CN113337849B - Aluminum electrolysis metal ceramic inert anode and near-net-shape preparation method thereof - Google Patents

Aluminum electrolysis metal ceramic inert anode and near-net-shape preparation method thereof Download PDF

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CN113337849B
CN113337849B CN202110647805.5A CN202110647805A CN113337849B CN 113337849 B CN113337849 B CN 113337849B CN 202110647805 A CN202110647805 A CN 202110647805A CN 113337849 B CN113337849 B CN 113337849B
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metal
ceramic
metal ceramic
inert anode
phase
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CN113337849A (en
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张雷
周科朝
何勇
熊慧文
李志友
沈廷
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Central South University
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    • 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
    • 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
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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
    • B22F3/22—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip
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    • 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
    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/06—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools
    • 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
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00—Products made by additive manufacturing
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    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
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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
    • B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling

Abstract

The invention discloses a cermet inert anode and a near net shape forming preparation method thereof, wherein the structure of the cermet inert anode is T-shaped and consists of an electrically connected metal guide rod and a cermet shell coating the electrically connected metal guide rod, the cermet shell consists of a metal phase and a ceramic phase, and the metal phase contains Cu and Fe and also contains at least one of Ni, Cr, Co and Mn; the ceramic phase comprises NiFe 2 O 4 A base ceramic. The cermet inert anode is net-shaped by gel casting or 3D printing. The invention can accelerate the film forming speed of the electrode surface in the electrolytic process by adding alloying elements in the metal phase, the formed stable oxide film is stable and compact, meanwhile, the metal ceramic inert anode structure can ensure that the anode working surface has uniform current density distribution, and the corrosion resistance of the metal ceramic inert anode provided by the invention is greatly improved by the synergistic action of the components and the structure.

Description

Aluminum electrolysis metal ceramic inert anode and near-net-shape preparation method thereof
Technical Field
The invention belongs to the technical field of aluminum electrolysis, and particularly relates to a metal ceramic inert anode and a near-net-shape preparation method thereof.
Background
The inert anode technology can reduce the production cost of electrolytic aluminum, save energy and increase yield, is environment-friendly, and brings the technical revolution of the traditional aluminum electrolysis industry. By optimizing the material preparation technology and the electrolysis process conditions, NiFe 2 O 4 The metal ceramic inert anode has better conductivity and greatly improved high temperature and molten salt corrosion resistance. The alloy composition and content of the metal phase in the cermet play a role in determining the corrosion resistance of the anode, meanwhile, the structure of the anode and the arrangement mode of the anode in the electrolytic bath also have certain influence on the potential and current distribution of the surface of the electrode, and the uneven distribution of the surface current density can possibly cause local excessive corrosion of the anode, thereby influencing the service life of the electrode.
At present, the metal phases in the aluminum electrolysis inert anode cermet material are mainly Cu, Fe and Ni metals and Cu-Ni and Fe-Ni base alloys, and the corrosion and stripping rates of the Cu and Fe metals determine the service life of the electrode in the use process. In order to reduce the corrosion rate of the metal ceramic, on one hand, the alloy components are optimized to improve the corrosion resistance of the metal phase; meanwhile, the whole content of the metal phase is both the conductivity and the corrosion resistance of the metal ceramic. Therefore, when the corrosion resistance of the alloy is improved, the content of the metal phase can be properly improved, which is beneficial to improving the comprehensive performance of the inert anode.
In addition, the structure of the prior inert anode has vertical, grid, deep cup and other novel structures besides the conventional cuboid and cylindrical structures. Although the electrode structures consider various factors such as processing, connection and replacement of the electrodes, and exhaust, electrode potential and the like in the electrolytic process, in the practical application process, most of inert anodes with the existing structures have the phenomenon of uneven current density distribution on the surface, and generate excessive charge accumulation in tip and edge areas, so that the current efficiency is influenced, the local over-corrosion phenomenon is easy to occur, the structural integrity of the surface of the anode is damaged, and the service life of the anode is shortened.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a cermet inert anode with excellent corrosion resistance and a structure with uniform current density distribution characteristics, and a near-net-shape preparation method thereof.
In order to achieve the purpose, the invention provides the following technical scheme:
the invention relates to an aluminum electrolysis metal ceramic inert anode, which is in a T-shaped structure and consists of an electric connection metal guide rod and a metal ceramic shell for coating the electric connection metal guide rod, wherein the metal ceramic shell is formed by connecting an ellipsoid end at the bottom and a cylindrical vertical rod at the upper part through a fillet, the metal ceramic shell consists of a metal phase and a ceramic phase, the mass fraction of the metal phase in the metal ceramic is 20-70%, preferably 38-62%, the metal phase contains Cu and Fe, and at least one of Ni, Cr, Co and Mn; the ceramic phase comprises NiFe 2 O 4 A base ceramic.
The cermet inert anode provided by the invention has the advantages that the cermet shell takes Fe-Cu alloy as the main body of a metal phase, Ni, Co, Cr and Mn elements are introduced into the metal phase to optimize alloy components, and NiFe with excellent corrosion resistance is combined 2 O 4 The cermet material finally obtained can be rapidly filmed, can effectively resist the corrosion of electrolyte, and has high-temperature oxidation resistance and hot corrosion resistance.
In a preferred scheme, the ellipsoid end is a Boolean intersection part of five oblate ellipsoidsThe equatorial radius of the central part is a, the polar radius is b, and the center is a point O S0 And four oblate ellipsoids with equator radius of 2a and polar radius of 2b, which are symmetrically arranged and have center of point O S1 、O S2 、O S3 、O S4 (ii) a The centers of the five oblate ellipsoids are positioned in the same plane in the vertical direction, and the arrangement mode in the horizontal direction is O S1 -O S4 Around O S1 Uniformly arranged, the two connecting lines are mutually vertical, and | - [ O ] S0 O S1 ∣＝∣O S0 O S2 ∣＝∣O S0 O S3 ∣＝∣O S0 O S4 | a (13/12) a, the diameter of the vertical rod being (2/3) a, and the fillet radius being 20-30 mm.
In the preferred scheme, the height of the metal ceramic shell is H, H is more than or equal to 80mm and less than or equal to 400mm, and H is more than or equal to 120mm and less than or equal to 240mm is preferred.
Further preferably, a is more than or equal to 60mm and less than or equal to 360mm, and preferably more than or equal to 120mm and less than or equal to 240 mm;
more preferably, a/b is 2 to 6.
Further preferably, the wall thickness of the cermet sheath is 10-50mm, preferably 25-35 mm.
In a preferable scheme, in the metal phase, the mass fraction of Fe is 30-80%, and preferably 45-60%; the mass fraction of Cu is 5-50%, preferably 10-20%; in the metal phase, the sum of mass fractions of Ni, Cr, Co and Mn is less than 20%.
More preferably, in the metal phase, the mass fraction of Ni is less than or equal to 15%, the mass fraction of Cr is less than or equal to 12%, the mass fraction of Co is less than or equal to 10%, and the mass fraction of Mn is less than or equal to 5%.
Preferably, the metal phase further comprises at least one of Nb, Mo, Zn, Sn, Pb, Ta and Zr, and the sum of the mass fractions of Nb, Mo, Zn, Sn, Pb, Ta and Zr is less than or equal to 5%. The metal element can reinforce the metal phase and supplement the consumed metal phase, so that the corrosion resistance of the cermet material is further improved.
In a preferable scheme, in the metal phase, the mass fraction of Zn is less than or equal to 2%, the sum of the mass fractions of Nb, Mo, Ta and Zr is less than or equal to 1%, and the mass fraction of Sn and Pb is less than or equal to 1%.
Preferably, the ceramic phase further comprises NiO ceramic, and the mass fraction of the NiO ceramic in the ceramic phase is less than or equal to 20%, preferably 10%.
Preferably, the electric connection metal guide rod is formed by connecting a round-corner rectangular rotating body end at the bottom and a cylindrical vertical rod at the upper part through a round corner.
Preferably, the material of the electric connection metal guide rod is Fe alloy or Cu alloy,
in the preferred scheme, the metal ceramic shell and the electric connection metal guide rod are formed together by a powder metallurgy process and then sintered together to obtain the aluminum electrolysis metal ceramic inert anode.
The invention also provides a near net shape forming preparation method of the metal ceramic inert anode, which comprises the following steps: preparing metal phase powder and ceramic phase powder according to a designed proportion according to the components of a metal ceramic shell, mixing the metal phase powder and the ceramic phase powder to obtain metal ceramic powder, adding the metal ceramic powder, an organic monomer A, a gel cross-linking agent A and a surfactant A into an organic solvent A, carrying out first ball milling to obtain a metal ceramic suspension, and adding an initiator A to obtain metal ceramic slurry; preparing alloy powder according to the components of the electrically connected metal guide rod, adding the alloy powder, an organic monomer B, a gel cross-linking agent B and a surfactant B into an organic solvent B, performing ball milling for the second time to obtain an alloy powder suspension, and adding an initiator B to obtain alloy powder slurry; and then sequentially pouring and molding the alloy powder slurry and the metal ceramic powder slurry, standing and curing to obtain a metal ceramic inert anode green body, and drying, removing the glue and sintering the metal ceramic inert anode green body to obtain the metal ceramic inert anode.
In the technical scheme, in the process of preparing the metal ceramic slurry and the alloy powder slurry, an n-octanol solvent system is adopted, and a small amount of high molecular copolymer alkyl ammonium salt is contained in a surfactant to be used as a dispersing agent, so that the alloy powder and the ceramic powder in the metal ceramic powder can be stably and uniformly dispersed, meanwhile, hydroxyethyl methacrylate is taken as an organic monomer (HEMA), 1, 6-hexanediol diacrylate (HDDA) is taken as a gel crosslinking agent, the HEMA-HDDA gel system has high crosslinking speed, the strength of the formed crosslinking network is high, and the content is small, the formed initial blank of the metal ceramic gel can be further ensured to have good component uniformity and enough strength, the shrinkage is small during degreasing, and finally, the high compactness, high dimensional accuracy and component uniformity of the metal ceramic are ensured while the rapid net forming of the metal ceramic inert anode is realized.
Preferably, the average particle diameter of the metal phase powder is 1 to 10 μm, preferably 1 to 5 μm; the ceramic phase powder has an average particle diameter of 0.5 to 12 μm, preferably 1 to 5 μm.
Preferably, in the cermet powder slurry, the volume fraction of the cermet powder is 30-60%, and preferably 42-56%.
In a preferred embodiment, the organic solvent A is n-octanol.
In a preferred embodiment, the organic monomer A is hydroxyethyl methacrylate, and the volume fraction of the organic monomer A in the cermet powder slurry is 15-30%.
Preferably, the gel cross-linking agent A is 1, 6-hexanediol diacrylate, and the volume ratio of the organic monomer A to the gel cross-linking agent A is 5-15.
Preferably, the surfactant A is a mixed solution of polyvinyl alcohol and octadecyl amine acetate, and the mass fraction of the polyvinyl alcohol in the surfactant A is 60-80%.
In a preferred embodiment, the volume fraction of the surfactant a in the cermet powder slurry is 0.5-2.0%.
Preferably, the initiator A is selected from peroxidation type oxidants, and the initiator is added in per 100mL of the metal ceramic suspension and is less than or equal to 0.1 mL.
Preferably, the rotation speed of the first ball milling is 120-240r/min, and the time of the first ball milling is 10-24 h.
Preferably, the average particle size of the alloy powder is 1 to 10 μm, preferably 1 to 5 μm.
Preferably, in the alloy powder slurry, the volume fraction of the alloy powder is 30-60%, and preferably 42-56%.
In a preferred embodiment, the volume fraction of the organic monomer B in the alloy powder slurry is 15-30%.
In a preferred embodiment, the organic solvent B is n-octanol.
Preferably, the organic monomer B is hydroxyethyl methacrylate, and the volume fraction of the organic monomer B in the alloy powder slurry is 15-30%.
Preferably, the gel crosslinking agent B is 1, 6-hexanediol diacrylate, and the volume ratio of the organic monomer B to the crosslinking agent is 5-15.
Preferably, the surfactant B is a mixed solution of polyvinyl alcohol and octadecyl amine acetate, and the mass fraction of the polyvinyl alcohol in the surfactant B is 60-80%.
Preferably, the volume fraction of the surfactant B in the alloy powder slurry is 0.5-2.0%.
Preferably, the initiator B is selected from peroxidation type oxidants, and the initiator is added in per 100mL of the alloy powder suspension to be less than or equal to 0.1 mL.
Preferably, the rotation speed of the second ball milling is 120-240r/min, and the time of the second ball milling is 10-24 h.
Preferably, the alloy powder slurry is poured into a reverse mould die electrically connected with the metal guide rod, and is kept stand and cured for more than 24 hours at 50-60 ℃ to obtain an electrically connected metal guide rod gel blank, then the electrically connected metal guide rod gel blank is taken as a core rod and is placed into a metal ceramic shell reverse mould die, the metal ceramic slurry is poured into a gap between the metal ceramic shell reverse mould die and the electrically connected metal guide rod gel blank, and is kept stand and cured for more than 24 hours at 50-60 ℃ to obtain a metal ceramic inert anode green body.
Preferably, the drying temperature is 80-150 ℃, and the drying time is more than 72 h.
Preferably, the rubber discharging is carried out in vacuum or in a circulating protective atmosphere, the rubber discharging temperature is 380-440 ℃, and the rubber discharging time is 12-24 h.
In a preferable scheme, the sintering temperature is 1100-1400 ℃, and the sintering time is 1-6 h.
Further preferably, the sintering is performed in a flowing nitrogen atmosphere or a nitrogen-oxygen mixed atmosphere, and preferably, a nitrogen-oxygen mixed atmosphere having an oxygen partial pressure of 200 to 2000Pa and a gas flow rate of 60 to 120mL/min is used.
The invention also provides another near-net-shape preparation method of the metal ceramic inert anode, which comprises the following steps: preparing metal phase powder and ceramic phase powder according to the components of the metal ceramic shell according to a design proportion, adding a binder A, and then carrying out primary mixing granulation to prepare a metal ceramic particle feed; and then according to the components of the electrically connected metal guide rod, preparing alloy powder, adding a binder B, then carrying out secondary mixing granulation to obtain an alloy particle feed, then placing the alloy particle feed and the metal ceramic particle feed in a double-extrusion head type fused deposition printer, carrying out alternate 3D printing to obtain a metal ceramic inert anode green body, and then carrying out pretreatment, binder removal and sintering to obtain the metal ceramic inert anode.
In the actual operation process, according to a design structure drawing of the metal ceramic inert anode, a three-dimensional graphic file is imported into slicing software to slice the three-dimensional modeling, and a numerical control programming instruction file is output; feeding the metal ceramic particles into a material bin of a corresponding printer head, operating a numerical control programming instruction file, and performing 3D printing to obtain a metal ceramic green body; in the invention, a double-extrusion head type fused deposition printer is adopted, and the double-extrusion head is adopted to alternately print the inner layer alloy particle feeding material and the outer layer metal ceramic particle feeding material for each layer, thus obtaining the metal ceramic inert anode.
Preferably, the metal phase powder has an average particle diameter of 1 to 10 μm, preferably 2 to 5 μm; the ceramic phase powder has an average particle diameter of 0.5 to 12 μm, preferably 1 to 5 μm.
Preferably, the adhesive a is selected from polyethylene glycol.
In the preferable scheme, the cermet feed comprises, by mass, 15-60 parts of metal phase powder, 35-80 parts of ceramic phase powder and 0-5 parts of binder.
In a preferred embodiment, the feed of cermet particles has a particle size of 1 to 10mm, preferably 2 to 4 mm.
Preferably, the binder B is selected from polyethylene glycol.
In the preferable scheme, in the feeding of the alloy particles, 50-95 parts of alloy powder and 5-50 parts of binder are calculated according to parts by weight.
Preferably, the particle size of the alloy particle feed is 1-10mm, preferably 2-4 mm.
Preferably, during 3D printing, the printing extrusion temperature is set to be 150-; setting the temperature of a molding platform to be 40-150 ℃, preferably 60-110 ℃; setting the printing environment temperature to be 40-120 ℃, preferably 60-80 ℃;
further preferably, the default printing speed is set to be 20-100mm/s, preferably 40-60 mm/s; setting the wall printing speed to be 10-80mm/s, preferably 20-48 mm/s; setting the filling speed to be 20-120mm/s, preferably 50-80 mm/s; setting the idle running speed to be 50-300mm/s, preferably 50-80 mm/s; setting the printing speed of the initial layer to be 10-50mm/s, preferably 20-30 mm/s;
preferably, the pretreatment process comprises: immersing the green metal ceramic inert anode in deionized water at the temperature of 50-80 ℃ for 6-120 h; then the mixture is placed in a drying box to be dried for 2-6h at the temperature of 100-120 ℃.
Preferably, the temperature of the rubber discharge is 300-500 ℃, and the time is 12-48 h.
In a preferable scheme, the sintering temperature is 1100-1400 ℃, and the sintering time is 1-6 h.
Further preferably, the sintering is performed in a flowing nitrogen atmosphere or a nitrogen-oxygen mixed atmosphere, preferably a nitrogen-oxygen mixed atmosphere with an oxygen partial pressure of 200 to 2000Pa, and a gas flow rate of 60 to 120 mL/min.
Compared with the prior art, the invention has the following advantages:
(1) the cermet inert anode with Fe-Cu alloy as metal phase is provided, and Ni, Cr, Co, Mn and other alloy elements are introduced into the alloy system to promote the formation of anticorrosive layer on the surface of the electrode, so as to raise the anticorrosive performance of the cermet.
(2) The inventor surprisingly found that the anode working surface of the structure has uniform current density distribution characteristics, and can effectively prevent local corrosion of the electrode surface due to uneven current distribution while improving the current efficiency of the anode.
(3) The rapid preparation process is provided, the metal ceramic inert anode with the guide rod structure can be directly obtained by taking powder as a raw material, extra connection and redundant machining of the guide rod are not needed, rapid and clean forming of the inert anode is realized, the process flow is simple, and the operability is high.
Drawings
FIG. 1 is a schematic structural view of a cermet inert anode according to the present invention.
Wherein, 1, T-shaped inert anode material shell, 2, T-shaped electric connection metal guide rod.
FIG. 2 is a block diagram of a cermet inert anode material casing of the present invention.
FIG. 3 is a finite element simulation of the surface current density distribution of a cermet inert anode of example 1.
FIG. 4 is an SEM image of the sintered body of the cermet inert anode of example 1.
Fig. 5 is a surface current density finite element simulation of a deep cup anode of comparative example 2.
Detailed Description
The following detailed description of the preferred embodiments of the present invention, taken in conjunction with the accompanying drawings, will make the advantages and features of the invention easier to understand by those skilled in the art, and thus will clearly and clearly define the scope of the invention. The embodiment of the invention comprises the following steps:
example 1
A cermet inert anode of an aluminum electrolysis inert anode. The specific implementation steps are as follows:
step 1, preparing metal slurry. Providing Cu-20Ni powder with the average grain diameter of 4-5 mu m, and then adding 60 percent of metal powder, 20 percent of hydroxyethyl methacrylate, 2.5 percent of 1, 6-hexanediol diacrylate and 1 percent of surfactant into n-octanol with the balance of volume ratio, wherein the content of polyvinyl alcohol in the surfactant is 80 percent, and the balance is octadecylamine acetate. And then carrying out wet ball milling, wherein the ball milling rotation speed is 200r/min, and the ball milling time is 12 h. And (2) obtaining a metal ceramic suspension liquid with all components uniformly mixed by ball milling, then adding tert-butyl peroxybenzoate initiator into the metal ceramic suspension liquid, and quickly carrying out physical defoaming operation to remove bubbles to obtain metal slurry, wherein 0.05mL of initiator is added into each 100mL of metal ceramic suspension liquid.
And 2, preparing the metal ceramic slurry. Calculated by mass fraction, the content of the alloy phase is 40 percent, and the elements and the contents contained in the alloy phase are as follows: 40% of Fe, 5% of Cu, 45% of Ni, 8% of Co and 2% of Cr, and the alloy phase is obtained by mixing metal elementary powder in proportion; the ceramic phase component is NiFe 2 O 4 + 10% NiO. Mixing alloy phase powder and ceramic phase powder in proportion, performing ball milling and screening to obtain metal ceramic powder with the average particle size of 4-5 mu m, and then adding 40% of metal ceramic powder, 15% of hydroxyethyl methacrylate, 2% of 1, 6-hexanediol diacrylate and 1% of surfactant in percentage by volume into n-octanol in the balance, wherein the content of polyvinyl alcohol in the surfactant is 80%, and the balance is octadecylamine acetate. And then carrying out wet ball milling, wherein the ball milling rotation speed is 200r/min, and the ball milling time is 12 h. And (2) obtaining a metal ceramic suspension liquid with all components uniformly mixed by ball milling, then adding tert-butyl peroxybenzoate initiator into the metal ceramic suspension liquid, and quickly carrying out physical defoaming operation to remove bubbles to obtain the metal ceramic slurry, wherein 0.05mL of initiator is added into each 100mL of metal ceramic suspension liquid.
And 3, casting and curing the connecting guide rod. And pouring metal slurry into a pre-designed electric connecting rod die, standing and aging in a constant-temperature drying box at 55 ℃ for 24 hours, and demolding to obtain a guide rod green body with certain strength.
And 4, pouring and curing the metal ceramic shell. Pouring metal ceramic slurry into a pre-designed inert anode mold by taking the guide rod green body as a core rod, standing and aging in a constant-temperature drying box at 60 ℃ for 48h, and demolding to obtain the guide rod-provided inert anode green body with certain strength.
And 5, sequentially drying, degreasing and sintering the green metal ceramic blank to obtain the metal ceramic inert anode, wherein the step comprises the following steps of:
substep 1, placing the green metal ceramic blank in a drying oven for drying for 96 hours, wherein the drying temperature is 120 ℃.
Substep 2, the green cermet is degummed at 400 ℃ for 18 h.
And substep 3, sintering the metal ceramic green body at 1200 ℃ for 2h in an atmosphere, wherein the sintering atmosphere is a circulating nitrogen-oxygen mixed gas, and the oxygen partial pressure is 800 ppm.
The cermet inert anode with a 120mm, a/b 2 and H180 mm was obtained by the above method, and the minimum wall thickness of the outer casing was found to be 10.2 μm. Fig. 3 is a surface current density distribution simulation image of the anode in the electrolysis process, and it can be seen that the current density distribution of the lower surface part of the electrode is relatively uniform. Fig. 4 is an SEM topography of the sintered cermet shell, showing that the sintering uniformity and consistency are good, the alloy phase is uniformly dispersed in the ceramic phase matrix, and the density after sintering reaches 91.23%. The surface after 48h corrosion forms a corrosion layer of 40 μm, and the growth rate of the layer thickness is fast first and slow later along with the time extension and tends to be stable after 40 h. The element composition in the corrosion layer is mainly Co and Cr, and the contents of Fe and Cu are very small, which shows that the introduction of the elements can promote the formation of a stable compact oxide layer.
Example 2
A cermet inert anode of an aluminum electrolysis inert anode. The specific implementation steps are as follows:
step 1, preparing a metal ceramic feed. The cermet raw material powder adopted in this example includes, by weight, 30 parts of 50Fe-30Ni-20Cu alloy powder and 67 parts of NiFe 2 O 4 -10NiO ceramic composite powder, 3 parts binder of polyethylene glycol and polyvinyl butyral. Wherein the average grain diameter of the Cu-Ni-Fe alloy powder is 3.8 mu m, and the NiFe alloy powder 2 O 4 The average grain size of the-10 NiO ceramic composite powder was 1.3. mu.m. Mixing metal powder and potteryMixing and granulating the porcelain powder and the adhesive to prepare a metal ceramic particle feed with the granularity of 1.5-2.5 mm.
And step 2, preparing metal feed. The Cu-20Ni alloy powder used in this example was mixed with 97 parts of the alloy powder, 3 parts of polyethylene glycol and a binder of polyvinyl butyral, and then granulated by kneading to obtain a cermet pellet feed having a particle size of 1.5 to 2.5mm, wherein the average particle size of the alloy powder was 2.6. mu.m.
And 3, slicing the model and setting parameters. Guiding three-dimensional graphic files of a guide rod and a shell into slicing software to slice three-dimensional modeling, setting a nozzle 1 as a metal feed printing outlet, setting the diameter of the nozzle to be 0.6mm, setting the wiring width to be 0.6mm, setting the layer thickness to be 0.2mm, setting the thicknesses of a top layer and a bottom layer to be 1.5mm, setting the wall wiring times to be 5 times, setting the filling density to be 100%, and setting the printing extrusion temperature to be 180 ℃; set up nozzle 2 and print the export for the cermet feed, the diameter is 0.8mm, and the line width is 0.8mm for setting up, sets up the bed thickness and is 0.3 mm, sets up top layer and bottom thickness and is 1.5mm, sets up the wall and walks the line number of times and be 5 times, sets up packing density and is 100%, sets up to print extrusion temperature and is 180 ℃.
And 4, outputting the numerical control programming instruction file. The temperature of a forming platform is set to be 110 ℃, the temperature of a printing environment is set to be 80 ℃, the default printing speed is set to be 60mm/s, the wall printing speed is set to be 45mm/s, the filling speed is set to be 80mm/s, the idle running speed is set to be 80mm/s, the printing speed of a starting layer is set to be 40mm/s, the attachment mode of the printing platform is set to be Brim, the support suspension angle is set to be 45 degrees, and the support density is set to be 40 percent.
And 5, feeding the metal ceramic and the metal particles into material bins of corresponding printer heads, operating a numerical control programming instruction file, and printing a metal ceramic green body.
And 6, sequentially carrying out pretreatment, degreasing and sintering on the green metal ceramic blank to obtain the metal ceramic inert anode, wherein the step comprises the following steps of:
step 1, immersing the metal ceramic green body in deionized water at 60 ℃ for 120 h;
substep 2, placing the metal ceramic green body in a drying oven, and drying for 6 hours at the temperature of 110 ℃;
substep 3, placing the green metal ceramic body at 440 ℃ to degrease the green metal ceramic body for 36 hours;
and substep 4, sintering the metal ceramic green body at 1350 ℃ for 3 hours in a circulating nitrogen-oxygen mixed gas atmosphere, wherein the oxygen partial pressure is 800 ppm.
This example produced a cermet inert anode with a 240mm, a/b 2 and H300 mm, a minimum wall thickness of the outer skin portion of 26.6 μm, a sintering line shrinkage of 13-16% and a sintering density of 93.2%. After the anode is subjected to an electrolysis test for 1000 hours, the thickness of a corrosion layer is 50 micrometers, the average working voltage is 4.05V, and the equivalent annual corrosion rate is 1.2 cm/a.
Comparative example 1
The other conditions were the same as in example 1, except that the components of the alloy phase in the cermet powder were 50% Fe and 50% Cu. After the sintered cermet is corroded for 48 hours by high-temperature melt, an oxide layer with the thickness of 8 mu m is obtained, and the thickness of the oxide layer is far lower than that of the oxide layer in the embodiment 1; the Cu content in the melt increased with the increase in the corrosion time, and the rate of increase did not slow down significantly within 48 h. The results show that the film forming speed of the alloy component cermet in the melt is low, the stability of the formed oxide film is poor, and the corrosion resistance is lower than that of the embodiment 1.
Comparative example 2
Other conditions were the same as in example 1, except that the electrodes were deep cup-shaped structures having a diameter of 120mm, as shown in FIG. 5. After finite element simulation, the current density at the bottom of the annular region is found to be discontinuously distributed, the current density at the bevel edge part of the bottom is higher, and the annular region is easy to excessively corrode. The uniformity of the current density distribution is inferior to that of the T-shaped structure electrode in the embodiment.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present specification and drawings, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.

Claims (8)

1. An inert anode of aluminum electrolysis metal ceramic, which is characterized in that: the metal ceramic inert anode is in a T-shaped structure and consists of an electric connection metal guide rod and a metal ceramic shell for coating the electric connection metal guide rod, the metal ceramic shell is formed by connecting an ellipsoid end at the bottom and a cylindrical vertical rod at the upper part through a fillet, the metal ceramic shell consists of a metal phase and a ceramic phase, the mass fraction of the metal phase in the metal ceramic is 20-70%, the metal phase contains Cu and Fe, and at least one of Ni, Cr, Co and Mn; the ceramic phase comprises NiFe 2 O 4 A base ceramic;
the ellipsoid end is a Boolean intersection part of five oblate ellipsoids, wherein the oblate ellipsoid comprises an oblate ellipsoid with a central part and an equatorial radius of a and a polar radius of b, and the center is a point O S0 And four oblate ellipsoids with equator radius of 2a and polar radius of 2b, which are symmetrically arranged and have center of point O S1 、O S2 、O S3 、O S4 (ii) a The centers of the five oblate ellipsoids are positioned in the same plane in the vertical direction, and the arrangement mode in the horizontal direction is O S1 -O S4 Around O S1 Uniformly arranged, the two connecting lines are mutually vertical, and | - [ O ] S0 O S1 ∣＝∣O S0 O S2 ∣＝∣O S0 O S3 ∣＝∣O S0 O S4 -said vertical bar has a diameter of (2/3) a and said fillet radius is 20-30mm (13/12) a;
the height of the metal ceramic shell is H, a is more than or equal to 60mm and less than or equal to 360mm, a/b is 2-6, and the wall thickness of the metal ceramic shell is 10-50 mm;
in the metal phase, the mass fraction of Fe is 30-80%, the mass fraction of Cu is 5-50%, and the sum of the mass fractions of Ni, Cr, Co and Mn in the metal phase is less than 20%;
the metal phase also comprises at least one of Nb, Mo, Zn, Sn, Pb, Ta and Zr, and the sum of the mass fractions of Nb, Mo, Zn, Sn, Pb, Ta and Zr is less than or equal to 5%;
the ceramic phase also comprises NiO ceramic, and the mass fraction of the NiO ceramic in the ceramic phase is less than or equal to 20%.
2. The inert anode of aluminum electrolysis cermet according to claim 1, wherein: the electric connection metal guide rod is formed by connecting a round-corner rectangular rotating body end at the bottom and a cylindrical vertical rod at the upper part through a round corner; the material of the electric connection metal guide rod is Fe alloy or Cu alloy.
3. A near net shape manufacturing method of an inert anode of an aluminum electrolysis cermet according to any of claims 1-2, characterized by: the method comprises the following steps: preparing metal phase powder and ceramic phase powder according to a designed proportion according to the components of a metal ceramic shell, mixing the metal phase powder and the ceramic phase powder to obtain metal ceramic powder, adding the metal ceramic powder, an organic monomer A, a gel cross-linking agent A and a surfactant A into an organic solvent A, carrying out first ball milling to obtain a metal ceramic suspension, and adding an initiator A to obtain metal ceramic slurry; preparing alloy powder according to the components of the electrically connected metal guide rod, adding the alloy powder, an organic monomer B, a gel cross-linking agent B and a surfactant B into an organic solvent B, performing ball milling for the second time to obtain an alloy powder suspension, and adding an initiator B to obtain alloy powder slurry; and then sequentially pouring and molding the alloy powder slurry and the metal ceramic powder slurry, standing and curing to obtain a metal ceramic inert anode green body, and drying, removing the glue and sintering the metal ceramic inert anode green body to obtain the metal ceramic inert anode.
4. The near-net-shape preparation method of the inert anode of the aluminum electrolysis cermet according to claim 3, characterized in that:
the average grain diameter of the metal phase powder is 1-10 mu m, the average grain diameter of the ceramic phase powder is 0.5-12 mu m, the volume fraction of the metal ceramic powder in the metal ceramic powder slurry is 30-60%,
the organic solvent A is n-octanol,
the organic monomer A is hydroxyethyl methacrylate, the volume fraction of the organic monomer A in the metal ceramic powder slurry is 15-30%,
the gel cross-linking agent A is 1, 6-hexanediol diacrylate, the volume ratio of the organic monomer A to the gel cross-linking agent A is 5-15,
the surfactant A is a mixed solution of polyvinyl alcohol and octadecyl amine acetate, the mass fraction of the polyvinyl alcohol in the surfactant A is 60-80%,
the volume fraction of the surfactant A in the metal ceramic powder slurry is 0.5-2.0%,
the initiator A is selected from peroxide oxidants, the initiator added in each 100mL of the metal ceramic suspension is less than or equal to 0.1mL,
the rotating speed of the first ball milling is 120-240r/min, the time of the first ball milling is 10-24h,
the average grain diameter of the alloy powder is 1-10 mu m,
in the alloy powder slurry, the volume fraction of the alloy powder is 30-60%,
the organic solvent B is n-octanol;
the organic monomer B is hydroxyethyl methacrylate, the volume fraction of the organic monomer B in the alloy powder slurry is 15-30%,
the gel crosslinking agent B is 1, 6-hexanediol diacrylate, the volume ratio of the organic monomer B to the crosslinking agent is 5-15,
the surfactant B is a mixed solution of polyvinyl alcohol and octadecyl amine acetate, the mass fraction of the polyvinyl alcohol in the surfactant B is 60-80%,
the volume fraction of the surfactant B in the alloy powder slurry is 0.5-2.0%,
the initiator B is selected from peroxidation type oxidants, the initiator added in each 100mL of alloy powder suspension is less than or equal to 0.1mL,
the rotation speed of the second ball milling is 120-240r/min, and the time of the second ball milling is 10-24 h.
5. The near-net-shape preparation method of the inert anode of the aluminum electrolysis cermet according to claim 3, characterized in that:
pouring alloy powder slurry into a reverse mould die electrically connected with a metal guide rod, standing and solidifying for more than 24h at 50-60 ℃ to obtain an electrically connected metal guide rod gel blank, then taking the electrically connected metal guide rod gel blank as a core rod, placing the electrically connected metal guide rod gel blank into a metal ceramic shell reverse mould die, pouring metal ceramic slurry into a gap between the metal ceramic shell reverse mould die and the electrically connected metal guide rod gel blank, and standing and solidifying for more than 24h at 50-60 ℃ to obtain a metal ceramic inert anode green body;
the drying temperature is 80-150 ℃, the drying time is more than 72 hours,
the glue discharging is carried out in vacuum or in a circulating protective atmosphere, the glue discharging temperature is 380-440 ℃, the glue discharging time is 12-24h,
the sintering temperature is 1100-1400 ℃, and the sintering time is 1-6 h.
6. The near-net-shape preparation method of the inert anode of the aluminum electrolysis cermet according to any one of claims 1-2, characterized by comprising the following steps: the method comprises the following steps: preparing metal phase powder and ceramic phase powder according to the design proportion according to the components of the metal ceramic shell, adding a binder A, and then carrying out primary mixing granulation to prepare metal ceramic particle feed; and then according to the components of the electrically connected metal guide rod, preparing alloy powder, adding a binder B, then carrying out secondary mixing granulation to obtain an alloy particle feed, then placing the alloy particle feed and the metal ceramic particle feed in a double-extrusion head type fused deposition printer, carrying out alternate 3D printing to obtain a metal ceramic inert anode green body, and then carrying out pretreatment, binder removal and sintering to obtain the metal ceramic inert anode.
7. The near net shape preparation method of the inert anode of the aluminum electrolytic cermet according to claim 6, characterized in that:
the average particle diameter of the metal phase powder is 1 to 10 μm, the average particle diameter of the ceramic phase powder is 0.5 to 12 μm,
the adhesive A is selected from polyethylene glycol,
in the metal ceramic feed, by mass, 15-60 parts of metal phase powder, 35-80 parts of ceramic phase powder and 0-5 parts of binder;
the grain diameter of the feed of the metal ceramic particles is 1-10mm,
the adhesive B is selected from polyethylene glycol,
in the feeding of the alloy particles, 50-95 parts of alloy powder and 5-50 parts of binder are counted by mass,
the grain diameter of the alloy particle feed is 1-10 mm.
8. The near-net-shape preparation method of the inert anode of aluminum electrolysis cermet according to claim 6, characterized in that:
during 3D printing, setting the printing extrusion temperature at 240-,
the pretreatment process comprises the following steps: immersing the green metal ceramic inert anode in deionized water at the temperature of 50-80 ℃ for 6-120 h; then drying the mixture in a drying box at the temperature of 100-120 ℃ for 2-6 h;
the temperature of the glue discharging is 300-500 ℃, and the time is 12-48 h;
the sintering temperature is 1100-1400 ℃, and the sintering time is 1-6 h.
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