CN113172221A - Large-size metal ceramic inert electrode and preparation method thereof - Google Patents

Large-size metal ceramic inert electrode and preparation method thereof Download PDF

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CN113172221A
CN113172221A CN202110473801.XA CN202110473801A CN113172221A CN 113172221 A CN113172221 A CN 113172221A CN 202110473801 A CN202110473801 A CN 202110473801A CN 113172221 A CN113172221 A CN 113172221A
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powder
metal ceramic
metal
inert electrode
sintering
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CN113172221B (en
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熊慧文
李志友
张雷
周科朝
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Central South University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/103—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing an organic binding agent comprising a mixture of, or obtained by reaction of, two or more components other than a solvent or a lubricating agent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/02—Compacting only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/1017—Multiple heating or additional steps
    • B22F3/1021—Removal of binder or filler
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/026—Spray drying of solutions or suspensions
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/06—Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
    • C25C3/08—Cell construction, e.g. bottoms, walls, cathodes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/1017—Multiple heating or additional steps
    • B22F3/1021—Removal of binder or filler
    • B22F3/1025—Removal of binder or filler not by heating only

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Abstract

The invention discloses a large-size metal ceramic inert electrode and a preparation method thereof, wherein the preparation method comprises the following steps: adding raw material powder, a dispersing agent and an organic monomer into an organic solvent to obtain a mixture, then adding an adhesive into the mixture, performing ball milling to obtain metal ceramic organic slurry, performing spray granulation to obtain metal ceramic composite powder, molding to obtain a metal ceramic green body, then placing the metal ceramic green body into cross-linking agent steam, reacting, machining to obtain an anode green body, degreasing and sintering to obtain the large-size metal ceramic inert electrode. The cermet obtained by the preparation method has the following effects that the two-phase structure of the cermet is uniform, and the problem of sintering overflow caused by poor wettability of a metal phase is obviously relieved; the metal ceramic green compact has better strength after being strengthened and can meet the machining requirement, the outline appearance of the metal ceramic can be complex shapes such as a curved surface, and the maximum equivalent outer diameter of the metal ceramic can be 150-400 mm.

Description

Large-size metal ceramic inert electrode and preparation method thereof
Technical Field
The invention belongs to the technical field of preparation of metal ceramic materials, and particularly relates to a large-size metal ceramic inert electrode and a preparation method thereof.
Background
The cermet material has comprehensive excellent performances of metal and ceramic, such as excellent conductivity, thermal shock resistance, corrosion resistance and the like, so that the cermet material becomes a preferable material system of the aluminum electrolysis inert electrode. At present, the inert electrode needs to satisfy the electrical connection, and the shape structure needs to match with the structure of the electrolytic cell and the arrangement of the electrical connection, so that the appearance is diversified and complicated. Based on the size of the conventional carbon anode approaching 500mm, the specification of the inert anode tends to be large-scale, and the target size of the inert anode needs to be 200-400 mm. The inert anode material is the basis of carbon-free aluminum electrolysis, and has important significance in breaking through the high-efficiency preparation of large-size and various-form cermet materials.
The difference of physical and chemical properties of metal and ceramic phases, such as melting point, density, thermal conductivity, powder dispersion characteristic and the like, is large, so that the preparation of large-size materials with complex shapes is difficult to realize by a conventional metal forging method or a wet forming process of a ceramic component. The powder metallurgy process is an effective method for preparing the cermet material, and mainly comprises the steps of uniformly mixing metal and ceramic powder, preparing a blank from the mixed powder through cold isostatic pressing, and sintering and post-treating to obtain the cermet material with uniform structure and stable performance. However, the powder metallurgy process for preparing large-size metal ceramic inert electrodes has the following two problems: (1) the wettability of oxide ceramics and metals or alloys such as iron, nickel, copper, chromium and the like is poor, and if the distribution of the metals and the ceramics is not uniform, residual pores and metal phases of a final sintered blank are easy to overflow; (2) the large-size blank prepared by cold isostatic pressing has low strength to be processed, and can be machined in an early stage only by performing high-temperature pre-sintering to reach certain shrinkage and strength, so that the preparation cost and the process uncertainty are increased.
Disclosure of Invention
Aiming at the problems of high porosity, easy overflow of metal phase, low strength of green compact and incapability of direct processing in the existing method for preparing the metal ceramic inert electrode by powder metallurgy, the invention aims to provide a large-size metal ceramic inert electrode and a preparation method thereof.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
the invention relates to a powder metallurgy preparation method of a large-size metal ceramic inert electrode, which comprises the following steps:
adding raw material powder, a dispersing agent and an organic monomer into an organic solvent to obtain a mixture, then adding an adhesive into the mixture, performing ball milling to obtain metal ceramic organic slurry, performing spray granulation to obtain metal ceramic composite powder, molding to obtain a metal ceramic green body, then placing the metal ceramic green body into cross-linking agent steam, reacting, machining to obtain an anode green body, degreasing and sintering to obtain the large-size metal ceramic inert electrode.
In addition, a small amount of organic monomer is added into the ceramic slurry, and then the slurry is subjected to cold isostatic pressing after spray granulation to obtain a metal ceramic green body with a certain specification; and then placing the metal ceramic green body in cross-linking agent steam, inducing the organic monomer in the metal ceramic green body to perform polymerization reaction with the cross-linking agent, so that the metal ceramic green body is greatly enhanced, the strength can meet the machining requirement, machining the green body to meet the subsequent electric connection structure, and finally performing high-temperature degreasing and sintering on the metal ceramic green body to obtain the large-size metal ceramic inert electrode.
In a preferred scheme, the raw material powder comprises, by mass, 40-85 parts of metal oxide ceramic powder, 15-60 parts of metal powder and 0-5.0 parts of sintering aid powder;
the metal oxide ceramic powder is at least one metal oxide ceramic powder composed of at least one metal of nickel, iron, aluminum and copper,
the metal in the metal powder is selected from at least one of iron, copper, nickel and chromium.
Preferably, the metal oxide ceramic powder is NiFe2O4-10NiO ceramic composite powder.
Wherein NiFe2O4-10NiO ceramic composite powder, which means NiO in NiFe2O4The mass fraction in the-10 NiO ceramic composite powder was 10 wt%.
Further preferably, the metal powder is selected from Cu-20Ni alloy powder.
Wherein the Cu-20Ni alloy powder means that the mass fraction of Ni in the Cu-20Ni alloy powder is 20%.
In a preferred embodiment, the sintering aid powder is Y2O3And (3) powder.
Preferably, the particle size of the metal oxide ceramic powder is 1.0 to 5.0 μm, preferably 2.0 to 3.0 μm.
Preferably, the particle size of the sintering aid powder is 0.2-1.5 μm.
Preferably, the dispersant is at least one selected from the group consisting of fatty acid dispersants, fatty amide dispersants, and alcohol dispersants.
Further preferably, the dispersant is at least one selected from 3-butenamine and tertiary amine.
In a preferable scheme, the addition amount of the dispersing agent is 0.3-2.0% of the mass of the raw material powder, and is preferably 0.8-1.2%.
Preferably, the organic monomer is selected from hydroxyethyl methacrylate.
In a preferred scheme, the adding amount of the organic monomer is 1.0-8.0% of the mass of the raw material powder, and is preferably 3.0-6.0%.
In a preferred embodiment, the organic solvent is at least one selected from the group consisting of isopropanol and n-octanol.
In a preferable scheme, the volume fraction of the raw material powder in the mixture is 25-40%, and preferably 30-35%.
In a preferable scheme, the adding amount of the adhesive is 1-3% of the mass of the raw material powder.
Preferably, the adhesive is selected from polyvinyl butyral.
In a preferable scheme, the ball milling time is 10-100 h, preferably 30-60 h, and the ball milling rotation speed is 60-120 r/min, preferably 80-100 r/min.
Preferably, the viscosity of the metal ceramic organic slurry is 50 to 200 mPaS, and preferably 100 to 150 mPaS.
Under the coordination of the slurry formula and the ball milling parameters, the low-viscosity and uniformly-dispersed metal ceramic slurry can be obtained, so that the interface diffusion distance of two phases of the metal ceramic in the sintering process is shorter, and more uniform and compact metal ceramic is obtained.
In a preferable scheme, the particle size of the metal ceramic composite powder is 8-20 μm, and preferably 10-15 μm. And spray granulation and drying are carried out to obtain the metal ceramic composite powder with good fluidity.
The forming process can be compression forming, and inert anode green bodies with certain hollow or complex shapes can be obtained through mold design, so that large-size metal ceramic green bodies can be obtained.
Preferably, the forming mode is cold isostatic pressing, the pressure of the cold isostatic pressing is 50-300 MPa, preferably 100-200 MPa, and the pressure maintaining time is 1-20 min, preferably 5-10 min.
In a preferred scheme, the compactness of the metal ceramic green body is 50-60%.
By the aid of the compression molding process, the compactness of the metal ceramic green body is controlled to be 50-60%, and finally the obtained green body has the highest strength after polymerization reaction of the organic monomer.
In a preferred embodiment, the crosslinking agent is 1, 6-hexanediol diacrylate.
In the preferable scheme, the pressure of the cross-linking agent steam is 0.1-2.0 MPa, preferably 0.5-1.5 MPa, the reaction temperature is 0-80 ℃, preferably 30-60 ℃, and the reaction time is 1-20 hours, preferably 5-12 hours.
In the invention, a green body containing organic monomer hydroxyethyl methacrylate is placed in an environment containing cross-linking agent steam, and the organic monomer and the cross-linking agent are subjected to cross-linking reaction at a certain speed and are cured under proper steam pressure and temperature, so that the green body strength is greatly enhanced, and surface machining such as hole turning, surface milling and the like can be carried out, and the anode green body with a specific morphology is obtained.
In a preferable scheme, the degreasing temperature is 400-600 ℃, and the degreasing time is 2-20 h.
The degreasing can be carried out in a vacuum environment and a protective atmosphere.
In a preferable scheme, the sintering is carried out in a protective atmosphere, the sintering temperature is 1200-1400 ℃, the sintering time is 1-5 hours, and the air pressure is 50-5000 Pa.
The protective atmosphere is preferably a nitrogen atmosphere.
The invention also provides the large-size metal ceramic inert electrode prepared by the preparation method.
Has the advantages that:
the preparation method of the invention is characterized in that the metal ceramic mixed powder and a proper amount of organic monomer are dispersed in an organic solvent by adding a dispersant; the mixed slurry has low viscosity and high suspension stability, so that the mixture after ball milling has better uniformity, and organic monomers in dried green bodies have high activity, and are reacted and cured in a crosslinking agent steam environment subsequently, so that the strength of the metal ceramic green bodies is effectively enhanced, and the high-efficiency preparation of large-specification metal ceramic inert electrodes is realized.
Compared with the prior art, the invention has the advantages that:
(1) the cermet slurry obtained by the preparation method has low viscosity, good dispersibility and difficult sedimentation, and the uniformity of the obtained cermet mixed powder is better after ball milling; therefore, the interface diffusion distance of the two phases of the metal ceramic is shorter, the phenomenon of metal phase aggregation and even overflow caused by non-wetting of the metal ceramic during sintering can be obviously reduced, and more uniform and compact metal ceramic can be obtained.
(2) The pressed green body obtained by the method contains a certain amount of organic monomers, and the porous green body can be reinforced, so that the machining can be carried out at the green body stage, the machining difficulty is greatly reduced, and the machining requirement of the polymorphic large-size anode is met.
(3) The large-size metal ceramic inert electrode obtained by the invention has a larger outline, high sintering relative density and a complex outline structure. The equivalent outer diameter of the metal ceramic can reach 150-400 mm, the sintering relative density of the metal ceramic can be better than 97%, the metal phase and the ceramic phase are uniformly distributed, and the mechanical property is excellent.
Detailed Description
Example 1
The raw material powder used in this example includes 55 parts by weight of NiFe2O4-10NiO ceramic composite powder, 43 parts of Cu-20Ni alloy powder, 2.0 parts of Y2O3Sintering aid ceramic powder. Wherein NiFe2O4-10NiO ceramic composite powder having an average particle diameter of 3.0. mu.m, Y2O3Has an average particle diameter of 0.30. mu.m. The preparation method of this example comprises the following steps:
(1) preparing a metal ceramic slurry: taking n-octanol as an organic solvent, and adding 1.2 parts by weight of aliphatic amide dispersant: 3-butenamide; 4.0 parts of hydroxyethyl methacrylate monomer; adding 100 parts of the raw material powder to obtain a mixture, wherein the volume fraction of the raw material powder in the mixture is controlled to be 30%. Before ball milling, adding 2% polyvinyl butyral ester which accounts for the weight of the raw material powder and is dissolved in an organic solvent as an adhesive; ball milling is carried out for 50 hours at the rotating speed of 80r/min, and the high-stability dispersed metal ceramic organic slurry with 120 Pa.S can be obtained.
(2) Spray drying is adopted to obtain the metal ceramic spherical mixed powder with the average grain diameter of 15 mu m.
(3) And (3) pressing the powder by adopting isostatic cool pressing to obtain a green compact, wherein the pressing pressure is 180MPa, the pressure maintaining time is 15min, the maximum outer diameter of the green compact is 300mm, and the density of the obtained green compact is 57%.
(4) And (3) placing the cold isostatic pressing green compact in steam of a certain 1, 6-hexanediol diacrylate solvent, controlling the steam pressure to be 0.5MPa, controlling the temperature to be 60 ℃, and controlling the steam treatment time of the green compact to be 8 h.
(5) Machining the strengthened pressed blank, and performing subsequent degreasing sintering, wherein the degreasing temperature is 600 ℃, and the degreasing time is 20 hours; the sintering temperature is 1200 ℃, the sintering is performed in a nitrogen protective atmosphere, the air pressure is 2000Pa, and the sintering heat preservation time is 3h, so that the large-size metal ceramic inert electrode material can be obtained.
The cermet inert ceramic phase obtained in this example had an average particle size of 8.0 μm, a metal phase in the form of a connected network morphology, and no agglomeration. The relative density of the metal ceramic is 98.5%, the three-point bending strength is 500MPa, and the thermal shock resistance temperature is 500 ℃.
Example 2
The raw material powder used in this example includes 80 parts by weight of NiFe2O4-10NiO ceramic composite powder, 18 parts of Cu-20Ni alloy powder, 2.0 parts of Y2O3Sintering aid ceramic powder. Wherein NiFe2O4-10NiO ceramic composite powder having an average particle diameter of 3.0. mu.m, Y2O3Has an average particle diameter of 0.30. mu.m. The preparation method of this example comprises the following steps:
(1) and preparing the metal ceramic slurry. Taking n-octanol as an organic solvent, and adding 0.9 part of tertiary amine according to parts by weight; 3.0 parts of hydroxyethyl methacrylate monomer; adding 100 parts of the raw material powder to obtain a mixture, wherein the volume fraction of the raw material powder in the mixture is controlled to be 35%. Before ball milling, adding 2% polyvinyl butyral ester which accounts for the weight of the raw material powder and is dissolved in an organic solvent as an adhesive; ball milling is carried out for 60 hours at the rotating speed of 100r/min, and the metal ceramic organic slurry with the viscosity of 180mPa & S and high stable dispersion can be obtained.
(2) Spray drying is adopted to obtain the metal ceramic spherical mixed powder with the average grain diameter of 12 mu m.
(3) And (3) pressing the powder by adopting isostatic cool pressing to obtain a green compact, wherein the pressing pressure is 200MPa, the pressure maintaining time is 15min, the maximum outer diameter of the green compact is 250mm, and the density of the obtained green compact is 59%.
(4) Placing the cold isostatic pressing green compact in steam of a certain 1, 6-hexanediol diacrylate solvent, controlling the steam pressure at 0.7MPa, the temperature at 50 ℃, and the steam treatment time of the green compact at 12 h.
(5) Machining the strengthened pressed blank, and performing subsequent degreasing sintering, wherein the degreasing temperature is 600 ℃, and the degreasing time is 18 h; the sintering temperature is 1200 ℃, the sintering is performed in a nitrogen protective atmosphere, the air pressure is 5000Pa, and the sintering heat preservation time is 5h, so that the large-size metal ceramic inert electrode material can be obtained.
The cermet inert ceramic phase obtained in this example had an average particle size of 6.0 μm, and the metal phase was uniformly dispersed around the ceramic phase without agglomeration. The relative density of the metal ceramic reaches 97 percent, the three-point bending strength is 360MPa, and the thermal shock resistance temperature is 400 ℃.
Comparative example 1
The raw material powder used in this example includes 55 parts by weight of NiFe2O4-10NiO ceramic composite powder, 43 parts of Cu-20Ni alloy powder, 2.0 parts of Y2O3Sintering aid ceramic powder. Wherein NiFe2O4-10NiO ceramic composite powder having an average particle diameter of 3.0. mu.m, Y2O3Has an average particle diameter of 0.30. mu.m. The preparation method of this example comprises the following steps:
(1) and preparing the metal ceramic slurry. Taking n-octanol as an organic solvent, and adding 1.2 parts of aliphatic amide dispersant by weight of total powder; simultaneously adding hydroxyethyl methacrylate monomer accounting for 4.0 parts of the total powder weight; the feedstock powder is then added to the ball milling media such that the volume of the feedstock powder is between 30% of the total volume of the powder and water. Before ball milling, adding 2% polyvinyl butyral ester which accounts for the weight of the raw material powder and is dissolved in an organic solvent as an adhesive; ball milling for 50h to obtain the low-viscosity and high-stability dispersed metal ceramic organic slurry.
(2) Spray drying is adopted to obtain the metal ceramic spherical mixed powder with the average grain diameter of 15 mu m.
(3) And (3) pressing the powder by adopting isostatic cool pressing to obtain a green compact, wherein the pressing pressure is 180MPa, the pressure maintaining time is 15min, the maximum outer diameter of the green compact is 300mm, and the density of the obtained green compact is 57%.
(4) Placing the cold isostatic pressing green compact in steam of a certain 1, 6-hexanediol diacrylate solvent, controlling the steam pressure at 0.02MPa, the temperature at 60 ℃, and the steam treatment time of the green compact at 8 h.
(5) And (3) machining the strengthened green compact, wherein the green compact has insufficient strength, edges and corners are removed during machining, and the next step of degreasing and sintering cannot be performed.
Comparative example 2
The raw material powder used in this example includes 80 parts by weight of NiFe2O4-10NiO ceramic composite powder, 18 parts of Cu-20Ni alloy powder, 2.0 parts of Y2O3Sintering aid ceramic powder. Wherein NiFe2O4-10NiO ceramic composite powder having an average particle diameter of 0.50 μm and Y2O3Has an average particle diameter of 3.0. mu.m. The preparation method of this example comprises the following steps:
(1) and preparing the metal ceramic slurry. Taking n-octanol as an organic solvent, and adding 0.9 part of aliphatic amide dispersant by weight of total powder; simultaneously adding hydroxyethyl methacrylate monomer accounting for 3.0 parts of the total powder weight; the feedstock powder was then added to the ball milling media such that the volume of the feedstock powder was 35% of the total volume of water and powder. Before ball milling, adding 2% polyvinyl butyral ester which accounts for the weight of the raw material powder and is dissolved in an organic solvent as an adhesive; ball milling is carried out for 60 hours, and then the metal ceramic organic slurry with low viscosity and high stable dispersion can be obtained.
(2) Spray drying is adopted to obtain the metal ceramic spherical mixed powder with the average grain diameter of 12 mu m.
(3) And (3) pressing the powder by adopting isostatic cool pressing to obtain a green compact, wherein the pressing pressure is 200MPa, the pressure maintaining time is 15min, the maximum outer diameter of the green compact is 250mm, and the density of the obtained green compact is 59%.
(4) Placing the cold isostatic pressing green compact in steam of a certain 1, 6-hexanediol diacrylate solvent, controlling the steam pressure at 0.7MPa, the temperature at 50 ℃, and the steam treatment time of the green compact at 12 h.
(5) Machining the strengthened pressed blank, and performing subsequent degreasing sintering, wherein the degreasing temperature is 600 ℃, and the degreasing time is 18 h; the sintering temperature is 1200 ℃, the sintering is performed in a nitrogen protective atmosphere, the air pressure is 5000Pa, and the sintering heat preservation time is 5h, so that the large-size metal ceramic inert electrode material can be obtained.
The cermet inert ceramic phase obtained in this comparative example had an average particle size of 2.0 μm, and the metal phase was uniformly dispersed around the ceramic phase without agglomeration. The relative density of the metal ceramic is lower than 95%, the three-point bending strength is 180MPa, and the thermal shock resistance temperature is lower than 300 ℃.

Claims (10)

1. A preparation method of a large-size metal ceramic inert electrode is characterized by comprising the following steps: the method comprises the following steps:
adding raw material powder, a dispersing agent and an organic monomer into an organic solvent to obtain a mixture, then adding an adhesive into the mixture, performing ball milling to obtain metal ceramic organic slurry, performing spray granulation to obtain metal ceramic composite powder, molding to obtain a metal ceramic green body, then placing the metal ceramic green body into cross-linking agent steam, reacting, machining to obtain an anode green body, degreasing and sintering to obtain the large-size metal ceramic inert electrode.
2. The method of making a large format cermet inert electrode of claim 1, wherein: the raw material powder comprises the following components in parts by weight: 40-85 parts of metal oxide ceramic powder; 15-60 parts of metal powder and 0-5.0 parts of sintering aid powder;
the metal oxide ceramic powder is at least one metal oxide ceramic powder composed of at least one metal of nickel, iron, aluminum and copper,
the metal in the metal powder is selected from at least one of iron, copper, nickel and chromium,
the sintering aid powder is Y2O3Powder;
the volume fraction of the raw material powder in the mixture is 25-40%.
3. The method of making a large format cermet inert electrode of claim 1, wherein:
the particle size of the metal oxide ceramic powder is 1.0-5.0 μm,
the particle size of the sintering aid powder is 0.2-1.5 mu m.
4. The method of making a large format cermet inert electrode of claim 1, wherein:
the dispersant is at least one selected from fatty acid dispersants, fatty amide dispersants and alcohol dispersants;
the addition amount of the dispersing agent is 0.3-2.0% of the mass of the raw material powder;
the organic monomer is selected from hydroxyethyl methacrylate;
the addition amount of the organic monomer is 1.0-8.0% of the mass of the raw material powder.
5. The method of making a large format cermet inert electrode of claim 1, wherein:
the addition amount of the adhesive is 1-3% of the mass of the raw material powder;
the adhesive is selected from polyvinyl butyral.
6. The method of making a large format cermet inert electrode of claim 1, wherein: the ball milling time is 10-100 h, and the ball milling speed is 60-120 r/min;
the viscosity of the metal ceramic organic slurry is 50-200 mPa & S.
7. The method of making a large format cermet inert electrode of claim 1, wherein: the forming mode is cold isostatic pressing, the pressure of the cold isostatic pressing is 50-300 MPa, and the pressure maintaining time is 1-20 min;
the density of the metal ceramic green body is 50-60%.
8. The method of making a large format cermet inert electrode of claim 1, wherein:
the cross-linking agent is 1, 6-hexanediol diacrylate;
the pressure of the cross-linking agent steam is 0.1-2.0 MPa, the reaction temperature is 0-80 ℃, and the reaction time is 1-20 h.
9. The method of making a large format cermet inert electrode of claim 1, wherein:
the degreasing temperature is 400-600 ℃, and the degreasing time is 2-20 h.
The sintering is carried out in a protective atmosphere, the sintering temperature is 1200-1400 ℃, the sintering time is 1-5 hours, and the air pressure is 50-5000 Pa.
10. A large format cermet inert electrode prepared according to the preparation process of any one of claims 1-9.
CN202110473801.XA 2021-04-29 2021-04-29 Large-size metal ceramic inert electrode and preparation method thereof Active CN113172221B (en)

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