 1 SiO2: 1B2O3: 17 Cu-Ti;
and 2, uniformly mixing the mixed powder and polyvinyl alcohol, heating at 82 ℃, then carrying out spray granulation, and then carrying out vacuum sintering to obtain the low-temperature self-propagating composite material.
Example 2:
on the basis of the above embodiment, the steps of this embodiment are:
the preparation method of the low-temperature self-propagating composite material comprises the following steps:
step 1, uniformly mixing graphene powder and Al powder, wherein the graphene is of a lamellar structure, and the mass percentage of the graphene to the Al is 0.2: 99.8 of the total weight of the powder;
adding Fe2O3Powder, ZnO powder, SiO2Powder B2O3Uniformly mixing the powder and Cu-Ti alloy powder to obtain mixed powder, wherein the mass percentage of Cu to Ti is 96: 4;
the mass percentage of each component in the mixed powder is 14 of graphene and Al: 63 Fe2O3: ZnO of 8: SiO of 22: 2B2O3: 11 of Cu-Ti;
and 2, uniformly mixing the mixed powder and polyvinyl alcohol, heating at 83 ℃, then carrying out spray granulation, and then carrying out vacuum sintering to obtain the low-temperature self-propagating composite material.
The lamella thickness of lamella structure is 1~5 nm.
Example 3:
on the basis of the above embodiment, the steps of this embodiment are:
the preparation method of the low-temperature self-propagating composite material comprises the following steps:
step 1, uniformly mixing graphene powder and Al powder, wherein the graphene is of a lamellar structure, and the mass percentage of the graphene to the Al is 0.4: 99.6;
adding Fe2O3Powder, ZnO powder, SiO2Powder B2O3Uniformly mixing the powder and Cu-Ti alloy powder to obtain mixed powder, wherein the mass percentage of Cu to Ti is 95: 5;
the mass percentage of each component in the mixed powder is 16 graphene and Al: fe of 642O3: ZnO of 8: SiO of 22: 2B2O3: 4 Cu-Ti;
and 2, uniformly mixing the mixed powder and polyvinyl alcohol, heating at 84 ℃, performing spray granulation, and performing vacuum sintering to obtain the low-temperature self-propagating composite material.
Example 4:
on the basis of the above embodiment, the steps of this embodiment are:
the preparation method of the low-temperature self-propagating composite material comprises the following steps:
step 1, uniformly mixing graphene powder and Al powder, wherein the graphene is of a lamellar structure, and the mass percentage of the graphene to the Al is 0.5: 99.5;
adding Fe2O3Powder, ZnO powder, SiO2Powder B2O3Uniformly mixing the powder and Cu-Ti alloy powder to obtain mixed powder, wherein the Cu and Ti areThe weight percentage is 92: 8;
the mass percentage of each component in the mixed powder is 18 graphene and Al: 65 of Fe2O3: ZnO of 9: 3 SiO2: 3B2O3: 2 of Cu-Ti;
and 2, uniformly mixing the mixed powder and polyvinyl alcohol, heating at 82-85 ℃, performing spray granulation, and performing vacuum sintering to obtain the low-temperature self-propagating composite material.
The thickness of the lamella structure is 5 nm.
It will be understood that modifications and variations can be made by persons skilled in the art in light of the above teachings and all such modifications and variations are intended to be included within the scope of the invention as defined in the appended claims.
Claims (10)
1. A preparation method of a low-temperature self-propagating composite material comprises the following steps:
step 1, uniformly mixing graphene powder and Al powder, wherein the graphene is of a lamellar structure, and the mass percentage of the graphene to the Al is (0.1-0.5): (99.5 to 99.9);
adding Fe2O3Powder, ZnO powder, SiO2Powder B2O3Uniformly mixing the powder and Cu-Ti alloy powder to obtain mixed powder;
the mass percentage of each component in the mixed powder is (12-18) graphene and Al: (62-65) Fe2O3: (7-9) ZnO: (1-3) SiO2: (1-3) B2O3: (2-17) Cu-Ti;
and 2, uniformly mixing the mixed powder and polyvinyl alcohol, heating at 82-85 ℃, performing spray granulation, and performing vacuum sintering to obtain the low-temperature self-propagating composite material.
2. A method for preparing a low temperature self-propagating composite material as claimed in claim 1, wherein: the lamella thickness of lamella structure is 1~5 nm.
3. A method for preparing a low temperature self-propagating composite material as claimed in claim 1, wherein: in the step 1, the granularity of Al powder is 10-15 nm, graphene and Al powder are mixed in a liquid medium in a ball milling mode, the ball milling speed is 5-9 rpm/s, and the ball milling mixing time is 7-10 hours; performing ultrasonic dispersion treatment for 2-3 hours after ball milling, wherein the ultrasonic dispersion frequency is 20-25 Hz; and drying for 2-3 hours at 60-90 ℃ after ultrasonic dispersion treatment to obtain mixed powder with the particle size of 1-3 mu m.
4. A method for preparing a low temperature self-propagating composite material as claimed in claim 1, wherein: fe in step 12O3Powder particle size of 1-3 μm, ZnO powder particle size of 1 μm, SiO2The particle size of the powder is 1-2 μm, B2O3The particle size of the powder is 1-2 μm, and the particle size of the Cu-Ti powder is 1 μm.
5. A method for preparing a low temperature self-propagating composite material as claimed in claim 1, wherein: in the step 2, the mass ratio of the polyvinyl alcohol to the mixed powder after uniform mixing is 5-8%, and the stirring speed is 330-380 rpm/min.
6. A method for preparing a low temperature self-propagating composite material as claimed in claim 1, wherein: the low-temperature self-propagating composite material is a powder material, and the particle size is 15-20 mu m.
7. A method for preparing a low temperature self-propagating composite material as claimed in claim 1, wherein: the time for heating and stirring the mixed powder and polyvinyl alcohol after mixing is 30-60 min, and the stirring speed is 300-500 rpm/min.
8. A method for preparing a low temperature self-propagating composite material as claimed in claim 1, wherein: in step 2, the degree of vacuum of the vacuum sintering reaction is 1X 10-3Pa, the sintering temperature is 810-830 ℃, the heating rate of the sintering temperature is 10-15 ℃/min,in the sintering process, high-purity argon is used as shielding gas, and the sintering time is 1-2 hours.
9. A method for preparing a low temperature self-propagating composite material as claimed in claim 1, wherein: in the step 1, the mass percentage of Cu and Ti of the Cu-Ti alloy powder is (92-98): (8-2).
10. A method of preparing a low temperature self-propagating composite material as claimed in claim 9, wherein: in the step 1, the mass percentage of Cu and Ti of the Cu-Ti alloy powder is 95: 5.
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