CN108484213B - Ceramic metal porous composite material and preparation method thereof - Google Patents

Ceramic metal porous composite material and preparation method thereof Download PDF

Info

Publication number
CN108484213B
CN108484213B CN201810611574.0A CN201810611574A CN108484213B CN 108484213 B CN108484213 B CN 108484213B CN 201810611574 A CN201810611574 A CN 201810611574A CN 108484213 B CN108484213 B CN 108484213B
Authority
CN
China
Prior art keywords
metal
ceramic
composite material
porous
slurry
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201810611574.0A
Other languages
Chinese (zh)
Other versions
CN108484213A (en
Inventor
叶枫
马杰
刘强
张标
叶健
高晔
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Harbin Institute of Technology
Original Assignee
Harbin Institute of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Harbin Institute of Technology filed Critical Harbin Institute of Technology
Priority to CN201810611574.0A priority Critical patent/CN108484213B/en
Publication of CN108484213A publication Critical patent/CN108484213A/en
Application granted granted Critical
Publication of CN108484213B publication Critical patent/CN108484213B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/08—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by adding porous substances
    • 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
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
    • 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
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • 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
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • C04B35/63404—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B35/63416—Polyvinylalcohols [PVA]; Polyvinylacetates
    • 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
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3256—Molybdenum oxides, molybdates or oxide forming salts thereof, e.g. cadmium molybdate
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/349—Clays, e.g. bentonites, smectites such as montmorillonite, vermiculites or kaolines, e.g. illite, talc or sepiolite
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/40—Metallic constituents or additives not added as binding phase
    • C04B2235/405—Iron group metals
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/40—Metallic constituents or additives not added as binding phase
    • C04B2235/407—Copper
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/444—Halide containing anions, e.g. bromide, iodate, chlorite
    • C04B2235/445—Fluoride containing anions, e.g. fluosilicate
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/602—Making the green bodies or pre-forms by moulding
    • C04B2235/6022—Injection moulding
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6562—Heating rate
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6567—Treatment time

Abstract

The invention provides a ceramic metal porous composite material and a preparation method thereof, wherein kaolin, alumina powder and industrial alumina sol are mixed, added with mineralizer and sintering aid and mixed uniformly, the mixed ceramic powder is mixed with solvent and binder to prepare slurry, then the slurry is poured into a freezing mould with foam metal, after the slurry is frozen and solidified, the slurry is frozen and dried to obtain a ceramic metal composite green body, and then the ceramic metal composite green body is sintered by low-temperature reaction in inert atmosphere, thus finally the ceramic metal porous composite material is prepared; the method has the advantages of easily obtained raw materials, simple and reliable process and obvious advantages in industrial production.

Description

Ceramic metal porous composite material and preparation method thereof
Technical Field
The invention relates to the technical field of ceramic composite material preparation, in particular to a ceramic metal porous composite material and a preparation method thereof.
Background
The porous material generally has the advantages of low relative density, high specific strength, high specific surface area, light weight, sound insulation, heat insulation, good permeability and the like, wherein due to the electromagnetic and high heat conduction characteristics of metal, the porous metal material has good application value in the functional fields of sensors, electromagnetic shielding, electrode materials, heat exchange and the like, and the porous ceramic has important application value in the fields of fluid filtration, catalyst carriers, adsorption materials and the like due to the characteristics of high temperature resistance and corrosion resistance. The porous metal and the porous ceramic are compounded into a whole, so that the porous metal and the porous ceramic have the common characteristics of the porous metal and the porous ceramic, and the application field of the porous metal and the porous ceramic can be greatly expanded.
At present, due to the difference of the preparation processes of the porous ceramic and the porous metal, the two materials are difficult to be compounded into a whole, and the porous ceramic is difficult to be compounded with the metal due to the high sintering temperature of the porous ceramic.
In view of the above-mentioned drawbacks, the present inventors have made the present invention through long-term research and practice.
Disclosure of Invention
The invention utilizes the commercially available foam metal, selects ceramic powder with lower sintering temperature, and combines the freeze drying process to prepare the ceramic metal porous composite material with high porosity. The technical scheme adopted by the invention is that the preparation method of the ceramic metal porous composite material comprises the following steps:
the first step is as follows: mixing the raw materials in a mass ratio of 1: 0.3-0.6: 1.2-3.1, putting kaolin, alumina powder and industrial alumina sol into a mixing tank, mixing, drying and sieving, adding a mineralizer and a sintering aid, mixing again, drying and sieving to obtain mixed powder A;
the second step is that: placing the mixed powder A, a solvent and a binder in a mixing tank, adding alumina balls, mixing for 6-12 h, pouring into a beaker, adding a defoaming agent, and defoaming for 4-10min under vacuum to obtain stably dispersed slurry, wherein the mixed powder A accounts for 5-40% of the total volume of the slurry;
the third step: ultrasonically cleaning porous foam metal in acetone, drying and cutting the porous foam metal into a required shape, putting the porous foam metal into a mold with the shape consistent with that of the porous foam metal, and then putting the mold into a refrigerating device for refrigerating at the temperature of-196-0 ℃;
the fourth step: pouring the slurry obtained in the second step into the mould obtained in the third step, and enabling the slurry to submerge the porous foam metal to obtain solidified slurry;
the fifth step: freeze-drying the slurry solidified in the fourth step for 1-5 days at the temperature of-10-40 ℃ and under the pressure of 1-100 Pa to obtain a porous ceramic/metal composite green body;
and a sixth step: and (4) placing the composite green body obtained in the fifth step into a sealed alumina crucible, and performing reaction sintering in an inert atmosphere, wherein the sintering temperature is 900-1300 ℃, the temperature is kept for 1-3h, and the heating rate is 1-5 ℃/min, so that the ceramic/metal porous composite material is finally obtained.
Preferably, the solid phase content of the industrial alumina sol in the first step is 25%, the size of colloidal particles in the sol is 20-80nm, the kaolin is calcined at the high temperature of 900 ℃ in the first step and is subjected to ball milling to ensure that the particle size of the kaolin is distributed between 0.2 and 1 mu m, and the alumina powder is α -Al in the first step2O3And the particle size of the powder is 1-2 μm.
Preferably, the mineralizer in the first step is anhydrous aluminum fluoride, the particle size of the mineralizer is 5-10 μm, and the addition amount of the mineralizer accounts for 8-12% of the total mass of the mixed powder A.
Preferably, the sintering aid in the first step is one of MoO3, MnO2 or CuO, the particle size of the sintering aid is 5-10 μm, and the addition amount of the sintering aid accounts for 6-10% of the total mass of the mixed powder a.
Preferably, the solvent in the second step is one of deionized water, tert-butyl alcohol or camphene.
Preferably, the binder in the second step is one of polyvinyl alcohol, polyvinyl butyral or gelatin, and the binder accounts for 0.5-1.6% of the mass of the mixed powder A in the first step.
Preferably, the defoaming agent in the second step is n-butyl alcohol, and the defoaming agent accounts for 0.3-0.5% of the mass of the mixed powder A in the first step.
Preferably, in the third step, the porous foam metal is one of iron, copper, nickel, titanium, gold, zirconium and molybdenum or one of the alloys of the porous foam metal, and the pore diameter of the porous foam metal is 0.1-5 mm.
Preferably, the inert gas in the sixth step is high-purity nitrogen or argon.
The ceramic metal porous composite material prepared by the method is provided.
Compared with the prior art, the invention has the beneficial effects that:
1. the porous metal and the ceramic are compounded into a whole, so that the porous ceramic has the functions of electric conduction, sensing and heating, and is convenient for integration or multi-functionalization of downstream application;
2. the porosity of the prepared ceramic/metal porous composite material can be adjusted within the range of 40-90%, and the aperture can be adjusted within the range of 1-70 μm;
3. because of the good heat conductivity of the foam metal in the freezing and forming process, a temperature gradient can be formed around the pore ribs of the foam metal to induce the directional growth of ice crystals, ceramic particles in the slurry are directionally arranged to form a unique pore structure, and the foam metal has a very good application prospect in the fields of catalysis, adsorption and the like;
4. the method has the advantages of easily obtained raw materials, simple and reliable process and obvious advantages in industrial production.
Detailed Description
The above and further features and advantages of the present invention are explained in more detail below with reference to examples.
Example 1
The embodiment provides a ceramic metal porous composite material, which comprises the following steps:
the first step is as follows: weighing 100g, 42g and 205g of kaolin, alumina powder and industrial alumina sol respectively, putting the kaolin, the alumina powder and the industrial alumina sol into a mixing tank, adding 400g of alumina grinding balls and 150ml of absolute ethyl alcohol as ball milling media, continuously mixing for 24 hours, drying and sieving the slurry at 80 ℃, adding 8.5g of aluminum fluoride, 6g of molybdenum oxide powder, 400g of alumina grinding balls and 100ml of absolute ethyl alcohol, mixing for 8 hours, drying at 80 ℃ and sieving by a 100-mesh steel sieve to obtain uniformly mixed powder A;
the second step is that: adding the mixed powder A, solvent deionized water and adhesive polyvinyl alcohol solution into a mixing tank, adding 300g of alumina balls, mixing for 6-12 h at room temperature, pouring into a beaker, adding defoamer n-butyl alcohol, and defoaming for 4-10min under vacuum to obtain stably dispersed slurry, wherein the concentration of the adhesive polyvinyl alcohol solution is 10 wt%, the polyvinyl alcohol accounts for 0.5% of the mass of the mixed powder A, the mixed powder A accounts for 30% of the total volume of the slurry, and the defoamer n-butyl alcohol accounts for 0.3% of the mass of the mixed powder A.
The third step: selecting copper foam with the average pore size of 400 mu m, ultrasonically cleaning the copper foam with acetone for 20 minutes, putting the copper foam into a mold with the shape consistent with the copper foam, then putting the mold into a refrigerating device, freezing the copper foam at-50 ℃, and waiting for 30 minutes until the temperature of the copper foam is stable.
The fourth step: and pouring the slurry obtained in the second step into the mould obtained in the third step to enable the slurry to submerge the copper foam, and obtaining solidified slurry.
The fifth step: placing the solidified slurry obtained in the fourth step under the conditions that the temperature is-10 ℃ and the pressure is less than 50Pa, and freeze-drying for 4 days to obtain a porous ceramic metal composite green body;
and a sixth step: and (3) placing the ceramic metal composite green body obtained in the fifth step into a sealed alumina crucible, and performing reaction sintering in high-purity argon, wherein the sintering temperature is 950 ℃, the temperature is kept for 3 hours, and the heating rate is 4 ℃/min, so that the ceramic metal porous composite material is finally obtained.
Wherein, the solid phase content of the industrial alumina sol in the first step is 25 percent, the size of the colloidal particles in the sol is 20-80nm, the kaolin in the first step needs to be calcined at the high temperature of 900 ℃ and is ball-milled to ensure that the particle size is distributed between 0.2-1 mu m, and the alumina powder in the first step is α -Al2O3The particle size of the powder is 1-2 μm, and the particle sizes of the mineralizer and the sintering aid are both 5-10 μm.
The porosity of the ceramic metal porous composite material prepared in the embodiment is 65%, the average pore diameter measured by a mercury intrusion method is 12 mu m, and the specific surface area is 6.5m2/g。
Therefore, due to the high thermal conductivity of metal, in the process of freezing and forming, ceramic particles can form a special porous structure with a divergence shape around the porous metal pore ribs, which is very favorable for fluid diffusion or adsorption, and the prepared product has the electromagnetic property of metal and also has the characteristics of high specific surface area and easy adjustment of pore diameter of porous ceramic, so that the composite material has the functions of electric conduction, sensing, heating and the like while filtering or adsorbing fluid, is convenient for integration or multifunctionalization of downstream application, and has very good application prospect in the fields of catalysis, adsorption and the like; the kaolin used in the method is white powder which is calcined at high temperature and ball-milled, other reagents are commercial products, and analytical pure reagents except industrial alumina sol are adopted, so that the method has the advantages of easily obtained raw materials, simple and reliable process and obvious advantages in industrial production.
Example 2
The present embodiment is different from embodiment 1 in that:
in the first step, the mass of the kaolin, the mass of the alumina powder and the mass of the industrial alumina sol are respectively 100g, 20g and 309 g;
in the second step, the mixed powder A accounts for 10% of the total volume of the slurry;
in the third step, the porous foam metal is foam nickel with the average pore diameter of 100 mu m;
and sixthly, the sintering temperature is 1200 ℃, and the heat preservation time is 2 hours.
The porosity of the ceramic metal porous composite material prepared by the embodiment is 80%, the average pore diameter measured by a mercury intrusion method is 8.3 mu m, and the specific surface area is 3.5m2/g。
Example 3
The present embodiment is different from embodiment 1 in that:
in the second step, the solvent is tert-butyl alcohol, the adhesive is a polyvinyl butyral aqueous solution with the concentration of 10 wt%, and the mass fraction of the adhesive accounts for 0.8% of the mass of the mixed powder A;
fourthly, the freezing temperature is-30 ℃;
the porosity of the ceramic metal porous composite material prepared in the embodiment is 60%, the average pore diameter measured by a mercury intrusion method is 24 mu m, and the specific surface area is 2.1m2/g。
Example 4
The present embodiment is different from embodiment 1 in that:
in the first step, the mass of the kaolin, the mass of the alumina powder and the mass of the industrial alumina sol are respectively 100g, 62g and 104 g;
thirdly, the porous foam metal is foam iron with the average pore diameter of 5 mm;
and sixthly, the sintering temperature is 1300 ℃.
The porosity of the ceramic metal porous composite material prepared in the embodiment is 55%, the average pore diameter measured by a mercury intrusion method is 13 mu m, and the specific surface area is 2.3m2/g。
Example 5
The present embodiment is different from embodiment 1 in that:
in the second step, the mixed powder A accounts for 5% of the total volume of the slurry;
the third step is that the porous foam metal is foam gold with the average pore diameter of 200 mu m;
and sixthly, the sintering temperature is 925 ℃.
The porosity of the ceramic metal porous composite material prepared in the embodiment is 90%, the average pore diameter measured by a mercury intrusion method is 37 mu m, and the specific surface area is 4.6m2/g。
Example 6
The present embodiment is different from embodiment 1 in that:
thirdly, the porous foam metal is foam molybdenum with the average pore diameter of 3 mm;
and sixthly, the sintering temperature is 1300 ℃.
The porosity of the ceramic metal porous composite material prepared in the embodiment is 60%, the average pore diameter measured by a mercury intrusion method is 24 mu m, and the specific surface area is 1.6m2/g。
Example 7
The present embodiment is different from embodiment 1 in that:
secondly, the solvent is camphene, the adhesive is polyvinyl butyral aqueous solution, the mass fraction of the adhesive accounts for 0.8% of the mass of the mixed powder A, and the slurry is mixed at the temperature of 50 ℃;
fourthly, the freezing temperature is 0 ℃;
this example preparationThe porosity of the ceramic metal porous composite material is 60%, the average pore diameter measured by a mercury intrusion method is 42 mu m, and the specific surface area is 3.6m2/g。
Example 8
The present embodiment is different from embodiment 1 in that:
in the second step, the mixed powder A accounts for 40% of the total volume of the slurry;
the third step is that the porous foam metal is zirconium foam with the average pore diameter of 5 mm;
and sixthly, the sintering temperature is 1300 ℃.
The porosity of the ceramic metal porous composite material prepared in the embodiment is 40%, the average pore diameter measured by a mercury intrusion method is 7 mu m, and the specific surface area is 2.8m2/g。
Example 9
The present embodiment is different from embodiment 1 in that:
the sintering aid in the first step is copper oxide, and the average particle size of the sintering aid is 8 mu m;
secondly, the n-butyl alcohol serving as the defoaming agent accounts for 0.5 percent of the mass of the mixed powder A;
and the third step is that the porous foam metal is foam iron-nickel alloy with the average pore diameter of 3 mm.
The porosity of the ceramic metal porous composite material prepared by the embodiment is 56%, the average pore diameter measured by a mercury intrusion method is 48 mu m, and the specific surface area is 6.2m2/g。
The foregoing is merely a preferred embodiment of the invention, which is intended to be illustrative and not limiting. It will be understood by those skilled in the art that various changes, modifications and equivalents may be made therein without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (10)

1. The preparation method of the ceramic metal porous composite material is characterized by comprising the following steps of:
the first step is as follows: mixing the raw materials in a mass ratio of 1: 0.3-0.6: 1.2-3.1, putting kaolin, alumina powder and industrial alumina sol into a mixing tank, mixing, drying and sieving, adding a mineralizer and a sintering aid, mixing again, drying and sieving to obtain mixed powder A;
the second step is that: placing the mixed powder A, a solvent and a binder in a mixing tank, adding alumina balls, mixing for 6-12 h, pouring into a beaker, adding a defoaming agent, and defoaming for 4-10min under vacuum to obtain stably dispersed slurry, wherein the mixed powder A accounts for 5-40% of the total volume of the slurry;
the third step: ultrasonically cleaning porous foam metal in acetone, drying and cutting the porous foam metal into a required shape, putting the porous foam metal into a mold with the shape consistent with that of the porous foam metal, and then putting the mold into a refrigerating device for refrigerating at the temperature of-196-0 ℃;
the fourth step: pouring the slurry obtained in the second step into the mould obtained in the third step, and enabling the slurry to submerge the porous foam metal to obtain solidified slurry;
the fifth step: freeze-drying the slurry solidified in the fourth step for 1-5 days at the temperature of-10-40 ℃ and under the pressure of 1-100 Pa to obtain a porous ceramic/metal composite green body;
and a sixth step: and (4) placing the composite green body obtained in the fifth step into a sealed alumina crucible, and performing reaction sintering in an inert atmosphere, wherein the sintering temperature is 900-1300 ℃, the temperature is kept for 1-3h, and the heating rate is 1-5 ℃/min, so that the ceramic/metal porous composite material is finally obtained.
2. The preparation method of the ceramic-metal porous composite material according to claim 1, wherein the solid phase content of the industrial alumina sol in the first step is 25%, the size of colloidal particles in the sol is 20-80nm, the kaolin is calcined at a high temperature of 900 ℃ in the first step and is subjected to ball milling to ensure that the particle size of the kaolin is distributed between 0.2 and 1 μm, and the alumina powder is α -Al in the first step2O3And the particle size of the powder is 1-2 μm.
3. The preparation method of the ceramic-metal porous composite material according to claim 1, wherein the mineralizer is anhydrous aluminum fluoride in the first step, the particle size of the mineralizer is 5-10 μm, and the addition amount of the mineralizer accounts for 8-12% of the total mass of the mixed powder A.
4. The method for preparing the ceramic-metal porous composite material according to claim 1, wherein the sintering aid in the first step is MoO3、MnO2Or CuO, the particle size of the sintering aid is 5-10 mu m, and the addition amount of the sintering aid accounts for 6-10% of the total mass of the mixed powder A.
5. The method of claim 1, wherein the solvent in the second step is one of deionized water, tert-butanol or camphene.
6. The method for preparing the ceramic-metal porous composite material according to claim 1, wherein the binder in the second step is one of polyvinyl alcohol, polyvinyl butyral or gelatin, and the binder accounts for 0.5-1.6% of the mass of the mixed powder A in the first step.
7. The preparation method of the ceramic-metal porous composite material as claimed in claim 1, wherein the defoaming agent in the second step is n-butanol, and the defoaming agent accounts for 0.3-0.5% of the mass of the mixed powder A in the first step.
8. The method for preparing a ceramic-metal porous composite material according to claim 1, wherein the porous metal foam in the third step is one of iron, copper, nickel, titanium, gold, zirconium, molybdenum or one of alloys thereof, and the pore diameter of the porous metal foam is 0.1-5 mm.
9. The method of claim 1, wherein the inert atmosphere in the sixth step is a high purity nitrogen or argon atmosphere.
10. A ceramic metal porous composite material prepared by the method of any one of claims 1-9.
CN201810611574.0A 2018-06-14 2018-06-14 Ceramic metal porous composite material and preparation method thereof Active CN108484213B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810611574.0A CN108484213B (en) 2018-06-14 2018-06-14 Ceramic metal porous composite material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810611574.0A CN108484213B (en) 2018-06-14 2018-06-14 Ceramic metal porous composite material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN108484213A CN108484213A (en) 2018-09-04
CN108484213B true CN108484213B (en) 2020-06-30

Family

ID=63342483

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810611574.0A Active CN108484213B (en) 2018-06-14 2018-06-14 Ceramic metal porous composite material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN108484213B (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109482882B (en) * 2018-10-22 2021-05-18 中国科学院金属研究所 Foam metal with micro-oriented pore structure and preparation method thereof
CN111847888A (en) * 2020-07-30 2020-10-30 深圳绿蓝技术有限公司 Multifunctional ceramic and its production method and application
CN112390653B (en) * 2020-11-16 2022-11-25 中国工程物理研究院材料研究所 Method for preparing ceramic powder based on freezing casting molding
CN113308713A (en) * 2021-05-25 2021-08-27 西部金属材料股份有限公司 Metal ceramic anode and preparation method and application thereof
CN114368194B (en) * 2021-12-31 2024-03-26 八龙应用材料科技(海南)有限公司 High-temperature-resistant heat-insulating ceramic composite material and preparation method thereof
CN116573947A (en) * 2023-04-27 2023-08-11 郑州航空工业管理学院 Three-dimensional toughened ceramic cutter material and preparation method thereof
CN116536538B (en) * 2023-07-05 2023-09-08 太原理工大学 Preparation method of ultrasonic-assisted self-infiltration aluminum oxide reinforced magnesium-based composite material

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008054596B4 (en) * 2008-12-12 2011-04-14 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Open-cell ceramic and / or metal foam bodies with a rough, enveloping surface and process for their preparation
CN104073673B (en) * 2014-06-20 2016-03-02 西安工程大学 A kind of preparation method of Ceramic Reinforced MMCs
CN105750547B (en) * 2016-03-07 2018-10-02 中国科学院上海硅酸盐研究所 A kind of preparation method of pattern and the controllable porous metals/ceramic composite of performance

Also Published As

Publication number Publication date
CN108484213A (en) 2018-09-04

Similar Documents

Publication Publication Date Title
CN108484213B (en) Ceramic metal porous composite material and preparation method thereof
CN105903969B (en) A kind of porous copper material and preparation method thereof with oriented laminated hole
WO2017045273A1 (en) Aerogel-metal composite material, preparation method therefor and application thereof
US20060138716A1 (en) Method for producing a ceramic crucible
JP5825598B2 (en) Metal porous body and method for producing metal porous body.
US20170043399A1 (en) Method for Preparing Porous Metal Material and Application Thereof
WO2017107477A1 (en) Preparation method for ceramic membrane support
RU2456056C2 (en) Ceramic filter with carbon coat, and method of its production
WO2017004776A1 (en) Porous alumina ceramic ware and preparation method thereof
CN102417366B (en) Pore gradient silicon carbide porous ceramic and preparation method thereof
WO2018041031A1 (en) Thermal conductive copper powder with high capillary rate and low density under loose packing, and manufacturing method thereof
WO2018121214A1 (en) Metal-based aluminum nitride composite material and preparation method therefor
US10017423B2 (en) Method for preparing support of molecular sieve membrane
CN104014252A (en) Preparation method of ceramic membrane supporting body
WO2015014190A1 (en) Sintered fe-al based porous alloy material with high-temperature oxidization resistance and filtering elements
CN111020329A (en) Method for preparing porous tungsten material based on W-Fe-C system corrosion method
CN110976889A (en) Preparation method of high-W-content W-Cu composite material
WO2015000387A1 (en) Sintered porous material and filter element using same
JP5429526B2 (en) Method for producing ceramic porous body
CN103253980A (en) Method for preparing low-temperature liquid phase sintered silicon carbide foamed ceramic
JP6855292B2 (en) Ag-Cu alloy powder and its manufacturing method
CN111479791A (en) Method for preparing aluminum nitride foam
CN110981453B (en) Preparation method of light ceramic filtering membrane
CN110885254B (en) Porous Ti3SiC2/SiC composite material and preparation method thereof
CN104726775A (en) Iron-chromium-aluminum-based porous alloy material and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant