CN113215429A - Preparation method of high-density metal ceramic inert anode material for aluminum electrolysis - Google Patents
Preparation method of high-density metal ceramic inert anode material for aluminum electrolysis Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 116
- 239000002184 metal Substances 0.000 title claims abstract description 116
- 239000000919 ceramic Substances 0.000 title claims abstract description 102
- 239000010405 anode material Substances 0.000 title claims abstract description 32
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 28
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 117
- 238000005245 sintering Methods 0.000 claims abstract description 40
- 239000002994 raw material Substances 0.000 claims abstract description 35
- 238000005238 degreasing Methods 0.000 claims abstract description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000001301 oxygen Substances 0.000 claims abstract description 22
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 22
- 229910052574 oxide ceramic Inorganic materials 0.000 claims abstract description 19
- 239000011224 oxide ceramic Substances 0.000 claims abstract description 19
- 238000000498 ball milling Methods 0.000 claims abstract description 17
- 239000011268 mixed slurry Substances 0.000 claims abstract description 13
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 12
- 239000011029 spinel Substances 0.000 claims abstract description 12
- 239000000654 additive Substances 0.000 claims abstract description 9
- 239000012298 atmosphere Substances 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 230000000996 additive effect Effects 0.000 claims abstract description 7
- 230000003179 granulation Effects 0.000 claims abstract description 4
- 238000005469 granulation Methods 0.000 claims abstract description 4
- 239000007921 spray Substances 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000002131 composite material Substances 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 13
- 239000002002 slurry Substances 0.000 claims description 13
- 238000003825 pressing Methods 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 10
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 8
- 239000000853 adhesive Substances 0.000 claims description 8
- 230000001070 adhesive effect Effects 0.000 claims description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 8
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 6
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 239000011651 chromium Substances 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 239000005060 rubber Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims 1
- 239000011195 cermet Substances 0.000 abstract description 13
- 238000009826 distribution Methods 0.000 abstract description 8
- 239000007767 bonding agent Substances 0.000 abstract description 3
- 238000003892 spreading Methods 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 19
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 230000035939 shock Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229910003264 NiFe2O4 Inorganic materials 0.000 description 6
- 239000011812 mixed powder Substances 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 238000009694 cold isostatic pressing Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 238000013001 point bending Methods 0.000 description 5
- 238000004321 preservation Methods 0.000 description 5
- 238000001694 spray drying Methods 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 229910003303 NiAl2O4 Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- NQNBVCBUOCNRFZ-UHFFFAOYSA-N nickel ferrite Chemical compound [Ni]=O.O=[Fe]O[Fe]=O NQNBVCBUOCNRFZ-UHFFFAOYSA-N 0.000 description 3
- 229910001610 cryolite Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910002480 Cu-O Inorganic materials 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 229910001308 Zinc ferrite Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- NNGHIEIYUJKFQS-UHFFFAOYSA-L hydroxy(oxo)iron;zinc Chemical compound [Zn].O[Fe]=O.O[Fe]=O NNGHIEIYUJKFQS-UHFFFAOYSA-L 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
- C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
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- 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
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- 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
- B22F3/1003—Use of special medium during sintering, e.g. sintering aid
- B22F3/1007—Atmosphere
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- 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
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/005—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides comprising a particular metallic binder
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/12—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on oxides
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- 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
- C25C3/12—Anodes
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- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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Abstract
The invention discloses a preparation method of a high-density metal ceramic inert anode material for aluminum electrolysis, which comprises the following steps of mixing oxide ceramic powder, metal powder, single-phase oxide ceramic powder and an additive to obtain raw material powder, adding the raw material powder into a solvent to obtain mixed slurry, adding a bonding agent, carrying out ball milling, carrying out spray granulation, carrying out press forming to obtain a metal ceramic green body, degreasing, and sintering under oxygen partial pressure to obtain the inert anode material. According to the preparation method, on one hand, the single-phase oxide is additionally added into the raw materials, on the other hand, the sintering is carried out in the negative pressure atmosphere with certain oxygen partial pressure, the interface wettability of the metal phase and the spinel oxide ceramic is effectively improved, the spreading and distribution of the metal phase among ceramic phases are effectively improved, the combination and growth of ceramic grains are effectively inhibited, the connected network-shaped distribution of the metal phase is realized, and the cermet inert anode material for aluminum electrolysis with the sintering relative density superior to 97% is obtained.
Description
Technical Field
The invention belongs to the technical field of preparation of metal ceramic materials, and particularly relates to a preparation method of a high-density metal ceramic inert anode material for aluminum electrolysis.
Background
Under the strategic background of 'carbon neutralization', the carbon-free aluminum electrolysis technology has become a must-strive high technology field for the sustainable development of the international aluminum electrolysis industry. The aluminum electrolysis inert anode material needs to resist the corrosion of high-temperature cryolite molten salt at 800-900 ℃, and simultaneously has high conductivity and mechanical property to meet the long-term stable operation of aluminum electrolysis. Spinel type oxides such as nickel ferrite and the like become preferred components of a corrosion resistant phase in an aluminum electrolysis inert anode material due to the excellent corrosion resistance in cryolite. 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. The metal phase mainly comprises metals such as iron, copper, nickel and the like, but the wettability of the metal phase and the oxide ceramic is poor, so that the relative density of the metal ceramic such as nickel ferrite based metal ceramic is lower than 95%, and the metal phase is often distributed in an agglomerated form such as island-shaped form, thereby greatly reducing the regional conductivity connectivity and toughening effect of the metal phase in the metal ceramic.
Disclosure of Invention
Aiming at the problems of high porosity, overflow of metal phase, uneven tissue distribution and the like of the sintered material caused by non-infiltration of the metal and ceramic interface in the preparation process of the metal ceramic inert anode in the prior art, the invention aims to provide a preparation method of a high-density metal ceramic inert anode material for aluminum electrolysis.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
the invention relates to a preparation method of a high-density metal ceramic inert anode material for aluminum electrolysis, which comprises the following steps of mixing spinel type composite oxide ceramic powder, metal powder, single-phase oxide ceramic powder and an additive to obtain raw material powder, adding the raw material powder into a solvent to obtain mixed slurry, then adding a bonding agent into the mixed slurry, carrying out ball milling to obtain metal ceramic slurry, carrying out spray granulation to obtain metal ceramic composite powder, carrying out press forming to obtain a metal ceramic green body, degreasing, and sintering under oxygen partial pressure to obtain the inert anode material.
According to the preparation method, on one hand, the single-phase oxide is additionally added into the raw materials, on the other hand, the sintering is carried out in the negative pressure atmosphere with certain oxygen partial pressure, the interface wettability of the metal phase and the spinel oxide ceramic is effectively improved, the spreading and distribution of the metal phase among ceramic phases are effectively improved, the combination and growth of ceramic grains are effectively inhibited, the connected network-shaped distribution of the metal phase is realized, and the cermet inert anode material for aluminum electrolysis with the sintering relative density superior to 97% is obtained.
During experimental exploration, the inventors found that increasing the oxygen partial pressure of the sintering atmosphere both improves and worsens the wettability of the metallic phase with respect to the ceramic phase, which varies from material to material, for example with respect to Al2O3A Cu system, Al, when the partial pressure of oxygen is properly increased until a Cu-O composite oxide is formed2O3The method has the advantages that the wettability between the metal and the spinel oxide ceramic is improved through the partial pressure of the atmospheric oxygen, and the sintering driving force of the metal ceramic is improved.
In a preferred embodiment, the raw material powder comprises the following components in parts by weight: 50-80 parts of spinel composite oxide ceramic powder, 20-40 parts of metal powder, 2-15 parts of single-phase oxide powder and 0-5 parts of additive;
the spinel type composite oxide ceramic powder is AB composed of at least two metals selected from nickel, iron, aluminum, copper and zinc2O4Form oxygenAt least one of the ceramic powders, preferably NiFe2O4、NiAl2O4、ZnFe2O4、Ni(Fe，Zn)2O4At least one of ceramic powders;
the metal in the metal powder is selected from at least one of iron, copper, nickel and chromium;
the single-phase oxide powder is selected from NiO and Cu2O、Fe2O3At least one of ZnO powder and ZnO powder;
the additive is selected from Mn, Ti, Sn, Y2O3、La2O3、SiO2And CaO.
In the invention, a small amount of additives can be added, and metal addition elements or/and other ceramic addition auxiliaries can be added to adjust the corrosion resistance, the ceramic sintering activity and the like of the metal phase of the metal ceramic.
Further preferably, the raw material powder comprises the following components in parts by weight: 52-55 parts of spinel composite oxide ceramic powder, 22-38 parts of metal powder, 5-8 parts of single-phase oxide powder and 0-5 parts of additive.
Preferably, the spinel-type composite oxide ceramic powder has an average particle diameter of 0.5 to 5.0 μm, preferably 1.0 to 3.0 μm.
Preferably, the single-phase oxide powder has an average particle diameter of 0.2 to 5.0 μm, preferably 0.5 to 2.0 μm.
In a preferable scheme, the volume fraction of the raw material powder in the mixed slurry 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 at least one selected from the group consisting of polyvinyl alcohol, paraffin wax and rubber, and is preferably polyvinyl alcohol.
In a preferable scheme, the ball milling time is 10-100 h, preferably 30-60 h, and the rotating speed of the ball milling is 60-100 r/min.
The high-dispersion uniform metal ceramic slurry obtained by ball milling is subjected to spray granulation to obtain spherical metal ceramic mixed powder with good fluidity.
In a preferable scheme, the particle size of the metal ceramic composite powder is 8-20 μm, and is preferably 12-18 μm.
In a preferable scheme, the pressure of the pressing type is 100-300 MPa, and preferably 150-250 MPa.
In a preferable scheme, the degreasing temperature is 400-600 ℃, and the degreasing time is 2-10 h.
The degreasing can be carried out in a vacuum environment and a protective atmosphere.
According to the preferable scheme, the sintering is carried out in a mixed atmosphere containing oxygen and protective atmosphere, wherein the oxygen partial pressure is 50-2000 Pa, the total pressure of the mixed gas is 1000-10000 Pa, the sintering temperature is 1150-1350 ℃, and the sintering time is 1-5 h.
Further preferably, the oxygen partial pressure is 200-800 Pa, and the total pressure of the mixed gas is 2200-3500 Pa
Principles and advantages
According to the invention, a proper amount of single oxide or/and sintering is carried out in a certain oxygen partial pressure negative pressure atmosphere, the interface wettability of the metal phase and the spinel oxide ceramic is effectively improved, the spreading and distribution of the metal phase among ceramic phases are effectively improved, the combination and growth of ceramic grains are effectively inhibited, the connected network-like distribution of the metal phase is realized, and the metal ceramic inert anode material for aluminum electrolysis with the sintering relative density superior to 97% is obtained.
The method has the advantages that: (1) formation of a three-dimensional network of metallic phases: under the condition of the same volume fraction of metal phase, the metal ceramic has better conductivity, and the strengthening and toughening effects of the metal phase are exerted more fully. (2) The metal phase is uniformly distributed, and the limited and rapid peeling of the metal ceramic in the inert electrolysis process due to the agglomeration of the metal phase can be effectively avoided. (3) The relative density of the cermet is better than 97%: compared with an inert anode with lower relative density, the corrosion rate of the metal ceramic is obviously reduced, and the phenomena of anode swelling and the like caused by the electrolyte permeating into the anode are avoided.
In a word, the metal phase of the ceramic inert anode material obtained by the invention is distributed in a connected network shape, and meanwhile, the ceramic phase grains are refined, so that the relative density of the material is high; has better conductivity, thermal shock resistance and corrosion resistance, and is a preparation method of a high-performance metal ceramic inert anode material for aluminum electrolysis.
Drawings
FIG. 1: the microstructure of the highly dense cermet inert anode material obtained in example 2; it can be seen from the figure that the metal phase is distributed in a connected network, the ceramic grains are uniform, and the sample is compact.
FIG. 2: comparative example 2 a cermet microstructure with island-like distribution of a metal phase; it can be seen from the figure that the metal phase is distributed in island shape, the ceramic grains are coarse, and the sample has residual pores.
Detailed Description
Example 1
The raw material powder used in this example includes 55 parts by weight of NiFe2O4-10NiAl2O4Ceramic composite powder, 38 parts of Cu-20Ni-10Fe alloy powder and 4 parts of Cu2O powder and 1 part of Fe2O3Powder, 2.0 parts of Y2O3Sintering aid ceramic powder. Wherein NiFe2O4And NiAl2O4The average particle diameters of the ceramic composite powders were 3.0 μm and 1.5 μm, respectively, and Cu was2O powder and Fe2O3The average particle size of the powder was 0.5 μm and 1.5. mu.m, Y2O3Has an average particle diameter of 0.50. mu.m. The preparation method of this example comprises the following steps:
(1) and preparing the metal ceramic slurry. Adding raw material powder into deionized water serving as a solvent to obtain mixed slurry, controlling the volume fraction of the raw material powder in the mixed slurry to be 30%, and adding 2% polyvinyl alcohol which is soluble in an organic solvent and accounts for the weight of the raw material powder as an adhesive; and ball milling for 40h at the rotating speed of 90r/min to obtain the low-viscosity and uniform metal ceramic slurry.
(2) Spray drying is adopted to obtain the metal ceramic spherical mixed powder with the average grain diameter of 10 mu m.
(3) And pressing the powder by adopting cold isostatic pressing to obtain a green body, wherein the pressing pressure is 180MPa, and the pressure maintaining time is 15 min.
(4) Carrying out subsequent degreasing sintering on the metal ceramic pressed compact, wherein the degreasing temperature is 600 ℃, and the degreasing time is 20 h; the sintering temperature is 1280 ℃, the sintering is carried out by using mixed gas of nitrogen and oxygen, wherein the oxygen partial pressure is 800Pa, the nitrogen partial pressure is 2200Pa, and the sintering heat preservation time is 2h, thus obtaining the metal ceramic inert anode material.
The cermet inert ceramic phase obtained in this example had an average particle size of 4.0 μm and the metal phase was in the form of an interconnected network. The relative density of the metal ceramic is better than 99.2%, the three-point bending strength is 550MPa, and the thermal shock resistance temperature is better than 600 ℃.
Example 2
The raw material powder used in this example includes 70 parts by weight of NiFe2O4-10Ni(Fe,Zn)2O4Ceramic composite powder, 22 parts of Cu-10Ni-5Fe-5Cr alloy powder and 6 parts of Cu2O powder and 2 parts of NiO powder. Wherein NiFe2O4And Ni (Fe, Zn)2O4The average particle diameters of the ceramic composite powders were 2.5 μm and 0.8. mu.m, respectively, and Cu was added2O powder and Fe2O3The average particle size of the powder was 0.5 μm and 0.8. mu.m. The preparation method of this example comprises the following steps:
(1) and preparing the metal ceramic slurry. Deionized water is used as a solvent, raw material powder is added to obtain mixed slurry, and the volume fraction of the raw material powder in the mixed slurry is controlled to be 35%. Then adding 1.5 percent of polyvinyl alcohol which accounts for the weight of the raw material powder and is dissolved in an organic solvent as an adhesive; and ball milling for 40h at the rotating speed of 80r/min to obtain the low-viscosity and uniform metal ceramic 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 pressing the powder by adopting cold isostatic pressing to obtain a green body, wherein the pressing pressure is 220MPa, and the pressure maintaining time is 10 min.
(4) Carrying out subsequent degreasing sintering on the metal ceramic pressed compact, wherein the degreasing temperature is 500 ℃, and the degreasing time is 25 h; sintering at 1320 ℃, wherein the sintering temperature is mixed gas of nitrogen and oxygen, the oxygen partial pressure is 200Pa, the nitrogen partial pressure is 3500Pa, and the sintering heat preservation time is 4h, thus obtaining the metal ceramic inert anode material.
The cermet inert ceramic phase obtained in this example had an average particle size of 3.5 μm and the metal phase was in the form of an interconnected network. The relative density of the metal ceramic is better than 98.5%, the three-point bending strength is 420MPa, and the thermal shock resistance temperature is better than 500 ℃.
Example 3
The raw material powder used in this example includes NiFe in an amount of 52 parts by weight2O4-10NiAl2O4Ceramic composite powder, 38 parts of Cu-20Ni-10Fe alloy powder and 4 parts of Cu2O powder and 1 part of Fe2O3Powder, 2.0 parts of Y2O3Ceramic powder as sintering aid, metal Mn powder in 2.0 weight portions and metal Cr powder in 1.0 weight portion. Wherein NiFe2O4And NiAl2O4The average particle diameters of the ceramic composite powders were 3.0 μm and 1.5 μm, respectively, and Cu was2O powder and Fe2O3The average particle size of the powder was 0.5 μm and 1.5. mu.m, Y2O3Has an average particle diameter of 0.50 μm, and the metal Mn powder and Cr powder have average particle diameters of 15 μm and 8 μm. The preparation method of this example comprises the following steps:
(5) and preparing the metal ceramic slurry. Adding raw material powder into deionized water serving as a solvent to obtain mixed slurry, controlling the volume fraction of the raw material powder in the mixed slurry to be 30%, and adding 2% polyvinyl alcohol which is soluble in an organic solvent and accounts for the weight of the raw material powder as an adhesive; and ball milling for 40h at the rotating speed of 90r/min to obtain the low-viscosity and uniform metal ceramic slurry.
(6) Spray drying is adopted to obtain the metal ceramic spherical mixed powder with the average grain diameter of 10 mu m.
(7) And pressing the powder by adopting cold isostatic pressing to obtain a green body, wherein the pressing pressure is 180MPa, and the pressure maintaining time is 15 min.
(8) Carrying out subsequent degreasing sintering on the metal ceramic pressed compact, wherein the degreasing temperature is 600 ℃, and the degreasing time is 20 h; the sintering temperature is 1280 ℃, the sintering is carried out by using mixed gas of nitrogen and oxygen, wherein the oxygen partial pressure is 800Pa, the nitrogen partial pressure is 2200Pa, and the sintering heat preservation time is 2h, thus obtaining the metal ceramic inert anode material.
The cermet inert ceramic phase obtained in this example had an average particle size of 3.8 μm and the metal phase was in the form of an interconnected network. The relative density of the metal ceramic is better than 98.8%, the three-point bending strength is 500MPa, and the thermal shock resistance temperature is better than 550 ℃.
Comparative example 1
The raw material powder used in this example includes 55 parts by weight of NiFe2O4-10NiAl2O4Ceramic composite powder, 38 parts of Cu-20Ni-10Fe alloy powder and 4 parts of Cu2O powder and 1 part of Fe2O3Powder, 2.0 parts of Y2O3Sintering aid ceramic powder. Wherein NiFe2O4And NiAl2O4The average particle diameters of the ceramic composite powders were 3.0 μm and 1.5 μm, respectively, and Cu was2O powder and Fe2O3The average particle size of the powder was 0.5 μm and 1.5. mu.m, Y2O3Has an average particle diameter of 0.50. mu.m. The preparation method of this example comprises the following steps:
(1) and preparing the metal ceramic slurry. Deionized water is used as a solvent, and raw material powder is added into a ball milling medium, so that the volume of the raw material powder accounts for 30% of the total volume of water and the powder. Before ball milling, adding 2% polyvinyl alcohol which is in the weight of the raw material powder and is dissolved in an organic solvent as an adhesive; ball milling for 40h to obtain the low-viscosity and uniform metal ceramic slurry.
(2) Spray drying is adopted to obtain the metal ceramic spherical mixed powder with the average grain diameter of 10 mu m.
(3) And pressing the powder by adopting cold isostatic pressing to obtain a green body, wherein the pressing pressure is 180MPa, and the pressure maintaining time is 15 min.
(4) Carrying out subsequent degreasing sintering on the metal ceramic pressed compact, wherein the degreasing temperature is 600 ℃, and the degreasing time is 20 h; sintering at 1280 deg.C to obtain nitrogen gas with nitrogen partial pressure of 3000Pa and sintering heat preservation time of 2h to obtain the cermet inert anode material.
The cermet inert ceramic phase obtained in this example had an average particle size of 5.0 μm, the metal phase was locally agglomerated and distributed in islands. The relative density of the metal ceramic is better than 96.2%, the three-point bending strength is 350MPa, and the thermal shock resistance temperature is better than 300 ℃.
Comparative example 2
The raw material powder used in this example includes 78 parts by weight of NiFe2O4-10Ni(Fe,Zn)2O4Ceramic composite powder, 22 parts of Cu-20Ni-10Fe alloy powder. Wherein NiFe2O4And Ni (Fe, Zn)2O4The average particle diameters of the ceramic composite powders were 2.5 μm and 0.8. mu.m, respectively. The preparation method of this example comprises the following steps:
(1) and preparing the metal ceramic slurry. Deionized water is used as a solvent, and raw material powder is added into a ball milling medium, so that the volume of the raw material powder accounts for 35% of the total volume of water and the powder. Before ball milling, adding 1.5 percent of polyvinyl alcohol which is in the weight of the raw material powder and dissolved in an organic solvent as a bonding agent; ball milling for 40h to obtain the low-viscosity and uniform metal ceramic 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 pressing the powder by adopting cold isostatic pressing to obtain a green body, wherein the pressing pressure is 220MPa, and the pressure maintaining time is 10 min.
(4) Carrying out subsequent degreasing sintering on the metal ceramic pressed compact, wherein the degreasing temperature is 500 ℃, and the degreasing time is 25 h; sintering at 1320 ℃, wherein the sintering temperature is mixed gas of nitrogen and oxygen, the oxygen partial pressure is 200Pa, the nitrogen partial pressure is 3500Pa, and the sintering heat preservation time is 4h, thus obtaining the metal ceramic inert anode material.
The cermet inert ceramic phase obtained in this example had an average particle size of 4.2 μm and the metal phase agglomerated "island-like". The relative density of the metal ceramic is better than 96.5%, the three-point bending strength is 280MPa, and the thermal shock resistance temperature is better than 300 ℃.
Claims (10)
1. A preparation method of a high-density metal ceramic inert anode material for aluminum electrolysis is characterized by comprising the following steps: the preparation method comprises the following steps of mixing spinel type composite oxide ceramic powder, metal powder, single-phase oxide ceramic powder and additives to obtain raw material powder, adding the raw material powder into a solvent to obtain mixed slurry, then adding a binder into the mixed slurry, carrying out ball milling to obtain metal ceramic slurry, carrying out spray granulation to obtain metal ceramic composite powder, carrying out press forming to obtain a metal ceramic green body, degreasing, and sintering under oxygen partial pressure to obtain the inert anode material.
2. The method for preparing the highly-dense metal ceramic inert anode material for aluminum electrolysis according to claim 1, wherein the method comprises the following steps: the raw material powder comprises the following components in parts by weight: 50-80 parts of spinel composite oxide ceramic powder, 20-40 parts of metal powder, 2-15 parts of single-phase oxide powder and 0-5 parts of additive;
the spinel type composite oxide ceramic powder is AB composed of at least two metals selected from nickel, iron, aluminum, copper and zinc2O4At least one of type oxide ceramic powders;
the metal in the metal powder is selected from at least one of iron, copper, nickel and chromium;
the single-phase oxide powder is selected from NiO and Cu2O、Fe2O3At least one of ZnO powder and ZnO powder;
the additive is selected from Mn, Ti, Sn, Y2O3、La2O3、SiO2And CaO.
3. The method for preparing the highly-dense metal ceramic inert anode material for aluminum electrolysis according to claim 1, wherein the method comprises the following steps: the spinel-type composite oxide ceramic powder has an average particle size of 0.5 to 5.0 [ mu ] m, and the single-phase oxide powder has an average particle size of 0.2 to 5.0 [ mu ] m.
4. The method for preparing the highly-dense metal ceramic inert anode material for aluminum electrolysis according to claim 1, wherein the method comprises the following steps: in the mixed slurry, the volume fraction of the raw material powder is 25-40%.
5. The method for preparing the highly-dense metal ceramic inert anode material for aluminum electrolysis according to claim 1, wherein the method comprises the following steps: the addition amount of the adhesive is 1-3% of the mass of the raw material powder; the adhesive is at least one selected from polyvinyl alcohol, paraffin and rubber.
6. The method for preparing the highly-dense metal ceramic inert anode material for aluminum electrolysis according to claim 1, wherein the method comprises the following steps: the ball milling time is 10-100 h, and the ball milling speed is 60-100 r/min.
7. The method for preparing the highly-dense metal ceramic inert anode material for aluminum electrolysis according to claim 1, wherein the method comprises the following steps: the particle size of the metal ceramic composite powder is 8-20 mu m.
8. The method for preparing the highly-dense metal ceramic inert anode material for aluminum electrolysis according to claim 1, wherein the method comprises the following steps: the pressure of the pressing type is 100-300 MPa.
9. The method for preparing the highly-dense metal ceramic inert anode material for aluminum electrolysis according to claim 1, wherein the method comprises the following steps: the degreasing temperature is 400-600 ℃, and the degreasing time is 2-10 h.
10. The method for preparing the highly-dense metal ceramic inert anode material for aluminum electrolysis according to claim 1, wherein the method comprises the following steps: the sintering is carried out in a mixed atmosphere containing oxygen and protective atmosphere, wherein the partial pressure of oxygen is 50-2000 Pa, the total pressure of the mixed gas is 1000-10000 Pa, the sintering temperature is 1150-1350 ℃, and the sintering time is 1-5 h.
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