CN117227272A - Metal ceramic composite material and preparation method thereof - Google Patents
Metal ceramic composite material and preparation method thereof Download PDFInfo
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- CN117227272A CN117227272A CN202311026542.1A CN202311026542A CN117227272A CN 117227272 A CN117227272 A CN 117227272A CN 202311026542 A CN202311026542 A CN 202311026542A CN 117227272 A CN117227272 A CN 117227272A
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- 239000000919 ceramic Substances 0.000 title claims abstract description 93
- 239000002131 composite material Substances 0.000 title claims abstract description 74
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 72
- 239000002184 metal Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title abstract description 42
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 97
- 239000002245 particle Substances 0.000 claims abstract description 85
- 230000001070 adhesive effect Effects 0.000 claims abstract description 75
- 239000000853 adhesive Substances 0.000 claims abstract description 70
- 238000005507 spraying Methods 0.000 claims description 67
- 239000003822 epoxy resin Substances 0.000 claims description 46
- 229920000647 polyepoxide Polymers 0.000 claims description 46
- 229910001220 stainless steel Inorganic materials 0.000 claims description 40
- 239000010935 stainless steel Substances 0.000 claims description 40
- 239000000843 powder Substances 0.000 claims description 31
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 27
- 239000002994 raw material Substances 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- 239000011248 coating agent Substances 0.000 claims description 22
- 238000000576 coating method Methods 0.000 claims description 22
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000004593 Epoxy Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- HTPGOQRGCUSPGR-UHFFFAOYSA-N phosphoric acid silane Chemical compound [SiH4].OP(O)(O)=O HTPGOQRGCUSPGR-UHFFFAOYSA-N 0.000 claims description 13
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 12
- 238000007750 plasma spraying Methods 0.000 claims description 12
- 229910000077 silane Inorganic materials 0.000 claims description 12
- 229910052580 B4C Inorganic materials 0.000 claims description 9
- 229910052582 BN Inorganic materials 0.000 claims description 9
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 9
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 8
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 8
- 238000002161 passivation Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000005245 sintering Methods 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 3
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- 238000001035 drying Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
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- 238000003756 stirring Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000007751 thermal spraying Methods 0.000 claims 1
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 91
- 239000007789 gas Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 10
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- 239000012790 adhesive layer Substances 0.000 description 6
- 229920006332 epoxy adhesive Polymers 0.000 description 6
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 6
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 6
- QXLPXWSKPNOQLE-UHFFFAOYSA-N methylpentynol Chemical compound CCC(C)(O)C#C QXLPXWSKPNOQLE-UHFFFAOYSA-N 0.000 description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 5
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
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Abstract
The application relates to the field of ceramic materials, in particular to a metal/ceramic composite material and a preparation method thereof: the metal/ceramic composite material comprises a ceramic layer and a metal layer, and the ceramic layer and the metal layer are bonded through an adhesive; and modified alumina particles are sprayed on one surface of the metal layer, which is close to the ceramic layer. The metal/ceramic composite material has better bonding strength.
Description
Technical Field
The application relates to the field of oxide ceramics, in particular to a metal ceramic composite material and a preparation method thereof.
Background
The ceramic material has many advantages of high temperature resistance, high strength, high hardness, corrosion resistance, abrasion resistance and the like, is widely applied to the fields of aerospace, power electronics, energy traffic and the like, and becomes an indispensable supporting material in economic and national defense development. However, the brittleness of the ceramic itself makes it difficult to manufacture large-sized and complex-shaped members, thereby limiting further applications and development thereof. The metal material has excellent room temperature strength, ductility, electrical conductivity and thermal conductivity, and forms an obvious complementary relation with the ceramic material in performance. The two materials are combined together, so that the engineering materials meeting the requirements can be manufactured by fully utilizing the respective excellent properties. Because ceramics and metal bonds are different and the wettability of the surface is poor, how to connect the ceramics and the metal bonds is convenient, low in cost, firm and compact and is a problem to be solved.
Currently, the joining methods for ceramics and metals include mechanical joining, adhesive joining, brazing joining, solid-phase diffusion joining, transient liquid phase joining, fusion welding, self-propagating high temperature synthesis joining, friction welding, microwave joining, ultrasonic joining, and the like. If the ceramic material and the metal material are directly bonded by the adhesive, the bonding effect is not very good; if the two are connected through a mechanical joint, larger stress is generated; the joint strength of direct brazing is limited, the heat resistance is low, the corrosion resistance is poor, and the assembly requirement is high; the ceramic is metallized firstly and then indirectly soldered, the cost is high, and the difference of the thermal expansion coefficients of the ceramic and the metal, the pretreatment of the ceramic surface, the equipment requirement and the like are considered; the solid-phase diffusion connection requires higher connection temperature and longer time, the connection is required to increase the cost under vacuum, and the size of the composite material is limited to a certain extent; the instantaneous liquid phase welding has low production efficiency and high requirements on preparation and assembly; the manufacturing cost of equipment is high because the parameters of the fusion welding connection process are difficult to control; the burning time of the self-propagating high-temperature synthetic connecting solder is difficult to control, and the interface reaction is difficult to control.
Disclosure of Invention
The application provides a metal ceramic composite material and a preparation method thereof, in order to solve the problems that the metal ceramic composite material has simple preparation process and high bonding strength.
In a first aspect, the present application provides a cermet composite comprising a ceramic layer and a metal layer bonded by an adhesive; and modified alumina particles are sprayed on one surface of the metal layer, which is close to the ceramic layer.
By adopting the technical scheme, rough micropores can be formed on the surface of the metal to provide mechanical locking, so that the mechanical bonding capability is improved, the contact surface area between the metal and the adhesive is increased, and the bonding strength is further increased; meanwhile, as the preparation process is simple, the core steps are that modified alumina particles are sprayed on the metal surface and then bonded with the ceramic layer, and the metal layer and the ceramic layer can directly purchase finished products meeting the requirements on the market, thereby greatly reducing the equipment requirements and the process requirements.
In a specific embodiment, the modified alumina particles are silane modified alumina particles co-modified with an epoxy silane coupling agent and a phosphate silane coupling agent.
By adopting the technical scheme, the alumina particles are jointly modified by the epoxy silane coupling agent and the phosphate silane coupling agent, on one hand, the adhesion of the phosphate silane modified alumina particles to the metal layer is improved due to the excellent adhesion capability of the phosphate and the metal, and on the other hand, the epoxy silane coupling agent and the adhesive have good adhesion performance, a strong chemical bond is formed at an adhesion interface, and the adhesion strength of the alumina particles and the adhesive is further improved.
In a specific embodiment, the step of modifying the silane-modified alumina particles comprises: adding alumina micropowder, epoxy silane coupling agent and phosphate silane coupling agent into ethanol water solution, mixing, stirring at 70-90 ℃ for 2-4 hours, filtering, washing with purified water for 2-3 times, and drying in a baking oven at 100-120 ℃ to obtain silane modified alumina particles.
By adopting the technical scheme, the application successfully modifies the alumina particles by two silane coupling agents containing different functional groups, so that the alumina particles can be firmly adhered between the metal layer and the adhesive, and the adhesive property of the composite material is improved.
In a specific embodiment, the modified alumina particles are sprayed to a thickness of 0.1 to 0.3mm.
By adopting the technical scheme, the too thick spraying thickness of the modified alumina particles can lead to incomplete bonding of the two materials and poor adhesion; too thin a spray thickness may lead to aluminum oxide particles being filled with an adhesive layer, resulting in failure to achieve the bonding effect of mechanical keying.
In a specific embodiment, the adhesive comprises 55-70 parts by weight of epoxy resin and 20-30 parts by weight of curing agent.
By adopting the technical scheme, the epoxy resin adhesive has excellent cohesiveness, and the application discovers that the content of the curing agent is increased to enable the curing agent to fully cure the epoxy resin on one hand, and the excessive curing agent can be crosslinked with the epoxy groups of the modified alumina particles to increase the bonding strength of the modified alumina particles and the epoxy resin adhesive on the other hand, so that the bonding strength of the metal ceramic composite material is further improved.
In a specific embodiment, the ceramic layer comprises the following raw materials in parts by weight:
90-95 parts of alumina powder,
2-5 parts of boron carbide,
2-5 parts of boron nitride,
0.1-0.5 part of sintering auxiliary agent,
0.5-4 parts of dispersing agent.
By adopting the technical scheme, the ceramic layer is alumina ceramic taking alumina as a main component, the hardness of the alumina ceramic is very high, the wear resistance is very good, and the ceramic layer has the advantages of chemical corrosion resistance, heat resistance and the like; the boron carbide has the advantages of high hardness, high melting point and the like, and endows the ceramic layer with better hardness, wear resistance, corrosion resistance and heat resistance; the boron nitride has good heat conductivity, super-strong hardness and chemical corrosion resistance, and further improves the comprehensive properties of the ceramic layer, such as hardness, wear resistance, corrosion resistance and the like; the alumina is not easy to sinter, and the sintering temperature is reduced by adding the sintering auxiliary agent, so that the alumina ceramic balls have uniform and fine particles, and the strengthening and toughening are obtained; the alumina micropowder is easy to agglomerate, and the added dispersing agent is adsorbed on the surfaces of various tiny particles and generates electrostatic repulsive force to disperse the particles, so that the precipitation and aggregation are reduced, and the effect and the reliability of the ceramic layer are improved.
In a specific embodiment, the metal layer is one of a stainless steel layer and an aluminum layer.
By adopting the technical scheme, the stainless steel has higher hardness, excellent corrosion resistance and high temperature resistance, light aluminum has light and good heat conduction performance and manufacturability, and the aluminum are conveniently obtained on the market, can be flexibly selected according to specific use requirements, and increases the use range of the metal ceramic composite material and the convenience and rapidness of the preparation process.
In a second aspect, the application provides a method for preparing a cermet composite comprising the steps of:
s1: spraying modified alumina particles on one surface of the pretreated metal layer;
s2: coating a layer of adhesive on one surface of the sprayed modified alumina particles, and bonding the surface with one surface of the ceramic layer to obtain a composite layer; s3: and pre-curing the bonded composite layer at 60-90 ℃, heating to 100-120 ℃ after 2-4 hours, and standing and curing for 6-8 hours to obtain the metal ceramic composite material.
By adopting the technical scheme, the modified alumina particles are sprayed on one side of the metal layer, which is close to the ceramic layer, so that the contact area with the adhesive is increased; the application of the adhesive further improves the bonding strength, pre-cures and then stands still for curing, reduces the energy consumption, and further enhances the comprehensive properties of the bonding layer, such as bonding strength, high temperature resistance strength and the like.
In a specific embodiment, the spray is a plasma spray, and the parameters of the plasma thermal spray include: the current is 550-650A, the voltage is 60-90V, the powder feeding amount is 15-25g/min, the gas carrying amount is 2.5-3.5L/min, the spraying distance is 25-50 mm, and the spraying angle is 60-90 degrees.
By adopting the technical scheme, the speed of spraying particles to the stainless steel plate/aluminum plate by plasma spraying is high, the coating is uniform, and the bonding strength is high; the inert gas is used as the working gas, so that the spraying material is more stable; the thickness of the modified alumina spray coating on the metal layer and the porosity of the coating can be conveniently and flexibly controlled by controlling the powder feeding amount per minute and the powder feeding time and gas carrying amount; the sprayed powder feeding amount is not too large so that raw powder which cannot be melted yet is generated, and is not too small so that the powder is seriously oxidized and the matrix is overheated, thereby increasing the energy consumption and reducing the production efficiency; the velocity of the spray particles is increased to less than the semi-molten or plastic state necessary for deformation, and is not too small to cause overheating of the spray material, causing excessive melting or vaporization of the spray material, causing the melted powder particles to accumulate in the nozzle or powder orifice and then deposit in the coating in a larger sphere to form large voids; the air-carrying capacity is not too large, so that the spraying distance is not too large, the powder particle temperature and the powder particle speed are reduced, the binding force, the air holes and the spraying efficiency are obviously reduced, the temperature rise of the matrix is not too high, the matrix and the coating are oxidized, and the combination of the coating is affected; the spraying angle is proper so that a shadow effect does not appear, so that the coating structure is deteriorated to form cavities, and the coating is loose.
In a specific implementation, the metal layer is a stainless steel plate/aluminum plate, the pretreatment of the metal layer is oil removal, rust removal, phosphating and passivation treatment, and the surface of the ceramic layer is cleaned and roughened in advance before the coating of the adhesive; the adhesive is subjected to vacuum defoamation in advance for 1 hour; the bonding pressure in the bonding process is 1000-2000N/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The bonding time of the bonding process is 5-15 seconds.
By adopting the technical scheme, the surfaces of the stainless steel plate/aluminum plate and the ceramic plate are cleaner and smoother, the adhesive force is enhanced, the surface area is increased, and the subsequent processing is convenient; the viscosity of the adhesive is more stable due to the vacuum defoamation of the adhesive, the bonding surface is smoother, and the product quality is more stable; proper bonding pressure enables the contact between the adhesive and the bonding surface to be tighter, is favorable for diffusion, permeation and gas removal, enables the adhesive layer to be even and compact, can also discharge redundant adhesive, and avoids overlong curing time and influencing the performance of products.
In summary, the application has the following beneficial effects:
1. according to the application, the aluminum oxide particles are sprayed on one side of the stainless steel plate/aluminum plate and then bonded with the ceramic plate through the adhesive, so that the bonding strength of the stainless steel layer/aluminum layer and the adhesive part is increased compared with the conventional bonding mode of directly bonding through the adhesive, and the bonding strength of the whole composite material is further improved. The product has the advantages of high bonding strength and simple manufacture.
2. According to the application, the epoxy silane coupling agent and the phosphate silane coupling agent are used for jointly modifying the alumina particles, so that the alumina particles can simultaneously improve the adhesion force with the metal layer and the adhesive layer, and the adhesion effect of the metal layer and the ceramic layer is improved.
3. According to the application, the ratio of the curing agent in the adhesive is slightly increased, so that the curing agent is left with a margin except the cured epoxy resin, and can be further crosslinked with the alumina particles, so that the bonding strength of the alumina particles and the adhesive is further improved, and the bonding strength of the whole composite material is further improved.
4. According to the application, the spraying thickness of the modified alumina particles is adjusted, so that the incomplete bonding of two materials caused by excessive thickness can be avoided, and the weak adhesiveness is caused; and the bonding effect that the mechanical locking cannot be realized due to the fact that the aluminum oxide particles are filled by the adhesive layer due to the fact that the spraying thickness is too thin is avoided.
5. According to the application, by setting the current, voltage, powder feeding amount, gas carrying amount, spraying distance and spraying angle in the spraying process of the alumina particles, the modified alumina particles are uniformly distributed and tightly adhered on the stainless steel layer/aluminum layer.
Detailed Description
Preparation example
The experimental reagents in the preparation examples are all conventional commercial brands or obtained by conventional preparation processes unless specified otherwise.
Preparation example 1
A 301 stainless steel of size 1m×1m and thickness 8mm was pretreated: oil removal, rust removal, phosphating and passivation treatment; the ceramic plate with the size of 1m multiplied by 1m and the thickness of 4mm is pretreated: the surface is clean and coarsened, and the ceramic plate comprises the following components in percentage by mass: alumina powder: boron carbide: boron nitride: magnesium fluoride: methylpentanol=93: 3:3:0.3:2; vacuum defoaming was performed in the epoxy adhesive for 1 hour. The alumina particles are modified by the following steps:
10kg of alumina micropowder and 0.03kg of phosphate silane coupling agent are added into an ethanol water solution with the concentration of 85% to be mixed, stirred for 3 hours at 80 ℃, filtered, washed for 3 times with pure water and dried in a baking oven at 120 ℃ to obtain silane modified alumina particles.
Preparation example 2
A 301 stainless steel of size 1m×1m and thickness 8mm was pretreated: oil removal, rust removal, phosphating and passivation treatment; the ceramic plate with the size of 1m multiplied by 1m and the thickness of 4mm is pretreated: the surface is clean and coarsened, and the ceramic plate comprises the following components in percentage by mass: alumina powder: boron carbide: boron nitride: magnesium fluoride: methylpentanol=93: 3:3:0.3:2; vacuum defoaming was performed in the epoxy adhesive for 1 hour. The alumina particles are modified by the following steps:
10kg of alumina micropowder and 0.08kg of phosphate silane coupling agent are added into an ethanol water solution with the concentration of 85% to be mixed, stirred for 3 hours at 80 ℃, filtered, washed for 3 times with pure water and dried in a baking oven at 120 ℃ to obtain silane modified alumina particles.
Preparation example 3
A 301 stainless steel of size 1m×1m and thickness 8mm was pretreated: oil removal, rust removal, phosphating and passivation treatment; the ceramic plate with the size of 1m multiplied by 1m and the thickness of 4mm is pretreated: the surface is clean and coarsened, and the ceramic plate comprises the following components in percentage by mass: alumina powder: boron carbide: boron nitride: magnesium fluoride: methylpentanol=93: 3:3:0.3:2; vacuum defoaming was performed in the epoxy adhesive for 1 hour. The alumina particles are modified by the following steps:
10kg of alumina micropowder and 0.13kg of phosphate silane coupling agent are added into an ethanol water solution with the concentration of 85% to be mixed, stirred for 3 hours at 80 ℃, filtered, washed for 3 times with pure water and dried in a baking oven at 120 ℃ to obtain silane modified alumina particles.
Preparation example 4
A 301 stainless steel of size 1m×1m and thickness 8mm was pretreated: oil removal, rust removal, phosphating and passivation treatment; the ceramic plate with the size of 1m multiplied by 1m and the thickness of 4mm is pretreated: the surface is clean and coarsened, and the ceramic plate comprises the following components in percentage by mass: alumina powder: boron carbide: boron nitride: magnesium fluoride: methylpentanol=93: 3:3:0.3:2; vacuum defoaming was performed in the epoxy adhesive for 1 hour. The alumina particles are modified by the following steps:
10kg of alumina micropowder and 0.08kg of epoxy silane coupling agent are added into an ethanol water solution with the concentration of 85% to be mixed, stirred for 3 hours at 80 ℃, filtered, washed for 3 times with pure water and dried in a baking oven at 120 ℃ to obtain silane modified alumina particles.
Preparation example 5
A 301 stainless steel of size 1m×1m and thickness 8mm was pretreated: oil removal, rust removal, phosphating and passivation treatment; the ceramic plate with the size of 1m multiplied by 1m and the thickness of 4mm is pretreated: the surface is clean and coarsened, and the ceramic plate comprises the following components in percentage by mass: alumina powder: boron carbide: boron nitride: magnesium fluoride: methylpentanol=93: 3:3:0.3:2; vacuum defoaming was performed in the epoxy adhesive for 1 hour. The alumina particles are modified by the following steps:
10kg of alumina micropowder, 0.04kg of epoxy silane coupling agent and 0.04kg of phosphate silane coupling agent are added into an ethanol water solution with the concentration of 85% to be mixed, stirred for 3 hours at 80 ℃, filtered, washed with pure water for 3 times and dried in an oven at 120 ℃ to obtain silane modified alumina particles.
Preparation example 6
6060 aluminum of size 1m×1m and thickness 8mm was pretreated: oil removal, rust removal, phosphating and passivation treatment; the ceramic plate with the size of 1m multiplied by 1m and the thickness of 4mm is pretreated: the surface is clean and coarsened, and the ceramic plate comprises the following components in percentage by mass: alumina powder: boron carbide: boron nitride: magnesium fluoride: methylpentanol=93: 3:3:0.3:2; vacuum defoaming was performed in the epoxy adhesive for 1 hour. The alumina particles are modified by the following steps:
10kg of alumina micropowder, 0.04kg of epoxy silane coupling agent and 0.04kg of phosphate silane coupling agent are added into an ethanol water solution with the concentration of 85% to be mixed, stirred for 3 hours at 80 ℃, filtered, washed with pure water for 3 times and dried in an oven at 120 ℃ to obtain silane modified alumina particles.
Examples
Example 1
The raw materials of the metal ceramic composite material are from preparation example 1, the rest raw materials are from common commercial brands, and the preparation method is as follows:
s1: one side of the pretreated stainless steel plate is subjected to plasma spraying to prepare modified alumina particles in example 1, wherein the specific spraying parameters are as follows: the current is 600A, the voltage is 80V, the powder feeding amount is 20g/min, the gas carrying amount is 3L/min, the spraying distance is 30mm, the spraying angle is 80 degrees, and the spraying thickness is 0.2mm;
s2: coating one surface of the stainless steel plate sprayed with modified alumina particles with a layer of epoxy resin adhesive, and bonding the surface with one surface of the ceramic layer to obtain a composite layer, wherein the epoxy resin adhesive is an adhesive with the mass ratio of epoxy resin to curing agent of 55:20;
s3: and pre-curing the bonded composite layer at 80 ℃, heating to 120 ℃ after 3 hours, and standing and curing for 8 hours.
Example 2
The raw materials of the metal ceramic composite material are from preparation example 2, the rest raw materials are from common commercial brands, and the preparation method is as follows:
s1: one side of the pretreated stainless steel plate is subjected to plasma spraying to prepare modified alumina particles in example 2, wherein the specific spraying parameters are as follows: the current is 600A, the voltage is 80V, the powder feeding amount is 20g/min, the gas carrying amount is 3L/min, the spraying distance is 30mm, the spraying angle is 80 degrees, and the spraying thickness is 0.2mm;
s2: coating one surface of the stainless steel plate sprayed with modified alumina particles with a layer of epoxy resin adhesive, and bonding the surface with one surface of the ceramic layer to obtain a composite layer, wherein the epoxy resin adhesive is an adhesive with the mass ratio of epoxy resin to curing agent of 55:20;
s3: and pre-curing the bonded composite layer at 80 ℃, heating to 120 ℃ after 3 hours, and standing and curing for 8 hours.
Example 3
The raw materials of the metal ceramic composite material are from preparation example 3, the rest raw materials are from common commercial brands, and the preparation method is as follows:
s1: one side of the pretreated stainless steel plate is subjected to plasma spraying to prepare modified alumina particles in example 3, wherein the specific spraying parameters are as follows: the current is 600A, the voltage is 80V, the powder feeding amount is 20g/min, the gas carrying amount is 3L/min, the spraying distance is 30mm, the spraying angle is 80 degrees, and the spraying thickness is 0.2mm;
s2: coating one surface of the stainless steel plate sprayed with modified alumina particles with a layer of epoxy resin adhesive, and bonding the surface with one surface of the ceramic layer to obtain a composite layer, wherein the epoxy resin adhesive is an adhesive with the mass ratio of epoxy resin to curing agent of 55:20;
s3: and pre-curing the bonded composite layer at 80 ℃, heating to 120 ℃ after 3 hours, and standing and curing for 8 hours.
Example 4
The raw materials of the metal ceramic composite material are from preparation example 4, the rest raw materials are from common commercial brands, and the preparation method is as follows:
s1: one side of the pretreated stainless steel plate is subjected to plasma spraying to prepare modified alumina particles in example 4, wherein the specific spraying parameters are as follows: the current is 600A, the voltage is 80V, the powder feeding amount is 20g/min, the gas carrying amount is 3L/min, the spraying distance is 30mm, the spraying angle is 80 degrees, and the spraying thickness is 0.2mm;
s2: coating one surface of the stainless steel plate sprayed with modified alumina particles with a layer of epoxy resin adhesive, and bonding the surface with one surface of the ceramic layer to obtain a composite layer, wherein the epoxy resin adhesive is an adhesive with the mass ratio of epoxy resin to curing agent of 55:20;
s3: and pre-curing the bonded composite layer at 80 ℃, heating to 120 ℃ after 3 hours, and standing and curing for 8 hours.
Example 5
The raw materials of the metal ceramic composite material are from preparation example 5, the rest raw materials are from common commercial brands, and the preparation method is as follows:
s1: one side of the pretreated stainless steel plate is subjected to plasma spraying to prepare modified alumina particles in example 5, wherein the specific spraying parameters are as follows: the current is 600A, the voltage is 80V, the powder feeding amount is 20g/min, the gas carrying amount is 3L/min, the spraying distance is 30mm, the spraying angle is 80 degrees, and the spraying thickness is 0.2mm;
s2: coating one surface of the stainless steel plate sprayed with modified alumina particles with a layer of epoxy resin adhesive, and bonding the surface with one surface of the ceramic layer to obtain a composite layer, wherein the epoxy resin adhesive is an adhesive with the mass ratio of epoxy resin to curing agent of 55:20;
s3: and pre-curing the bonded composite layer at 80 ℃, heating to 120 ℃ after 3 hours, and standing and curing for 8 hours.
Example 6
The raw materials of the metal ceramic composite material are from preparation example 5, the rest raw materials are from common commercial brands, and the preparation method is as follows:
s1: one side of the pretreated stainless steel plate is subjected to plasma spraying to prepare modified alumina particles in example 5, wherein the specific spraying parameters are as follows: the current is 600A, the voltage is 80V, the powder feeding amount is 20g/min, the gas carrying amount is 3L/min, the spraying distance is 30mm, the spraying angle is 80 degrees, and the spraying thickness is 0.5mm;
s2: coating one surface of the stainless steel plate sprayed with modified alumina particles with a layer of epoxy resin adhesive, and bonding the surface with one surface of the ceramic layer to obtain a composite layer, wherein the epoxy resin adhesive is an adhesive with the mass ratio of epoxy resin to curing agent of 55:20;
s3: and pre-curing the bonded composite layer at 80 ℃, heating to 120 ℃ after 3 hours, and standing and curing for 8 hours.
Example 7
The raw materials of the metal ceramic composite material are from preparation example 5, the rest raw materials are from common commercial brands, and the preparation method is as follows:
s1: one side of the pretreated stainless steel plate is subjected to plasma spraying to prepare modified alumina particles in example 5, wherein the specific spraying parameters are as follows: the current is 600A, the voltage is 80V, the powder feeding amount is 20g/min, the gas carrying amount is 3L/min, the spraying distance is 30mm, the spraying angle is 80 degrees, and the spraying thickness is 0.05mm;
s2: coating one surface of the stainless steel plate sprayed with modified alumina particles with a layer of epoxy resin adhesive, and bonding the surface with one surface of the ceramic layer to obtain a composite layer, wherein the epoxy resin adhesive is an adhesive with the mass ratio of epoxy resin to curing agent of 55:20;
s3: and pre-curing the bonded composite layer at 80 ℃, heating to 120 ℃ after 3 hours, and standing and curing for 8 hours.
Example 8
The raw materials of the metal ceramic composite material are from preparation example 5, the rest raw materials are from common commercial brands, and the preparation method is as follows:
s1: one side of the pretreated stainless steel plate is subjected to plasma spraying to prepare modified alumina particles in example 5, wherein the specific spraying parameters are as follows: the current is 600A, the voltage is 80V, the powder feeding amount is 20g/min, the gas carrying amount is 3L/min, the spraying distance is 30mm, the spraying angle is 80 degrees, and the spraying thickness is 0.2mm;
s2: coating one surface of the stainless steel plate sprayed with modified alumina particles with a layer of epoxy resin adhesive, and bonding the surface with one surface of the ceramic layer to obtain a composite layer, wherein the epoxy resin adhesive is an adhesive with the mass ratio of epoxy resin to curing agent of 7:1;
s3: and pre-curing the bonded composite layer at 80 ℃, heating to 120 ℃ after 3 hours, and standing and curing for 8 hours.
Example 9
The raw materials of the metal ceramic composite material are from preparation example 5, the rest raw materials are from common commercial brands, and the preparation method is as follows:
s1: one side of the pretreated stainless steel plate is subjected to plasma spraying to prepare modified alumina particles in example 5, wherein the specific spraying parameters are as follows: the current is 600A, the voltage is 80V, the powder feeding amount is 20g/min, the gas carrying amount is 3L/min, the spraying distance is 30mm, the spraying angle is 80 degrees, and the spraying thickness is 0.2mm;
s2: coating one surface of the stainless steel plate sprayed with modified alumina particles with a layer of epoxy resin adhesive, and bonding the surface with one surface of the ceramic layer to obtain a composite layer, wherein the epoxy resin adhesive is an adhesive with the mass ratio of epoxy resin to curing agent of 55:40;
s3: and pre-curing the bonded composite layer at 80 ℃, heating to 120 ℃ after 3 hours, and standing and curing for 8 hours.
Example 10
The raw materials of the metal ceramic composite material are from preparation example 6, the rest raw materials are from common commercial brands, and the preparation method is as follows:
s1: one side of the pretreated aluminum plate was subjected to plasma spraying to prepare modified alumina particles in example 6, wherein the specific spraying parameters are as follows: the current is 600A, the voltage is 80V, the powder feeding amount is 20g/min, the gas carrying amount is 3L/min, the spraying distance is 30mm, the spraying angle is 80 degrees, and the spraying thickness is 0.2mm;
s2: coating one surface of aluminum plate sprayed with modified alumina particles with a layer of epoxy resin adhesive, and bonding the surface with one surface of the ceramic layer to obtain a composite layer, wherein the epoxy resin adhesive is an adhesive with the mass ratio of epoxy resin to curing agent of 55:20;
s3: and pre-curing the bonded composite layer at 80 ℃, heating to 120 ℃ after 3 hours, and standing and curing for 8 hours.
Comparative example
Comparative example 1
The raw materials of the metal ceramic composite material are from preparation example 5, the rest raw materials are from common commercial brands, and the preparation method is as follows:
s1: coating one side of the pretreated stainless steel plate with a layer of epoxy resin adhesive, and bonding the side with one side of the ceramic layer to obtain a composite layer, wherein the epoxy resin adhesive is an adhesive with the mass ratio of epoxy resin to curing agent of 55:20;
s3: and pre-curing the bonded composite layer at 80 ℃, heating to 120 ℃ after 3 hours, and standing and curing for 8 hours.
Comparative example 2
The raw materials of the metal ceramic composite material are from preparation example 5, the rest raw materials are from common commercial brands, and the preparation method is as follows:
s1: one surface of the pretreated stainless steel plate is sprayed with aluminum oxide particles which are not modified by any silane by plasma, and the specific spraying parameters are as follows: the current is 600A, the voltage is 80V, the powder feeding amount is 20g/min, the gas carrying amount is 3L/min, the spraying distance is 30mm, the spraying angle is 80 degrees, and the spraying thickness is 0.2mm;
s2: coating one surface of the stainless steel plate sprayed with alumina particles with a layer of epoxy resin adhesive, and bonding the surface with one surface of the ceramic layer to obtain a composite layer, wherein the epoxy resin adhesive is an adhesive with the mass ratio of epoxy resin to curing agent of 55:20;
s3: and pre-curing the bonded composite layer at 80 ℃, heating to 120 ℃ after 3 hours, and standing and curing for 8 hours.
Performance test one: and (3) peeling off the metal layer at one end of the sample by using a model MK-BL-X90-degree peeling strength tester by about 10mm, clamping the sample on a sample frame of the peeling machine, clamping the peeled metal layer by using a sample clamp, and starting the peeling machine to uniformly apply a tensile force. The allowable deviation of the pulling force direction and the plane of the base material is kept to be +/-5 degrees, so that the metal layer is carried out at a constant speed of 50 +/-5 mm/min, the minimum stripping force with the stripping length not less than 25mm is recorded in the stripping process, and the test is carried out for 4 times, and the minimum value is taken. The peel strength of the cermet composites prepared in examples 1-10 and comparative examples 1-2 was measured in the above manner, respectively.
The test results are summarized in table 1.
Table 1-example 10, comparative examples 1-2 Performance test data
In combination with examples 1 to 5, comparative example 1 and comparative example 2, the bonding strength of the modified alumina particles co-modified with the epoxy silane coupling agent and the phosphate silane coupling agent sprayed on the stainless steel plate is greater than that of the composite material in which only one kind of the silane coupling agent modified alumina particles is sprayed on the stainless steel plate, and is greater than that of the stainless steel plate on which the unmodified alumina particles are sprayed, and is far greater than that of direct bonding. This is probably due to the fact that the contact area between the steel plate/aluminum plate sprayed with the modified aluminum oxide and the epoxy resin adhesive is larger, and the epoxy silane coupling agent is combined with the curing agent in the epoxy resin adhesive on one hand, a strong chemical bond is formed at the bonding interface, on the other hand, the phosphate group improves the adhesion effect between the epoxy silane coupling agent and the metal layer, and the cohesiveness of the composite material is further improved.
In combination with examples 6 to 7, the adhesive effect is better when the spraying thickness of the alumina particles is 0.1 to 0.3mm, and the adhesive effect is slightly poorer when the spraying thickness is not in the range, which is probably due to incomplete bonding of the two materials caused by the excessive thickness of the spraying, and the adhesive property is not strong; too thin a spray thickness may lead to aluminum oxide particles being filled with an adhesive layer, resulting in failure to achieve the bonding effect of mechanical keying.
In combination with examples 8-9, the adhesive layer becomes brittle when the curing agent is excessive, the bonding strength is reduced, and a proper excess of the curing agent can be crosslinked with the epoxy groups of the modified alumina particles, so that the bonding strength of the modified alumina particles and the epoxy resin adhesive is increased, the bonding strength of the metal ceramic composite material is further improved, the curing time of the epoxy resin adhesive is prolonged and even the curing is impossible when the curing agent is less, and the bonding strength of the metal ceramic composite material is greatly weakened.
In combination with the embodiment 5 and the embodiment 10, the stainless steel layer in the metal ceramic composite material is replaced by an aluminum layer, so that the adhesive property is not greatly influenced, and the metal ceramic composite material can be flexibly selected according to actual production requirements.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (10)
1. A metal/ceramic composite material characterized by: the metal/ceramic composite material comprises a ceramic layer and a metal layer, and the ceramic layer and the metal layer are bonded through an adhesive; and modified alumina particles are sprayed on one surface of the metal layer, which is close to the ceramic layer.
2. The metal/ceramic composite according to claim 1, wherein: the modified alumina particles are silane modified alumina particles which are formed by modifying epoxy silane coupling agents and phosphate silane coupling agents together.
3. The metal/ceramic composite according to claim 2, wherein: the modification step of the silane modified alumina particles comprises: adding alumina micropowder, epoxy silane coupling agent and phosphate silane coupling agent into ethanol water solution, mixing, stirring at 70-90 ℃ for 2-4 hours, filtering, washing with purified water for 2-3 times, and drying in a baking oven at 100-120 ℃ to obtain silane modified alumina particles.
4. The metal/ceramic composite according to claim 1, wherein: the spraying thickness of the modified alumina particles is 0.1-0.3 mm.
5. The metal/ceramic composite according to claim 1, wherein: the adhesive comprises 55-70 parts by weight of epoxy resin and 20-30 parts by weight of curing agent.
6. The metal/ceramic composite according to claim 1, wherein: the ceramic layer comprises the following raw materials in parts by weight:
90-95 parts of alumina powder,
2-5 parts of boron carbide,
2-5 parts of boron nitride,
0.1-0.5 part of sintering auxiliary agent,
0.5-4 parts of dispersing agent.
7. The metal/ceramic composite according to claim 1, wherein: the metal layer is one of a stainless steel layer and an aluminum layer.
8. A method of making a metal/ceramic composite according to any one of claims 1 to 7, wherein: the method comprises the following steps:
s1: spraying modified alumina particles on one surface of the pretreated metal layer;
s2: coating a layer of adhesive on one surface of the sprayed modified alumina particles, and bonding the surface with one surface of the ceramic layer to obtain a composite layer;
s3: and pre-curing the bonded composite layer at 60-90 ℃, heating to 100-120 ℃ after 2-4 hours, and standing and curing for 6-8 hours to obtain the metal/ceramic composite material.
9. The method of manufacturing according to claim 8, wherein: the spraying is plasma spraying, and parameters of the plasma thermal spraying comprise: the current is 550-650A, the voltage is 60-90V, the powder feeding amount is 15-25g/min, the gas carrying amount is 2.5-3.5L/min, the spraying distance is 25-50 mm, and the spraying angle is 60-90 degrees.
10. The method of manufacturing according to claim 8, wherein: the metal layer is made of a stainless steel plate/aluminum plate, the pretreatment of the metal layer is oil removal, rust removal, phosphating and passivation treatment, and the surface bonding of the ceramic layer is cleaned and roughened in advance; the adhesive is subjected to vacuum defoamation in advance for 1 hour; the bonding pressure in the bonding process is 1000-2000N/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The bonding time of the bonding process is 5-15 seconds.
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