CN108129169B - Metal ceramic product and preparation method thereof - Google Patents
Metal ceramic product and preparation method thereof Download PDFInfo
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- CN108129169B CN108129169B CN201611094200.3A CN201611094200A CN108129169B CN 108129169 B CN108129169 B CN 108129169B CN 201611094200 A CN201611094200 A CN 201611094200A CN 108129169 B CN108129169 B CN 108129169B
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
- C04B41/90—Coating or impregnation for obtaining at least two superposed coatings having different compositions at least one coating being a metal
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Abstract
The invention relates to the field of appearance product, in particular to a metal ceramic product and a preparation method thereof. The metal ceramic product comprises a porous ceramic substrate, a metal layer and a metal oxide layer, wherein the metal layer and the metal oxide layer are sequentially coated on the surface of the porous ceramic substrate, and metal is filled in pores of the porous ceramic substrate; wherein the metal is one or more of aluminum and aluminum alloy; the porous ceramic substrate is formed from a ceramic powder composition containing first ceramic powder, second ceramic powder, and third ceramic powder, and the particle size of the first ceramic powder > the particle size of the second ceramic powder > the particle size of the third ceramic powder, and the content of the ceramic powder in the porous ceramic substrate is 50 vol% or more. The metal ceramic product has better rigidity and excellent cold and heat shock resistance, can be uniformly colored, and can be used for preparing appearance products with more excellent performances in all aspects.
Description
Technical Field
The invention relates to the field of appearance product, in particular to a metal ceramic product and a preparation method thereof.
Background
At present, the appearance piece of the aluminum product is in a very perfect stage due to the perfection of the processes such as anodic oxidation coloring and the like. However, due to the yield of aluminum metal in the stress and deformation processes, the product is easy to bend and deform, so that the product suffers from certain application bottlenecks, and particularly in the field of appearance articles, the product suffers from scaling caused by bending, deformation and the like.
Disclosure of Invention
The invention aims to provide a metal ceramic product with good rigidity and excellent cold and heat shock resistance and a preparation method thereof aiming at the defects of poor rigidity and poor cold and heat shock resistance of related appearance pieces prepared by the existing direct anodic oxidation of aluminum or aluminum alloy.
In order to achieve the above object, the present invention provides a metal-ceramic article, which includes a porous ceramic substrate, and a metal layer and a metal oxide layer sequentially coated on a surface of the porous ceramic substrate, wherein metal is filled in pores of the porous ceramic substrate; wherein the metal is one or more of aluminum and aluminum alloy; the porous ceramic substrate is formed from a ceramic powder composition containing first ceramic powder, second ceramic powder, and third ceramic powder, and the particle size of the first ceramic powder > the particle size of the second ceramic powder > the particle size of the third ceramic powder, and the content of the ceramic powder in the porous ceramic substrate is 50 vol% or more.
The present invention also provides a method for preparing the above-described cermet article, the method comprising:
(1) mixing a ceramic powder composition containing first ceramic powder, second ceramic powder and third ceramic powder with a binder, and performing compression molding, binder removal and sintering on the obtained mixture to obtain the porous ceramic substrate;
(2) impregnating the porous ceramic substrate with a molten metal so that pores of the porous ceramic substrate are filled with the metal and so that a surface of the porous ceramic substrate is coated with the metal layer;
(3) and carrying out anodic oxidation treatment on the metal layer to obtain the metal oxide layer.
By the preparation method, the metal ceramic product with better rigidity and excellent cold and hot shock resistance can be obtained, and the obtained metal ceramic product can be uniformly colored, so that an appearance product with more excellent performances in all aspects can be prepared.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a schematic view of a cermet article of the present invention.
Description of the reference numerals
1: a porous ceramic substrate; 2: a metal layer; 3: a metal oxide layer.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a metal ceramic product, which comprises a porous ceramic substrate, a metal layer and a metal oxide layer, wherein the metal layer and the metal oxide layer are sequentially coated on the surface of the porous ceramic substrate, and metal is filled in pores of the porous ceramic substrate; wherein the metal is one or more of aluminum and aluminum alloy; the porous ceramic substrate is formed from a ceramic powder composition containing first ceramic powder, second ceramic powder, and third ceramic powder, and the particle size of the first ceramic powder > the particle size of the second ceramic powder > the particle size of the third ceramic powder, and the content of the ceramic powder in the porous ceramic substrate is 50 vol% or more.
As shown in fig. 1, the substrate of the cermet article according to the present invention is a porous ceramic substrate having a porous structure, and the porous ceramic substrate 1 has a high content of ceramic, that is, a relatively low porosity, so that the ceramic component of the resultant cermet article occupies a considerable proportion although the pores of the porous ceramic substrate are filled with metal (not shown). The metal ceramic product of the invention adopts the porous ceramic substrate 1 with high ceramic powder content, and the porous ceramic substrate 1 is formed by the ceramic powder composition containing the first ceramic powder, the second ceramic powder and the third ceramic powder with different granularities, wherein, the ceramic powder with larger granularity can provide larger gaps, and the ceramic powder with smaller granularity is filled in the formed gaps, so that the porous ceramic substrate with the ceramic powder content of more than 50 volume percent can be obtained, and after the porous ceramic substrate is filled with one or more metals of aluminum and aluminum alloy and the surface is covered with the metal layer 2 of one or more metals of aluminum and aluminum alloy, more ceramic properties can be kept for the material, thus not only improving the rigidity of the obtained metal ceramic product and greatly improving the cold and hot shock resistance, but also obtaining a more uniform metal oxide layer 3 after the metal layer is subjected to anodic oxidation treatment, the coloring power is stronger, and the metallic ceramic product with better coloring effect can be obtained, which is very superior for preparing colored appearance pieces.
According to the present invention, although the content of the ceramic powder in the porous ceramic substrate is 50 vol% or more, it is possible to achieve a reasonable ratio of the ceramic component to the metal component, and preferably, the content of the ceramic powder in the porous ceramic substrate is 50 to 80 vol%, more preferably 60 to 70 vol%.
According to the present invention, the ceramic powder forming the porous ceramic substrate should contain the first ceramic powder, the second ceramic powder and the third ceramic powder of different particle sizes, wherein the particle size of the first ceramic powder > the particle size of the second ceramic powder > the particle size of the third ceramic powder, in such a configuration that the resulting porous ceramic substrate can obtain a relatively high density. Preferably, the particle size of the first ceramic powder is 40-100 μm, the particle size of the second ceramic powder is 15-40 μm, and the particle size of the third ceramic powder is 1-15 μm. More preferably, the particle size of the first ceramic powder is 50 to 70 μm, the particle size of the second ceramic powder is 20 to 30 μm, and the particle size of the third ceramic powder is 2 to 10 μm.
According to the present invention, in order to enable the first ceramic powder, the second ceramic powder, and the third ceramic powder to better exhibit a mutual interaction to obtain a porous ceramic substrate having more excellent properties, it is preferable that the ceramic powder composition has a weight ratio of the first ceramic powder, the second ceramic powder, and the third ceramic powder of 2 to 8: 0.5-5: 1, preferably 2 to 5: 0.5-3: 1, more preferably 3 to 5: 1-2: 1.
wherein, the first ceramic powder, the second ceramic powder and the third ceramic powder can be selected from a plurality of ceramic powders for preparing ceramics in the field, preferably, the first ceramic powder, the second ceramic powder and the third ceramic powder are respectively and independently selected from SiC ceramics and Al ceramics2O3Ceramics, ZrO2Ceramics, AlN ceramics and Si3N4One or more of ceramics. More preferably, the first ceramic powder, the second ceramic powder and the third ceramic powder are the same kind of ceramic powder.
According to the present invention, the porous ceramic substrate may be prepared by a method conventional in the art as long as the above requirements are satisfied, but the present invention preferably prepares the porous ceramic substrate by a method described hereinafter, so that the obtained porous ceramic substrate is more excellent in properties.
According to the invention, the metal will fill the pores in the porous ceramic substrate and will also form a metal layer coating the surface of the porous ceramic substrate and provide the elemental metal component of the metal oxide layer. The metal of the present invention is selected from one or more of aluminum and aluminum alloy, and the metal ceramic product with good rigidity and excellent cold and hot shock resistance is prepared by the action between the aluminum and the aluminum alloy and the porous ceramic substrate of the present invention, and is suitable for being used as an appearance piece, particularly suitable for obtaining an appearance piece product with excellent coloring. Wherein the elements other than aluminum contained in the aluminum alloy include Si, Fe, Cu, Mn, Mg, and the like.
In a preferred embodiment of the present invention, the aluminum alloy is preferably one or more of a 1-series aluminum alloy (e.g., aluminum alloy No. 1a99, aluminum alloy No. 1a97, aluminum alloy No. 1a95, etc.), A3-series aluminum alloy (e.g., aluminum alloy No. 3004, etc.), a 5-series aluminum alloy (e.g., aluminum alloy No. 5a01, aluminum alloy No. 5a02, aluminum alloy No. 5a03, etc.), a 6-series aluminum alloy (e.g., aluminum alloy No. 6061, aluminum alloy No. 6063), and a 7-series aluminum alloy (e.g., aluminum alloy No. 7475, aluminum alloy No. 7075, aluminum alloy No. 7003, aluminum alloy No. 7005, etc.), and more preferably one or more of a 6-series aluminum alloy (e.g.
According to the present invention, the thickness of the metal layer is not particularly limited, and may be appropriately selected according to the specific requirements for the cermet article, for example, the thickness of the metal layer is 0.1 to 0.5 mm. The thickness of the metal oxide layer is also not particularly limited, and may be a thickness of a metal oxide layer that is conventional in the art, for example, the thickness of the metal oxide layer is 1 to 10 μm, preferably 3 to 6 μm. The shape of the porous ceramic substrate is not particularly limited in the present invention, and may be, for example, a plate shape (the thickness may be, for example, 1 to 100mm, preferably 5 to 20 mm).
The present invention also provides a method for preparing the above-described cermet article, the method comprising:
(1) mixing a ceramic powder composition containing first ceramic powder, second ceramic powder and third ceramic powder with a binder, and performing compression molding, binder removal and sintering on the obtained mixture to obtain the porous ceramic substrate;
(2) impregnating the porous ceramic substrate with a molten metal so that pores of the porous ceramic substrate are filled with the metal and so that a surface of the porous ceramic substrate is coated with the metal layer;
(3) and carrying out anodic oxidation treatment on the metal layer to obtain the metal oxide layer.
According to the present invention, the first ceramic powder, the second ceramic powder and the third ceramic powder are as described above and will not be described herein again.
According to the invention, in the step (1), the ceramic powder composition containing the first ceramic powder, the second ceramic powder and the third ceramic powder and the binder can enable the ceramic powders to be bonded together under the action of the binder so as to form the ceramic body after compression molding. Among them, the binder may be various binders conventionally used in the art for preparing a porous ceramic substrate, and preferably, the binder is one or more of polyvinyl alcohol (PVA), epoxy resin (EP), phenol resin, furfural resin, and the like. The epoxy resin that can be used in the present invention includes, but is not limited to, one or more of epoxy resin of E-51 type, epoxy resin of E-44 type, epoxy resin of F-51 type, epoxy resin of F-44 type, and phenolic resin that can be used in the present invention includes, but is not limited to, one or more of phenolic resin of 2130 type, phenolic resin of 2124 type, phenolic resin of 2127 type, and modified phenolic resin. These binders have a strong binding power, allow the green body to be processed after press forming, and are easy to remove during the binder removal stage. Wherein the binder is typically provided in the form of a solution, for example in the form of a 2-10 wt% solution (the solvent may be, for example, ethanol, etc.).
According to the invention, the amount of binder can vary within wide limits, preferably from 0.01 to 20 parts by weight, preferably from 0.02 to 10 parts by weight, more preferably from 0.05 to 5 parts by weight, based on dry weight, of binder per 100 parts by weight of the ceramic powder composition.
According to the invention, the mixing of the ceramic powder composition and the binder in step (1) is preferably carried out by grinding, so that the ceramic powder composition is granulated during grinding and then is pressed to form the required green body. The pressure for the press molding may be, for example, 5 to 20 MPa.
According to the invention, after the green body is obtained by press forming, the green body needs to be subjected to binder removal and sintering, and the binder removal conditions can include: the temperature is 500-. The conditions for the sintering may include, for example: the temperature is 900-1800 deg.C (preferably 900-1400 deg.C), and the time is 30-300min (preferably 100-200 min). The binder removal may be directly performed in an air atmosphere, and the sintering may be performed in an air atmosphere or a nitrogen atmosphere, which is not particularly limited in the present invention. And cooling after sintering is finished to obtain the porous ceramic substrate.
According to the present invention, in the step (2), the pores of the porous ceramic substrate are filled with the metal and the surface of the porous ceramic substrate is coated with the metal layer by the operation of impregnating the metal solution. Preferably, the impregnation conditions include: the temperature is 500-800 deg.C (preferably 500-700 deg.C), more preferably 500-600 deg.C), the pressure is 1-10MPa (preferably 5-7MPa), and the time is 10-100min (preferably 20-40 min).
Wherein, in order to better enable the molten metal to be compatible with the porous ceramic substrate, preferably, the infiltration process comprises the following steps: the porous ceramic substrate is placed in a mold, and is vacuumized and heated to 500-800 ℃ (preferably 500-700 ℃, more preferably 500-600 ℃), and then metal liquid is introduced and kept for 10-100min (preferably 20-40min) under 1-10MPa (preferably 5-7 MPa). The mold may be, for example, a graphite mold. The process may specifically include: the method comprises the steps of firstly placing a porous ceramic substrate in a mold, reserving a certain gap for forming a metal layer, then vacuumizing a system (including enabling the mold and the porous ceramic substrate to be in a vacuum environment) and preheating to a specified temperature, then introducing molten metal at the pressure of 1-10MPa (preferably 5-7MPa) and maintaining the pressure for 10-100min (preferably 20-40min), and cooling to enable the metal and the porous ceramic substrate to be compounded.
According to the invention, step (3) adopts the means of anodic oxidation treatment which is conventional in the field, so that the surface of the metal layer forms an oxide layer of the corresponding metal. If necessary, the metal oxide layer can be dyed to obtain the appearance product with the required color.
The method of the invention can obtain the metal ceramic product with better rigidity and excellent cold and hot shock resistance, for example, the bending strength of the metal ceramic product is more than 300MPa, preferably 320-380 MPa; impact for more than 25 times without peeling.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples:
the volume fraction of the ceramic substrate refers to the percentage of the ceramic component of the ceramic substrate to the total volume of the ceramic substrate.
Preparation example 1
The 6061 aluminum alloy is prepared by a formula with the mixture ratio of 0.6 wt% of Si, 0.7 wt% of Fe, 0.3 wt% of Cu, 0.15 wt% of Mn, 1 wt% of Mg and the balance of Al, and the specific process comprises the following steps: melting pure aluminum in a well-type resistance furnace (under the protection of argon, the temperature is set to 700 ℃), then putting the particles of other element components into the melt according to the respective contents in the mixture ratio, stirring for 60min, refining, degassing for 20min, and finally casting into an ingot.
Preparation example 2
The 6063 aluminum alloy is prepared by a formula of 0.3 wt% of Si, 0.35 wt% of Fe, 0.1 wt% of Cu, 0.1 wt% of Mn, 0.6 wt% of Mg and the balance of Al, and the specific process comprises the following steps: melting pure aluminum in a well-type resistance furnace (under the protection of argon, the temperature is set to 700 ℃), then putting the particles of other element components into the melt according to the respective contents in the mixture ratio, stirring for 60min, refining, degassing for 20min, and finally casting into an ingot.
Example 1
This example illustrates the cermet articles of the present invention and their method of preparation.
(1) 1kg of SiC ceramic powder (the mass ratio is 3:1:1) with the particle sizes of 63 mu m, 28 mu m and 5 mu m is taken, 10g of PVA binder solution with the concentration of 5 weight percent is added for grinding and granulation; then pressing the granulated powder into a green body with the diameter of 60mm and the thickness of 6mm by adopting a manual molding press at the pressure of 10 MPa; placing the blank body into a box furnace (in air atmosphere) for binder removal and sintering, wherein the binder removal temperature is 575 ℃ and the time is 180 min; the sintering temperature is 1100 ℃, and the time is 120 min. Cooling along with the furnace to obtain the porous ceramic substrate with the volume fraction of 62%.
(2) The porous ceramic substrate is subjected to flat grinding to form a plate with the thickness of 5mm, the plate is placed in a graphite mold, the prefabricated gap is 0.2mm, then a chamber in which the graphite mold and the porous ceramic substrate are placed is vacuumized and preheated to 520 ℃, then aluminum alloy melt (self-made No. 6061 aluminum alloy) is filled into the graphite mold under the pressure of 6MPa, the pressure is maintained for 20min, and cooling is carried out to obtain a composite of the porous ceramic substrate and metal.
(3) The aluminum layer on the surface of the composite of the porous ceramic substrate and the metal was polished, and then subjected to anodic oxidation treatment (treatment at 20V in a sulfuric acid solution of 20 g/L) and dyeing treatment to obtain a black cermet article A1. The thickness of the aluminum alloy layer of the product was 0.1mm, and the thickness of the aluminum oxide film was 3 μm.
Example 2
This example illustrates the cermet articles of the present invention and their method of preparation.
The process as described in example 1, except that, in step (1), particle sizes of 60 μm, 25 μm and10 μm of Al2O3Preparing a porous ceramic substrate by using ceramic powder (the mass ratio is 3:1:1) instead of SiC ceramic powder, wherein the sintering temperature is 1200 ℃, and the sintering time is 180 min; cooling to obtain the porous ceramic substrate with the volume fraction of 60%;
the grey cermet article a2 was obtained in two subsequent steps. The aluminum metal layer of the article had a thickness of 0.15mm and the aluminum oxide film had a thickness of 4 μm.
Example 3
This example illustrates the cermet articles of the present invention and their method of preparation.
According to the process described in example 1, except that, in step (1), ZrO with a grain size of 63 μm, 28 μm and 5 μm was used2Preparing a porous ceramic substrate by using ceramic powder (the mass ratio is 3:1:1) instead of SiC ceramic powder, wherein the sintering temperature is 1000 ℃, and the sintering time is 180 min; cooling to obtain the porous ceramic substrate with the volume fraction of 61%;
the grey cermet article a3 was obtained in two subsequent steps. The aluminum metal layer of the article had a thickness of 0.2mm and the aluminum oxide film had a thickness of 5 μm.
Example 4
This example illustrates the cermet articles of the present invention and their method of preparation.
According to the method described in example 1, except that, in step (1), AlN ceramic powders (in a mass ratio of 3:2:1) having particle sizes of 63 μm, 28 μm and 5 μm were used in place of the SiC ceramic powders to prepare a porous ceramic substrate, and the sintering temperature was 1300 ℃ for 180 min; cooling to obtain a porous ceramic substrate with the volume fraction of 65%;
the grey cermet article a4 was obtained in two subsequent steps. The aluminum metal layer of the article had a thickness of 0.2mm and the aluminum oxide film had a thickness of 4 μm.
Example 5
This example illustrates the cermet articles of the present invention and their method of preparation.
According to the process described in example 1, except that, in step (1), Si with particle sizes of 63 μm, 28 μm and 5 μm is used3N4Ceramic powder (mass ratio is 3:1:1) generationPreparing a porous ceramic substrate instead of SiC ceramic powder, wherein the sintering temperature is 1300 ℃, and the sintering time is 180 min; cooling to obtain a porous ceramic substrate with the volume fraction of 65%;
the grey cermet article a5 was obtained in two subsequent steps. The aluminum metal layer of the article had a thickness of 0.1mm and the aluminum oxide film had a thickness of 3 μm.
Comparative example 1
No. 6063 aluminum alloy material (made into an aluminum alloy plate with a thickness of 5 mm) was subjected to anodizing treatment and dyeing treatment by the method of step 3 of example 1 directly to obtain a black metal product DA 1. The thickness of the aluminum oxide film of the product was 3 μm.
Comparative example 2
No. 6063 aluminum alloy material (made into an aluminum alloy plate with the thickness of 5 mm) is directly subjected to vacuum pressure infiltration of No. 6061 aluminum alloy melt by the method of step 2 in example 1 to form an aluminum metal layer on the surface of the No. 6063 aluminum alloy material, and then subjected to anodic oxidation treatment and dyeing treatment by the method of step 3 to obtain a black metal product DA 2. The thickness of the aluminum alloy 6061 layer of the product is 0.15mm, and the thickness of the aluminum oxide film is 3 μm.
Comparative example 3
The process of example 1, except that instead of preparing a porous ceramic substrate from a combination of 63, 28 and 5 μm SiC ceramic powders, a 63 μm particle size SiC ceramic powder was used in step (1), the final resulting porous ceramic substrate had a volume fraction of 55%;
the subsequent two steps yielded a black cermet article DA 3. The aluminum metal layer of the article had a thickness of 0.2mm and the aluminum oxide film had a thickness of 3 μm.
Comparative example 4
The process of example 1 was followed except that instead of preparing a porous ceramic substrate from a combination of 63, 28 and 5 μm SiC ceramic powders, a 28 μm particle size SiC ceramic powder was used in step (1), resulting in a 56 volume percent porous ceramic substrate;
the subsequent two steps yielded a black cermet article DA 4. The aluminum metal layer of the article had a thickness of 0.15mm and the aluminum oxide film had a thickness of 4 μm.
Comparative example 5
The process of example 1 was followed except that instead of preparing a porous ceramic substrate from a combination of 63, 28 and 5 μm SiC ceramic powders, a5 μm SiC ceramic powder was used in step (1), the final resulting porous ceramic substrate had a volume fraction of 53%;
the subsequent two steps yielded a black cermet article DA 5. The aluminum metal layer of the article had a thickness of 0.1mm and the aluminum oxide film had a thickness of 3 μm.
Comparative example 6
And the method according to example 1, except that, instead of preparing the porous ceramic substrate from the SiC ceramic powder combinations of 63 μm, 28 μm and 5 μm, a SiC ceramic powder combination of 63 μm, 28 μm and 28 μm (mass ratio of 3:1) was used in step (1), the volume fraction of the final resulting porous ceramic substrate was 58%;
the subsequent two steps yielded a black cermet article DA 6. The aluminum metal layer of the article had a thickness of 0.2mm and the aluminum oxide film had a thickness of 5 μm.
Test example 1
The flexural strength and thermal shock resistance of the above-mentioned articles A1-A5 and DA1-DA6 were measured, and the results are shown in Table 1, in which:
the bending strength is measured according to the metal bending mechanical property test method in YB/T5349-2006.
The test process of the cold and hot shock resistance specifically comprises the following steps: the product to be tested is insulated at 300 ℃ for 10 minutes, and is rapidly put into room temperature water (about 25 ℃) so as to realize 1 cold and hot impact, and then the insulation and delivery are repeated, and the bonding condition (whether the aluminum layer is peeled off) of the aluminum layer and the substrate is observed.
TABLE 1
As can be seen from Table 1, the method of the present invention can obtain a metal-ceramic product with good rigidity and excellent thermal shock resistance, for example, the bending strength of the metal-ceramic product is above 300MPa, preferably 320-380 MPa; no peeling after more than 25 times of impact; articles made only with aluminum and its alloys (e.g., comparative examples 1 and 2) have low bending strength, e.g., 220MPa or less; no peeling can be carried out for less than 10 times; in addition, the ceramic substrates formed by using the ceramic powders which do not satisfy the requirements of the present invention, the obtained cermet articles (such as comparative examples 3-6) also have difficulty in obtaining high bending strength and thermal shock resistance, such as bending strength below 260MPa, and no peeling below 20 times.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (9)
1. The metal ceramic product is characterized by comprising a porous ceramic substrate, a metal layer and a metal oxide layer, wherein the metal layer and the metal oxide layer are sequentially coated on the surface of the porous ceramic substrate, and metal is filled in pores of the porous ceramic substrate; wherein the metal is one or more of aluminum and aluminum alloy; the porous ceramic substrate is formed of a ceramic powder composition containing a first ceramic powder, a second ceramic powder and a third ceramic powder, and the particle size of the first ceramic powder > the particle size of the second ceramic powder > the particle size of the third ceramic powder, the content of the ceramic powder in the porous ceramic substrate being 60 to 70% by volume;
in the ceramic powder composition, the weight ratio of the first ceramic powder to the second ceramic powder to the third ceramic powder is 2-5: 0.5-3: 1;
the granularity of the first ceramic powder is 40-100 mu m, the granularity of the second ceramic powder is 15-40 mu m, and the granularity of the third ceramic powder is 1-15 mu m.
2. The cermet article of claim 1, wherein the first ceramic powder has a particle size of 50-70 μ ι η, the second ceramic powder has a particle size of 20-30 μ ι η, and the third ceramic powder has a particle size of 2-10 μ ι η.
3. The cermet article of claim 1 or 2, wherein the first, second, and third ceramic powders are each independently selected from SiC ceramic, Al ceramic2O3Ceramics, ZrO2Ceramics, AlN ceramics and Si3N4One or more of ceramics.
4. The cermet article of claim 1 or 2, wherein the aluminum alloy is one or more of a 1-series aluminum alloy, a 3-series aluminum alloy, a 5-series aluminum alloy, a 6-series aluminum alloy, and a 7-series aluminum alloy.
5. The cermet article of claim 1, wherein the metal layer has a thickness of 0.1-0.5mm, the metal oxide layer has a thickness of 1-10 μ ι η, and the porous ceramic substrate has a thickness of 1-100 mm.
6. A method of making the cermet article of any one of claims 1-5 comprising:
(1) mixing a ceramic powder composition containing first ceramic powder, second ceramic powder and third ceramic powder with a binder, and performing compression molding, binder removal and sintering on the obtained mixture to obtain the porous ceramic substrate;
(2) impregnating the porous ceramic substrate with a molten metal so that pores of the porous ceramic substrate are filled with the metal and so that a surface of the porous ceramic substrate is coated with the metal layer;
(3) and carrying out anodic oxidation treatment on the metal layer to obtain the metal oxide layer.
7. The method of claim 6, wherein the conditions of the sintering comprise: the temperature is 900 ℃ and 1800 ℃, and the time is 30-300 min.
8. The method of claim 6, wherein in step (2), the infiltration conditions comprise: the temperature is 500 ℃ and 800 ℃, the pressure is 1-10MPa, and the time is 10-100 min.
9. The method of claim 8, wherein the infiltrating comprises: and placing the porous ceramic substrate into a mold, vacuumizing and heating to 800 ℃ at 500-.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611094200.3A CN108129169B (en) | 2016-12-01 | 2016-12-01 | Metal ceramic product and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2148270A (en) * | 1983-10-22 | 1985-05-30 | British Ceramic Res Ass | Cermet materials |
| CN1049647A (en) * | 1989-07-22 | 1991-03-06 | 联合铝产品股份公司 | Ceramics-metall composite |
| CN105523765A (en) * | 2014-11-27 | 2016-04-27 | 比亚迪股份有限公司 | Porous SiC prefabricated product, its preparation method and ceramic-metal composite material |
| CN105712745A (en) * | 2014-12-02 | 2016-06-29 | 比亚迪股份有限公司 | Colored ceramic and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2148270A (en) * | 1983-10-22 | 1985-05-30 | British Ceramic Res Ass | Cermet materials |
| CN1049647A (en) * | 1989-07-22 | 1991-03-06 | 联合铝产品股份公司 | Ceramics-metall composite |
| CN105523765A (en) * | 2014-11-27 | 2016-04-27 | 比亚迪股份有限公司 | Porous SiC prefabricated product, its preparation method and ceramic-metal composite material |
| CN105712745A (en) * | 2014-12-02 | 2016-06-29 | 比亚迪股份有限公司 | Colored ceramic and preparation method thereof |
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