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WO2016189571A1 - Corps assemblé et électrode pour électrolyse - Google Patents

Corps assemblé et électrode pour électrolyse Download PDF

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Publication number
WO2016189571A1
WO2016189571A1 PCT/JP2015/002666 JP2015002666W WO2016189571A1 WO 2016189571 A1 WO2016189571 A1 WO 2016189571A1 JP 2015002666 W JP2015002666 W JP 2015002666W WO 2016189571 A1 WO2016189571 A1 WO 2016189571A1
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WO
WIPO (PCT)
Prior art keywords
cermet
metal
assembly body
phase
oxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2015/002666
Other languages
English (en)
Inventor
Ryoma NAKAZAWA
Kazuhiro YOSHIDOME
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rio Tinto Alcan International Ltd
TDK Corp
Original Assignee
Rio Tinto Alcan International Ltd
TDK Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rio Tinto Alcan International Ltd, TDK Corp filed Critical Rio Tinto Alcan International Ltd
Priority to PCT/JP2015/002666 priority Critical patent/WO2016189571A1/fr
Publication of WO2016189571A1 publication Critical patent/WO2016189571A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • B22F7/062—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 involving the connection or repairing of preformed parts
    • B22F7/064—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 involving the connection or repairing of preformed parts using an intermediate powder layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Complex oxides containing nickel and at least one other metal element
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/80—Compounds containing nickel, with or without oxygen or hydrogen, and containing one or more other elements
    • C01G53/82—Compounds containing nickel, with or without oxygen or hydrogen, and containing two or more other elements
    • 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
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/02—Electrodes; Connections thereof
    • C25C7/025—Electrodes; Connections thereof used in cells for the electrolysis of melts

Definitions

  • the present invention relates to an assembly body comprising a cermet member and a metal member made as one body, and an electrode for an electrolysis using said assembly body.
  • cermet member used as an electrode material under harsh environment such as a molten salt electrolysis or so comprising a ferrite electrode material to improve corrosion resistance and a metal component to improve conductivity is widely known (Patent document 1).
  • the cermet member is known as it can maintain high conductivity and corrosion resistance even at high temperature range for example of 900 to 1000 o C or so, thus the cermet material having good characteristics in many ways are being developed.
  • the cermet member When using the cermet member as the electrode, the cermet member becomes a part of the electric current path. Also, the cermet member has high electric resistance compared to a metal member. Thus, the volume of the cermet member can be reduced with advantage when an assembly body of a cermet member and a metal member is used as an electrode compared to the case wherein only the cermet member is used singularly as an electrode; thereby the electric resistance of the entire electrode can be reduced. An additional benefit is the reduction of the cost of the electrode.
  • the assembly body When bonding the cermet member and the metal member by simple heat treatment, the assembly body tends to easily crack. When the assembly body is cracked, then the mechanical strength becomes small; and when the assembly body is used as an electrode, there is a problem that the electric resistance raises compared to the case where there is no crack.
  • the patent document 2 discloses an assembly body used as an electrode material for aluminum production wherein the cermet member and the metal member are made as one body via an intermediate layer.
  • said metal member becomes a part of the electric current path, thus the volume of the cermet member can be reduced compared to the case wherein only the cermet member is used singularly as the electrode.
  • the electric resistance can be reduced more than for an electrode using said cermet member alone, thus the electric power consumption of aluminum production or so can be reduced.
  • the carbon electrode used for the aluminum production or so by the cermet electrode or by the composite electrode the amount of emission of CO 2 can be reduced.
  • Patent document 2 discloses an assembly body wherein the intermediate member is composed of foam having many voids and forming a particular network structure. It is believed that thanks to this network structure of the stress of entire assembly body is relieved, and thus no crack forms in the cermet member. However, when the intermediate member has the network structure as in patent document 2, a continuous, reproducible electrical contact cannot be ensured at working temperature which can result in heterogeneous electric current density distribution, thus when used as the electrode for the electrolysis, the electrolysis efficiency may deteriorate.
  • the present invention was attained in view of such situation, and its object is to provide the assembly body having only little voids and cracks in the intermediate member and nearby thereof forming the assembly body, and further the assembly body made of the metal member and the cermet member having sufficient bonding strength; and the electrode for the electrolysis using said assembly body.
  • the assembly body comprises a cermet member, a metal member, and an intermediate member bonding said cermet member and said metal member, wherein said cermet member includes a cermet oxide phase and a cermet metal phase, said intermediate member includes an intermediate oxide phase and an intermediate metal phase, and said intermediate oxide phase includes at least one or more metal oxide.
  • the assembly body according to the present invention comprises the above mentioned constitution; thereby the voids at said intermediate member are reduced, thus improves the bonding strength. Further, the crack does not appear.
  • the reason for the improvement of the bonding strength and the suppression of the crack due to the above constitution is because 1) the oxide phase included in said intermediate member limits the metal phase in the intermediate member and as a consequence, limits the volume of voids due to metal solidification shrinkage 2) by making the values of the thermal expansion of the intermediate layer and that of the cermet member closer, the residual stress caused by the thermal strain is reduced, thus the cracking can be prevented and also the bonding strength of the assembly body can be improved.
  • At least one of metal oxide among said metal oxides is selected from metal oxides included in the cermet oxide phase.
  • an area ratio occupied by said intermediate oxide phase is 10% to 50% at a cut face of the assembly body being cut perpendicular with respect to a boundary between said cermet member and said intermediate member, when a total area including an area occupied by said intermediate oxide phase and an area occupied by said intermediate metal phase in a region where said intermediate oxide phase is present is defined as 100%.
  • an area ratio of voids occupying in entire said intermediate member is 30% or less.
  • a metal only layer constituted substantially only of metal is present at a region included in said intermediate member contacting a boundary between said cermet member and said intermediate member.
  • said oxide phase included in said cermet member includes at least oxide of Ni.
  • At least part of said oxide phase included in said cermet member comprises nickel ferrite.
  • said metal phase included in said cermet member includes at least one of Ni and Cu.
  • S o /S m satisfies below equation (1) when S o is an area of said oxide phase and S m is an area of said metal phase at a cross section of said cermet member, and S o /S m is an area ratio between said cermet oxide phase and said cermet metal phase.
  • a spinel ferrite phase expressed by a composition formula of Ni x Fe y M z O 4 (x + y + z
  • said nickel oxide phase is included in said cermet member, and the average composition of said nickel oxide phase is expressed by Ni x'1 Fe 1-x'1 O (0.70 ⁇ x'1 ⁇ 1.00).
  • the content ratio of Ni is 20 to 90 wt%
  • the content ratio of Cu is 10 to 80 wt% at said metal phase when entire said metal phase included in said cermet member is 100 wt%.
  • said metal member includes at least one of Ni, Cu, Fe.
  • said metal member includes at least Ni and Fe.
  • a content of Ni included in said metal member is 40 to 85 wt%, and the content of Fe is 15 to 60 wt% when entire said metal member is 100 wt%.
  • said intermediate metal phase comprises at least one of Cu, Ni and Fe.
  • said metal only layer includes at least Ni.
  • At least one oxide of said intermediate member is the same oxide as that included in said cermet member.
  • a difference in absolute value between an average linear expansion coefficient of said cermet member and the average linear expansion coefficient of said metal member being 2.0 ppm/ o C or less is present within a predetermined range of 1000 o C or higher.
  • the assembly body of the present invention it may be used for the electrodes for electrolysis.
  • the electrode for electrolysis comprising the assembly body according to the present invention is an electrode for electrolysis with excellent corrosion resistance and strength compared to conventional ones comprising the cermet member and the metal member. Further, in case the cermet member and/or the metal member includes Ni, and particularly when used for the molten salt electrolysis such as electrolytic refining of the aluminum, then the electrode for the electrolysis will have low solubility to the molten salt (particularly of fluoride), and will have excellent durability.
  • a process for producing an assembly body of the present invention is a process for producing an assembly body having a cermet member, a metal member and an intermediate member comprising the steps of producing a mixture comprising an oxide to become an intermediate oxide phase included in the intermediate member after heating and a metal to become an intermediate metal phase included in the intermediate member after heating, arranging the mixture between the cermet member and the metal member, and heating the cermet member and the metal member in order to bond the cermet member and the metal member.
  • Fig.1 is a schematic diagram of the cross section of the assembly body according to one embodiment of the present invention.
  • Fig.2 is a schematic diagram of enlarged cross section of the cermet member of the assembly body according to one embodiment of the present invention.
  • Fig.3 is a temperature profile during the bonding step.
  • Fig.4 is a schematic diagram showing the definition of the average linear expansion coefficient.
  • Fig.5 is a schematic diagram showing the example of the relationship between the temperature and the size of the thermal expansion of the cermet member and the metal member.
  • Fig.6 is a schematic diagram showing the condition of carrying out the strength measurement by four points bending.
  • Fig.7 is a schematic diagram showing the shape of the assembly body used for the strength measurement by four points bending.
  • Fig.8 is a BEI image of the comparative example 1.
  • Fig.9 is a BEI image of the example 8.
  • Fig.10 is a BEI image of the example 13.
  • Fig.11 is a schematic diagram showing the breakage at the inside of the intermediate member during the four points bending test.
  • Fig.12 is a schematic diagram showing the breakage at the inside of the cermet member during the four points bending test.
  • the assembly body according to the present invention comprises the cermet member 30, the metal member 50, and the intermediate member 40.
  • the size of each member included in the assembly body is not particularly limited, and it may be an appropriate size depending on the usage.
  • Fig.2 is the schematic diagram showing the internal structure of the cermet member 30.
  • the cermet member 30 according to the present invention comprises the cermet oxide phase 10 and the cermet metal phase 20.
  • the cermet oxide phase 10 preferably comprises at least the oxide of Ni.
  • the assembly body according to the present embodiment is used for the electrode for the molten salt electrolysis such as electrolysis of aluminum or so
  • the cermet member comprises Ni
  • the solubility against the molten salt can be lowered compared to the case of not comprising Ni.
  • the corrosion resistance of the cermet member at high temperature is enhanced.
  • the cermet oxide phase 10 is preferably made of nickel ferrite from the point of improving the conductivity and the corrosion resistance; and further preferably the cermet oxide phase 10 is made mainly of nickel ferrite.
  • Nickel ferrite has high conductivity; hence it can make the conductivity of the cermet member 30 higher.
  • the cermet oxide phase 10 is made mainly of nickel ferrite
  • the content ratio of the nickel ferrite is 70 wt% or more in case the entire oxide of Ni in the cermet oxide phase 10 is 100 wt%.
  • the oxide other than the nickel ferrite (for example, NiO, Fe 2 O 3 or so) may be mixed.
  • the conductivity of the cermet member 30, and the value of the thermal expansion of the cermet member 30 during the firing can be regulated.
  • S o is an area of said cermet oxide phase 10
  • S m is the area of said cermet metal phase 20
  • S o /S m is an area ratio between said cermet oxide phase 10 and said cermet metal phase 20, preferably S o /S m satisfies 60/40 ⁇ S o /S m ⁇ 90/10.
  • S o /S m is preferably within the above mentioned range, by covering the metal phase in the cermet member with the oxide phase, the metal phase can be prevented from dissolving into the fluorides.
  • the cermet metal phase 20 preferably includes at least one metal selected from Ni, and Cu; and further preferably in case the entire cermet metal phase 20 is 100 wt%, the content ratio of Ni is 20 to 90 wt%, and the content ratio of Cu is 10 to 80 wt%.
  • the cermet metal phase 20 preferably has the above mentioned constitution because the corrosion resistance of the cermet member can be improved. Also, the cermet metal phase 20 functions to enhance the conductivity of the cermet member 30.
  • the area ratio between the cermet oxide phase 10 and the cermet metal phase 20 is calculated by observing the cut face of the cermet member 30 using the backscattered electron image (BEI) by the electron microscope at the magnification of 300 to 1000x.
  • BEI backscattered electron image
  • the cermet oxide phase 10 can comprise the spinel ferrite phase 12 and the nickel oxide phase 14.
  • the nickel oxide phase 14 comprises the nickel oxide expressed by the composition formula of Ni x’ Fe 1-x’ O (x’ ⁇ 0).
  • the cermet oxide phase 10 preferably comprises at least the spinel ferrite phase 12.
  • the cermet metal phase 20 is dispersed in the cermet oxide phase 10, and preferably it is dispersed mainly in the spinel ferrite phase 12. In other words, preferably it forms the constitution that a lot of the cermet metal phase 20 is trapped in the spinel ferrite phase 12. Also, since the cermet member is a sintered body, the inside of the spinel ferrite phase 12, the inside of the nickel oxide phase 14, and/or the boundary part of each phase comprises small amount of voids (not shown in the figure).
  • the content ratio of the spinel ferrite phase 12 is 40 to 80 wt%, and the content ratio of the oxide nickel phase 14 is 0 to 10 wt% (including 0 wt%), and the content ratio of the cermet metal phase 20 is 15 to 45 wt%.
  • the content ratio of each phase is preferably within the above mentioned range, since the dissolving of the cermet member to the molten slat during the molten salt electrolysis can be prevented, and also since it has the conductivity, the electrolytic efficiency can be improved.
  • the average composition of the entire spinel ferrite phase 12 is preferably within the above mentioned range, because it is the best compromise between good electrical conductivity and good corrosion resistance.
  • the cermet member 30 preferably includes the nickel oxide phase 14, and more preferably the average composition of the entire nickel oxide phase 14 included in the cermet member 30 is within the range expressed by Ni x'1 Fe 1-x'1 O (0.70 ⁇ x'1 ⁇ 1.00).
  • the average composition of the nickel oxide phase 14 is within the above mentioned preferable range because it results from a chemical balance with the other phases (spinel ferrite phase 12 and metal phase 20).
  • the type of the metal included in the metal member 50 is not particularly limited.
  • the metal member 50 preferably includes at least one of Ni, Cu, Fe.
  • the metal member 50 preferably includes at least Ni and Fe.
  • the content of Ni included in the metal member 50 is preferably 40 to 85 wt%, and more preferably it is 55 to 80 wt%.
  • the content of Fe included in the metal member 50 is preferably 15 to 60 wt%, and more preferably the content of Fe is 20 to 45 wt%.
  • the metal member 50 preferably includes at least one of Ni or Cu, since the heat resistance and the anti-oxidant property of the assembly body obtained at the end can be enhanced.
  • the example including at least one of Ni or Cu pure Ni or the alloy between Ni, Cr and Fe may be mentioned.
  • said intermediate member 40 bonds with said cermet member 30 and said metal member 50, and comprise an intermediate metal phase 42 and an intermediate oxide phase 44.
  • the voids generated in the intermediate member 40 can be limited by said oxides.
  • said intermediate oxide phase 44 comprising said metal oxide limits the volume of the voids due to metal solidification shrinkage. That is, as the intermediate oxide phase 44 is present at the intermediate member 40, the ratio of the voids present in the intermediate member 40 can be reduced significantly.
  • the voids can become the point of the focus of the stress at the intermediate member 40, by reducing the amount of the voids, it is thought that the bonding strength of the assembly body can be increased.
  • the cracking of the assembly body 1 can be prevented, thus the bonding strength of the assembly body 1 can be improved significantly.
  • At least one oxide included in the internal oxide phase 44 is the oxide included in the cermet oxide phase 10.
  • the value of the thermal expansion of the intermediate member 40 can become closer to that of the cermet member 30.
  • the residual stress caused by the thermal strain is reduced, thus the cracking can be prevented and also the bonding strength of the assembly body 1 can be improved.
  • the type of the metal constituting the intermediate member 42 is not particularly limited.
  • the intermediate metal phase 42 may be constituted from single metal element, or it may be constituted from plurality of metal elements. Note that, it is preferable that the intermediate metal phase 42contain at least one of Cu, Ni and Fe.
  • the distance from the boundary between the cermet member 30 and the intermediate member 40 to the intermediate oxide phase 44 which is at the furthest position in the vertical direction is defined as "d".
  • the range from said boundary to the distance "d" is set as the measurement range.
  • the area ratio occupied by the intermediate oxide phase 44 is preferably 10% to 50%.
  • the voids in the intermediate member 40 is sufficiently filled with the metal oxide, and the cracking can be prevented and also the bonding strength can be improved.
  • the area ratio of the voids occupied by the said entire intermediate member is 30% or less.
  • the boundary between the cermet member 30 and the intermediate member 40, and the boundary between the intermediate member 40 and the metal member 50 can be determined by visual observation using the optical microscope against said cross section. Also, it may be determined by observing using BEI (backscattered electron) image obtained by scanning electron microscope. Also, the intermediate oxide phase 44 is the gray color part in the intermediate member 40 of BEI (backscattered electron) image obtained by scanning electron microscope.
  • the assembly body 1 according to the present invention preferably comprises a layer of pure metal which is in contact with the boundary between the cermet member 30 and the intermediate member 40, and said metal only layer 46 constituted substantially only by the metal is present at the region included in the intermediate metal member 40.
  • "constituted substantially only by the metal” means that no gray part was observed in the BEI (backscattered electron) image obtained by scanning electron microscope under the magnification of 100 to 500x.
  • the thickness of said metal only layer is 30 ⁇ m or more.
  • said metal only layer 46 In case said metal only layer 46 is present, the wettability of the intermediate member 40 against the cermet member 30 improves, and further the bonding strength of the assembly body 1 is further improved. Also, said metal only layer 46 preferably includes at least Ni.
  • the intermediate member 40 is not limited to the constitution made of single layer as shown in Fig.1, and it may be a constitution wherein the intermediate member 40 itself is made of two or more layers, or the layer made of solder may be present at the part contacting with the metal member 50. Also, the lower limit of the thickness of the intermediate member 40 is 20 ⁇ m. Further the thickness of the intermediate member 40 is preferably 20 to 1000 ⁇ m.
  • the metal included in the intermediate member 40 is substantially constituted of Cu and Ni only. “Substantially constituted of Cu and Ni only” means that the content ratio of Cu and Ni in the intermediate member is 80 wt% or more when the entire metal included in the intermediate member is 100 wt%. Also, the reason as why the above constitution is preferable is because it can improve the bonding strength of the cermet member and the metal member.
  • the production method of the cermet member constituting the assembly body of the present embodiment comprises, a mixing step of obtaining the mixed powder by mixing the ferrite oxide powder and the metal powder, a molding step of obtaining the molded body by molding the mixed powder, and a firing step of obtaining the fired body by firing the molded body under predetermined atmosphere and temperature.
  • the ferrite source material powder comprising iron oxide (for example Fe 2 O 3 ) and metal oxide (for example NiO) in a desired mol ratio is prepared. Then, said ferrite source material powder is calcined and pulverized to obtain the ferrite oxide powder.
  • the assembly body according to the present embodiment to the molten salt electrolysis such as the electrolytic refining of aluminum or so, since the cermet member which is obtained at the end comprises Ni, the solubility against the molten salt (particularly of fluorides) can be lowered compared to the case of not comprising Ni.
  • the metal powder is prepared separately from said ferrite oxide powder.
  • the type of said metal powder is not particularly limited, and it may be a powder of single metal such as powder of Ni metal alone or the powder of Cu metal alone, it may be metal powder of two or more types for example metal powder mixing the metal powder of Ni and metal powder of Cu in a specific weight ratio. Further, two or more metal powders may be melted to form alloy powder, and this may be used as the metal powder as well.
  • the metal powder preferably comprises Ni.
  • Ni in case of using the assembly body according to the present embodiment to the electrode for molten salt electrolysis such as the production of aluminum or so, by having Ni in the cermet member which is obtained at the end, the solubility against the molten salt (particularly of fluorides) can be lowered compared to the case of not comprising Ni.
  • said ferrite oxide powder and said metal powder are mixed to obtain the mixed powder.
  • the method of mixing said ferrite oxide powder and said metal powder is not particularly limited, and the usual mixing method such as by ball mill or so can be used. Also, the mixing method may be dry mixing method or wet mixing method, and it only needs to be a method which can uniformly mix said ferrite oxide powder and said metal powder.
  • the average primary particle diameter of the mixed powder obtained by the mixing step is not particularly limited as well, however usually the average primary particle diameter of the mixed powder having 1 to 30 ⁇ m is obtained.
  • said mixed powder is molded to produce the molded body.
  • the molding method is not particularly limited, and for example the molded body can be produced by the usual dry molding method which is used in general.
  • said mixed powder added with a binder is filled into the usual mold, and press molded to produce the molded body.
  • the type of the binder is not particularly limited, and the binder used for the usual molding can be used. From the point that a good molding property can be obtained, polyvinylalcohol (PVA) is preferably used as the binder.
  • the molding method is not limited to the dry molding method, and it may be a wet molding wherein the slurry including the mixed powder and the solvent is pressure molded while removing the solvent, further it may be other molding method.
  • the firing step can be carried out under the atmosphere of active gas; however it is preferable to carry out under the atmosphere of the inactive gas such as nitrogen gas or argon gas or so.
  • the inactive gas such as nitrogen gas or argon gas or so.
  • the firing temperature and the firing time during the firing step are not particularly limited, and it can be appropriately regulated by said ferrite oxide powder and said metal powder which is used as the source material.
  • the sintered body can be obtained by raising the temperature under the atmosphere of nitrogen gas or argon gas, and firing at the firing temperature of 1200 to 1400 o C, more preferably of 1300 to 1400 o C for preferably 1 to 10 hours and more preferably 2 to 6 hours.
  • the firing temperature within the above mentioned range, the amount of the nickel oxide phase in the oxide phase of the cermet member can be made small, thus the conductivity of the cermet member tends to improve.
  • the firing temperature is preferably 1400 o C or less.
  • the temperature increasing speed during the firing step is preferably 30 to 500 o C/hour, and more preferably 50 to 350 o C/hour.
  • the temperature increasing speed to 500 o C/hour or lower the density of the cermet member can be lowered.
  • the temperature increasing speed to 30 o C/hour or more the production cost of the cermet member can be reduced.
  • the temperature decreasing speed during the firing step it is preferably 10 to 500 o C/hour, and more preferably 30 to 350 o C/hour.
  • the temperature decreasing speed to 500 o C/hour or lower, the density of the cermet member can be lowered.
  • the temperature decreasing speed to 30 o C/hour or more the production cost of the cermet member can be reduced.
  • the sintered body obtained by the firing step may be used as the cermet member without any processing, or it may be used as cermet member having desired shape by carrying some degree of processing.
  • the metal being used is not particularly limited.
  • those used for the structure such as stainless steel or so may be selected.
  • the assembly body according to the present embodiment is used for the molten salt electrolysis such for aluminum production or so, it is preferable to select the Ni based alloy such as Ni-Fe alloy or so as the material of the metal member, since the heat resistance and the oxidation resistance are high and the solubility to the molten salt (particularly of fluoride) is low.
  • a metal member containing iron is preferred as the cermet member loses iron during electrolysis and can be refilled by the iron contained in the metal member.
  • the presence of Ni in the intermediate layer can advantageously allow a regulation of the iron migration from the metal member toward the cermet member.
  • commercially available pure Ni, the alloy including Ni and Cu, and the alloy including Ni, Cr and Fe or so can be selected as well.
  • the step of making the cermet member and the metal member as one body will be referred as a bonding step.
  • the metal constituting the intermediate member of the present embodiment it is preferable to select the metal which melts during the heating treatment of the bonding.
  • the metal which melts at relatively low temperature such as alloy of Cu and Ni.
  • the oxide constituting the intermediate member of the present embodiment it is preferable to use the oxide entirely or partially same as the oxide constituting said cermet member.
  • the oxide included in the cermet member is constituted by the mixture of Ni based ferrite and NiO, then as the oxide constituting the intermediate member, it is preferable to include Ni based ferrite and/or NiO.
  • Said metal and said oxide constituting said intermediate member is thoroughly mixed while in a powder form before the heat treatment.
  • said area ratio occupied by said intermediate oxide phase becomes 10% to 50% when the total area of the area occupied by said intermediate oxide phase and the area occupied by said intermediate metal phase in said intermediate member is 100%.
  • the powder of after the mixing may be made into molded body by applying a pressure, or an organic solvent may be used to the powder of after the mixing to make into a paste.
  • the powder of after the mixing is press molded so that the thickness is preferably 0.01 to 0.1 cm, more preferably 0.015 to 0.025 cm.
  • the thickness of after the molding By making the thickness of after the molding within said range, it allows to provide a sufficient amount of intermediate member during the bonding step, and the bonding strength of the assembly body obtained at the end is enhanced, further the deformation of the intermediate member during the bonding step becomes easy to suppress to a level which can be ignored.
  • the molding pressure preferably it is 140 MPa or more, and more preferably 200 MPa or more. By having the molding pressure within said range, the molded body becomes easy to have suitable thickness.
  • the mixed powder of metal and oxide which are the constitution element of the above mentioned intermediate member is further mixed with the organic solvent to form a paste.
  • the type of the organic solvent is not particularly limited, and for example the organic solvent such as ⁇ -terpineol, ethylcellulose, glycerin or so can be used.
  • the viscosity of the organic solvent can be appropriately regulated, and also ⁇ -terpineol and ethylcellulose does not separate, further the cellulose will not remain in a solid form, thus it tends to easily become uniform organic solvent.
  • the powder of after the mixing and the above mentioned organic solvent are mixed to obtain the mixed paste.
  • the mixed paste is coated on the bonding face of said cermet member and/or the bonding face of said metal member.
  • the thickness of the mixed paste is 0.03 cm to 0.3 cm, and more preferably it is 0.03 cm to 0.1 cm.
  • Fig.3 is the schematic diagram showing the time difference of the temperature in time during the bonding step according to the present embodiment.
  • the bonding step includes the temperature increasing step (step S1), the high temperature maintaining step (step S2), and the temperature decreasing step (step S3).
  • the bonding step is preferably carried out in vacuumed condition, or inactive gas atmosphere, for example Ar and N 2 or so. However, it is not limited thereto.
  • the temperature increasing step (step S1) is a step of gradually heating while applying a pressure to each member in the heating furnace.
  • the temperature increasing speed is preferably 30 o C/hour to 500 o C/hour, and more preferably 50 o C/hour to 300 o C/hour.
  • the high temperature maintaining step (step S2) is the step which maintains at the predetermined temperature, and it starts from time t1 of Fig.3. Preferably, it is carried out at the temperature where the average linear expansion coefficient difference in the absolute value between the metal member and the cermet member is 2.0 ppm/ o C or less, and further preferably at the temperature where the average linear expansion coefficient of the metal member and the cermet member matches.
  • T 0 is the room temperature
  • L 0 is the length of the sample at the room temperature T 0 .
  • the value wherein the amount of change in the length (L 1 -L 0 ) divided by L 0 is the thermal expansion between the temperature T 1 and the temperature T 0 . Further, the value which is obtained by dividing this thermal expansion by the temperature difference (T 1 -T 0 ) is the average linear expansion coefficient.
  • the average linear expansion coefficient ⁇ (T 1 ) between the temperature T 0 and the temperature T 1 is as shown in the below equation (A). Note that, the average linear expansion coefficient ⁇ (T 1 ) between the temperature T 0 and the temperature T 1 taking T 0 as the standard temperature may be referred simply as the average linear expansion coefficient at the temperature T 1 .
  • Fig.5 shows the change of the length of the cermet member and the change of the length of the metal member when the length of the member at the standard temperature T 0 is the same.
  • T 1 the average linear expansion coefficient of the cermet member and the average linear expansion coefficient of the metal member are matched, and the length of the cermet member and the length of the metal member are matched. That is, in the temperature T 1 , the difference between the average linear expansion coefficient of the cermet member and the average linear expansion coefficient of the metal member is 0.
  • the difference between the average linear expansion coefficient at the temperature T 1 is small (the difference in the absolute value is 2.0 ppm/ o C or less), and when the high temperature maintaining is carried out at the temperature T 1 , the thermal strain is small when it is returned to room temperature after the high temperature maintaining, thus a bonded body without the crack can be easily obtained.
  • the maintaining temperature maintained during the high temperature maintaining step is preferably 1100 to 1400 o C, and more preferably 1100 to 1250 o C.
  • the maintaining time is preferably 1 to 10 hours, and more preferably 2 to 6 hours.
  • the upper limit of the maintaining temperature is preferably 1400 o C.
  • the temperature decreasing step (step S3) is a step of gradually cooling the assembly body in the heating furnace.
  • the temperature decreasing speed is 10 o C/hour to 600 o C/hour, and more preferably 10 o C/hour to 300 o C/hour.
  • the bonding step is carried out under an inactive gas atmosphere (for example, nitrogen gas or argon gas or so).
  • an inactive gas atmosphere for example, nitrogen gas or argon gas or so.
  • the above mentioned metal only layer tends to easily exist in the intermediate member compared to the case of using the above molded body. Also, by having the metal only layer in the intermediate member, the wettability against said cermet member of said intermediate member improves, and the bonding strength can be improved.
  • the metal only layer is easily formed when using said mixed paste, because the part near the boundary between the cermet member and the intermediate member is reduced and metallized by having the above mentioned organic solvent in said mixed paste.
  • the method of forming the metal only layer is not particularly limited, and other methods for forming the intermediate member using the above mentioned mixed paste, for example the method of forming said metal only layer using CVD (chemical vapor deposition) or PVD (physical vapor deposition) or so can be used.
  • CVD chemical vapor deposition
  • PVD physical vapor deposition
  • the obtained assembly body may be used as it is, or it may be processed depending on the usage. Also, the usage of the obtained assembly body is not particularly limited; however it is preferable to be used as the electrode for the electrolysis.
  • the void of the intermediate member can be filled, thus the decline of the strength can be suppressed, and further the dispersed condition of the cermet member and the intermediate member becomes good, thus the bonding strength improves.
  • the wettability can be regulated by comprising Al, which easily forms alloy with Ni, in the intermediate member.
  • the metal member of the present invention may comprise 50 wt% or less of substance other than metal.
  • the type of the substance other than the metal is not particularly limited, and for example carbon, metal nitride or so can be mentioned.
  • the cermet member 30 may include other phases which are different from the spinel ferrite phase 12, the nickel oxide phase 14 and the metal phase 20.
  • the material of the metal member 50 is not particularly limited. In the present embodiment, pure Ni and Ni based alloy has been listed as the metal member 50, however other alloys may be selected. In case of using other alloy, it is preferable to use the alloy having equivalent expansion value as the pure Ni or Ni based alloy. Also, from the point of increasing the bonding strength, the diffusion bonding method utilizing the mechanical pressure may be used.
  • Example 1 The commercially available nickel oxide (NiO) powder and iron oxide (Fe 2 O 3 ) powder were blended so that the mol ratio of NiO against Fe 2 O 3 is 50/50, then it was mixed using the ball mill thereby the mixed powder was obtained. This calcination was carried out to the mixed powder by maintaining at the temperature of 1000 o C for 3 hours. The obtained calcined powder was pulverized in the ball mill, thereby the ferrite oxide powder was prepared.
  • NiO nickel oxide
  • Fe 2 O 3 iron oxide
  • the obtained ferrite oxide powder and the copper (Cu) powder were blended so that the weight ratio of the ferrite oxide powder against the copper powder is 83/17.
  • the blended powder was mixed in the ball mill, and 0.8 wt% of PVA (polyvinylalcohol) as the binder was added with respect to the total weight of the above mentioned ferrite oxide powder and the copper powder; then by mixing by the ball mill, the mixed powder was prepared.
  • PVA polyvinylalcohol
  • the obtained mixed powder is press molded, thereby plurality of molded body having a rectangular parallelepiped shape were obtained.
  • These molded bodies were fired by maintaining under N 2 atmosphere at the temperature of 1300 o C for 3 hours. Then it was gradually cooled in N 2 atmosphere, thereby plurality of the sintered body (the cermet member) having the rectangular parallelepiped shape of 1.5 cm x 1.5 cm x 2.0 cm were prepared.
  • One of the obtained cermet member was cut, and the cut face was observed by the backscattered electron image (BEI) using electron microscope (S-2100 made by Hitachi High-Technologies) for 30 random visual fields at 500x magnification, thereby the area ratio between the oxide phase and the metal phase was calculated.
  • BEI backscattered electron image
  • S-2100 made by Hitachi High-Technologies
  • Ni rod processed into 1.5 cm x 1.5 cm x 2.0 cm was prepared.
  • the mirror face polishing was carried out to one of the face of 1.5 cm x 1.5 cm of the cermet member and the one of the face of 1.5 cm x 1.5 cm of the metal member.
  • the mixed molded body which will become the intermediate member by the bonding step was produced.
  • the metal powder which becomes the source material of the mixed molded article Ni powder and Cu powder were selected.
  • the obtained mixed powder was applied with the pressure of 195 MPa so that the thickness is 0.02 cm, thereby the mixed molded body was produced.
  • the produced mixed molded article having the thickness of 0.02 cm was placed on the mirror polished side of the cermet member, then the firing was carried out by placing Ni rod thereon.
  • Ni rod was placed so that the mirror polished side is in contact against said mixed molded body.
  • the heat treatment was carried out while applying the load of 0.5 kPa towards the cermet member side from the metal member side.
  • the temperature increasing speed and the temperature decreasing speed were both 300 o C/hour, and the high temperature maintaining time in a vacuumed atmosphere was 3 hours, and the maintaining temperature was 1200 o C, thereby the bonding step was carried out.
  • the steps of the calculation comprises the step of determining the measuring range in BEI image of each sample, and the step of calculating the area ratio where the intermediate oxide phase occupies in said measurement range. For each steps, it is discussed in below.
  • the BEI image of the region where said intermediate member is placed between said cermet member and said metal member was observed at the magnification of 100x.
  • the distance "d" was measured which is to the intermediate oxide phase (the gray part of BEI image) which is present at the side of said intermediate member from the boundary between said cermet member and said intermediate member, and present at the position furthest from said boundary in perpendicular direction.
  • the distance "d” was measured which is between the boundary and the point furthest from said boundary among the intersections within the region where said intermediate oxide phase occupies in said BEI image and perpendicular line from the boundary between said cermet member and said intermediate member.
  • the region in said intermediate member wherein the distance from the boundary is "d" or less was defined as the measuring range.
  • the contrast of BEI image was analyzed, and the area ratio of the gray part which reflects said intermediate oxide phase against said entire BEI image was calculated. The same calculation was carried out to 10 visual fields, and the average area ratio of said gray part was calculated. The obtained value was defined as the area ratio of said intermediate oxide phase in said intermediate member.
  • the void ratio in the intermediate member was calculated.
  • the calculation of the void ratio was carried out by the analysis of the transmission X ray image taken by X ray CT machine (XVA-160 made by UNI-HITE SYSTEM Corporation). Also, the measuring area was set to 0.5 cm x 0.5 cm.
  • the X ray enters from the metal member and passes through the intermediate member and comes out from the cermet member, thereby the transmission image was obtained.
  • the void part appears in white color.
  • the contrast of said transmission image was analyzed, and the ratio of the white color part reflecting the void with respect to the entire transmission image was calculated. The same calculation was carried out to 10 visual fields, and the average area ratio of said white color part was calculated.
  • the obtained value was defined as the ratio of the void in the intermediate member.
  • each of the obtained assembly body was processed respectively, to have the size of 0.4 cm x 0.3 cm x 1.2 cm.
  • TMA measurement was carried out using the above sample.
  • the TMA measurement was carried out using the thermomechanical analysis apparatus (TMA 8310 made by Rigaku Corporation). From the obtained TMA curve, the average linear thermal expansion coefficient at the 1300 o C of the intermediate member was calculated. Note that the standard temperature was 25 o C. The results are shown in Table 1. Also, the places of the breakage were observed as well.
  • the four points bending strength test was carried out by the method shown in the schematic diagram of Fig.6. Note that, as the four points bending strength test machine (Model 11311-D made by AIKOH ENGINEERING CO., LTD) was used. In the present examples, the bonding strength of 20 MPa or more was defined as good bonding strength. Note that, the bonding strength is more preferably 50 MPa or more, and further preferably 100 MPa or more.
  • test results of the examples 1 to 12 and the comparative example 1 of the experiment 1 are show in in Table 1.
  • the average linear expansion coefficient of the intermediate member continuously declines. That is, the average linear expansion coefficient of the intermediate member can be regulated by changing the ratio of the oxide in the intermediate member.
  • the voids (the black colored part surrounded by the broken line in Fig.8 (the comparative example 1)) generated in the intermediate member contacting the cermet member were filled with the oxide NiO-NiFe 2 O 4 as shown in Fig.9 (Example 8). Note that, the filled part (the gray part surrounded by the broken line in Fig.9) is the intermediate oxide phase.
  • the void in said intermediate member decreases the residual stress inside the assembly body caused by the difference between the thermal expansion of the cermet member and the thermal expansion of the metal member, and it is thought to suppress the generation of the crack in the assembly body.
  • the cracks did not occur as same as or more than the comparative example 1.
  • the bonding strength of the examples 5 to 12 was improved compared to the comparative example 1 without the intermediate oxide phase. Further, in the examples 5 to 12 wherein the area ratio of the oxide phase in said intermediate member was 10% or more, the bonding strength was 50 MPa or more. The reason that the bonding strength of the examples 5 to 12 was higher than the bonding strength of examples 1 to 4 is because the voids of the intermediate member which becomes the point of focus of the stress has been reduced.
  • the four points bending strength was 100 MPa or more. Note that, the point of the breakage was all at the intermediate member.
  • the starting embodiment of the intermediate member may be said molded body or said mixed paste.
  • the starting embodiment of the intermediate member was said molded body.
  • the starting body of the intermediate member was mixed paste.
  • Ni and Cu were selected as the metal of the intermediate member.
  • NiO-NiFe 2 O 4 80 : 20 (wt%) was selected.
  • the obtained mixed powder and the organic solvent were mixed to form a paste.
  • the prepared mixed paste was coated on the mirror polished side of said cermet member so that the thickness is 0.1 cm. Then, Ni rod was placed thereon and the firing was carried out. Here, the Ni rod made the mirror polished side to contact with the paste.
  • the example 13 using the mixed paste did not have a crack. Also, the ratio of the void in the intermediate member was 6.5% which is below 30%.
  • Fig.10 in case of using the mixed paste, at the part included in the intermediate member 40 and near the boundary between the intermediate member including oxides NiO-NiFe 2 O 4 and the cermet member 30, the oxide of NiO-NiFe 2 O 4 does not mixed in, thus the metal only layer 46 constituted only from the metal was formed.
  • the breakage part has changed as mentioned in above, possibly because the strength of the intermediate member has improved, and it became difficult to break at the intermediate member. Since the strength of the intermediate member improved so much that the breakage part has changed, thus the even higher bonding strength was able to obtain in the example 13. Note that, in the example 13, the bonding strength became stronger as it got higher than 185 MPa.
  • the measurement of the thermal expansion rate was carried out using TMA, thereby the average linear expansion coefficient was measured at each temperature up to 1400 o C taking 25 o C as the standard temperature.
  • the assembly body having the intermediate oxide phase in the intermediate member as in the present invention shows high bonding strength of 20 MPa or more; and when the assembly body is regulated so that the presence ratio of said intermediate oxide phase is 10 to 50%, it shows high bonding strength of 50 MPa or more.
  • the electrode for the electrolysis having both advantages of the cermet material and the metal material can be made.

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Abstract

Un corps assemblé comprend un élément en cermet, un élément métallique et un élément intermédiaire liant ledit élément en cermet audit élément métallique. L'élément en cermet comprend une phase d'oxyde de cermet et une phase métallique en cermet. L'élément intermédiaire comprend une phase d'oxyde intermédiaire et une phase de métal intermédiaire. La phase d'oxyde intermédiaire comprend au moins un oxyde de métal.
PCT/JP2015/002666 2015-05-26 2015-05-26 Corps assemblé et électrode pour électrolyse Ceased WO2016189571A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4443314A (en) * 1983-03-16 1984-04-17 Great Lakes Carbon Corporation Anode assembly for molten salt electrolysis
US4495049A (en) * 1983-05-03 1985-01-22 Great Lakes Carbon Corporation Anode for molten salt electrolysis
US4529494A (en) * 1984-05-17 1985-07-16 Great Lakes Carbon Corporation Bipolar electrode for Hall-Heroult electrolysis
US4626333A (en) * 1986-01-28 1986-12-02 Great Lakes Carbon Corporation Anode assembly for molten salt electrolysis

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4443314A (en) * 1983-03-16 1984-04-17 Great Lakes Carbon Corporation Anode assembly for molten salt electrolysis
US4495049A (en) * 1983-05-03 1985-01-22 Great Lakes Carbon Corporation Anode for molten salt electrolysis
US4529494A (en) * 1984-05-17 1985-07-16 Great Lakes Carbon Corporation Bipolar electrode for Hall-Heroult electrolysis
US4626333A (en) * 1986-01-28 1986-12-02 Great Lakes Carbon Corporation Anode assembly for molten salt electrolysis

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Essential Readings in Light Metals", vol. 4, 1 March 2013, JOHN WILEY & SONS, INC., Hoboken, NJ, USA, ISBN: 978-1-11-863663-3, article R. P. PAWLEK: "Inert Anodes: An Update", pages: 1126 - 1133, XP055185837, DOI: 10.1002/9781118647745.ch150 *

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