CN1548586A - Ceramet material with gradient function for electrolyzing Al - Google Patents

Ceramet material with gradient function for electrolyzing Al Download PDF

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Publication number
CN1548586A
CN1548586A CNA031365981A CN03136598A CN1548586A CN 1548586 A CN1548586 A CN 1548586A CN A031365981 A CNA031365981 A CN A031365981A CN 03136598 A CN03136598 A CN 03136598A CN 1548586 A CN1548586 A CN 1548586A
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gradient
nife
phase
cermet
metal
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CN1291066C (en
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李劼
周科朝
赖延清
李志友
叶绍龙
邹忠
田忠良
张刚
张吉龙
孟杰
刘业翔
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Aluminum Corp of China Ltd
Central South University
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Aluminum Corp of China Ltd
Central South University
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Abstract

The present invention relates to aluminum electrolysis, and is especially inert ceramet anode. The ceramet material has structure of at least two layers and is rod shaped, plate shaped or cup shaped. The ceramic phase is spinelle type composite oxide; and the metal phase is made of Cu, Ni, Co, Fe, Ag, Pt, Au and other metal or their binary or multiple-element alloy. The composite material with gradient function has excellent comprehensive performance under electrolysis, and the anode of the composite material needs no frequent replacement. Using the composite material of the present invention can alter the electrolytic bath structure, raise production efficiency, lower aluminum ingot producing cost, improve environment, and reduce power consumption.

Description

Used for aluminium electrolysis gradient function cermet material
Technical field:
The present invention is relevant with electrolysis of aluminum, particularly cermet inert anode.
Background technology:
Aluminium electrolysis process betides in the fluoride salt melt more than 900 ℃, strict to inert anode material.Inert anode material for aluminium electrolysis is mainly metal oxide ceramic, alloy anode and sintering metal three classes.Wherein, sintering metal has been taken into account the advantages such as satisfactory electrical conductivity of the strong corrosion resistant and the metal of oxide ceramics.But, the domestic and international cermet of studying since a small amount of Metal Phase be scattered in the ceramic phase so that thermal shock resistance is poor, poorly conductive, is connected with metal guide rod difficult, be difficult to maximization; In the material preparation process, be difficult to realize the densified of material in addition, cause easily oxidation and the selective corrosion of Metal Phase under the electrolysis service condition, bring the slag that falls of ceramic phase to come off.
Summary of the invention:
The present invention is directed to the problems referred to above of used for aluminium electrolysis cermet inert anode, a kind of gradient function cermet material is provided, as the aluminium cell inert anode, replace existing carbon annode, realize the less energy-consumption of Aluminium Electrolysis process, pollution-free, target cheaply.
The ceramet material with gradient function for electrolyzing Al that the present invention manufactures and designs, its layer of structure is at least two-layer; Its ceramic phase adopts spinelle type composite oxides (AB 2O 4) pottery, wherein
A is Ni, Mg, Co, Zn, Cu, at least a among Li and the Fe;
B can be Fe, Al, Co, Mn, at least a among Cr and the Ge;
Metallographic phase is Cu, Ni, Co, Cr, Fe, Ag, Pt, binary or multicomponent alloy that single metal such as Au or these metallic elements are formed.
The corner of pole shape function-graded material is designed to right angle or arc, its composition radially and axially changes in gradient, promptly by outer 4 and bottom 9 to core 5, the metallographic phase concentration gradients increases, the ceramic phase concentration gradients reduces, the core 5 that metallographic phase content is the highest possesses good processing properties and welding property, between sidepiece gradient layer 1,2,3 and the bottom gradient layer 6,7,8 taper angle theta is arranged.
Tabular function-graded material be shaped as cubes, its radial section is designed to the Polygons of arbitrary shape, its edge is designed to right angle or arc; Its composition radially and axially changes in gradient, by outer 4 and bottom 9 to core 5; The metallographic phase concentration gradients increases, and the ceramic phase concentration gradients reduces, and the core 5 that metallographic phase content is the highest has good processing properties and welding property, between sidepiece gradient layer 1,2,3 and the bottom gradient layer 6,7,8 taper angle theta is arranged.
The cup 8 of cup-shaped function-graded material is a cermet material; Cup 8 is designed to right cylinder or cubes, and cup 8 inwall axial sections are designed to difform " U " shape; Realize that by a gradient function sintering metal guide rod sintering metal cup 8 is connected with the gradient of metal conductive bar l; The gradient guide rod is from bottom 7 to top layer 2, and the metallographic phase concentration gradients increases, and the ceramic phase concentration gradients reduces, and top layer 2 possesses good processing properties and welding property; Each gradient layer size optic cup body 8 size of gradient guide rod are adjusted, and that its axial slices is is trapezoidal, rectangle and other arbitrary shape; In addition, slit filled conductive material or binding agent between cup 8 and the gradient guide rod are to strengthen conductivity and the switching performance between cup 8 and the gradient function sintering metal.
Wherein pole shape and cup-shaped gradient function cermet material can cooperate with carbon anode/cathode or inertia wettability negative electrode, are used for existing aluminium cell or stream guidance type aluminum reduction cell; Tabular gradient function cermet material can cooperate with inertia wettability negative electrode, is used for novel vertical aluminium cell.
The advantage of used for aluminium electrolysis gradient function cermet material in production application demonstrates fully:
Adopting the prepared cermet material of the present invention is the matrix material that a kind of structure and performance change in gradient, characteristics are from inside to outside, ceramic phase content increases in gradient, gives full play to the superperformance of cladding material (ceramic phase is main) high temperature resistance fluoride salt electrolyte corrosion; From outside to inside, metallographic phase content increases (the metallographic phase constituent element also can be adjusted accordingly) in gradient, gives full play to its good electrical conductivity, heat-shock resistance, has solved the connectivity problem of cermet inert anode and metal guide rod; This gradient function matrix material possesses good comprehensive performances under electrolytic environments, periodically do not change anode in the production, thereby produces stable; What anode was discharged is oxygen, does not discharge CO 2And fluorocarbon, environment is greatly improved; Change existing aluminum cell structure, reduced pole span, improved production capacity, reduced the aluminium ingot production cost significantly, realized the less energy-consumption of Aluminium Electrolysis process, pollution-free, targets such as low cost.
Description of drawings:
Fig. 1: the gradient-structure synoptic diagram of pole shape gradient function cermet material.The sequence number implication is among the figure: sidepiece gradient layer 1,2,3; Outer 4; Core 5; Bottom gradient layer 6,7,8; Bottom 9.
Fig. 2: the gradient-structure synoptic diagram of tabular gradient function cermet material (is that tetragon is an example with the bottom surface), the sequence number implication is among the figure: sidepiece gradient layer 1,2,3; Outer 4; Core 5; Bottom gradient layer 6,7,8; Bottom 9.
Fig. 3: the axial section gradient-structure synoptic diagram of cup-shaped gradient function cermet material, the sequence number implication is among the figure: metal conductive bar]; Gradient rod top layer 2, gradient layer 3,4,5,6; Gradient rod bottom 7, cup 8.
Fig. 4: the NiFe of cup-shaped gradient function cermet material 2O 4-20wt%Ni and NiFe 2O 4The metallograph of-30wt%Ni gradient interface layer.
Fig. 5: the NiFe of cup-shaped gradient function cermet material 2O 4-30wt%Ni and NiFe 2O 4The metallograph of-40wt%Ni gradient interface layer.
Embodiment:
Be described further below in conjunction with accompanying drawing and example.
Embodiment 1:
Fig. 1 has described a kind of pole shape NiFe 2O 4The gradient-structure of/Cu gradient function cermet material, it is with NiFe 2O 4Be ceramic phase, Cu is Metal Phase; Be designed to 11 gradient layers, sidepiece gradient layer 1,2,3 and bottom gradient layer 6,7,8 disks between taper angle theta be 45 degree; The Metal Phase Cu content of skin 4 and bottom 9 is 5wt%, ceramic phase NiFe 2O 4Content is 95wt%; Core 5 cermets contain 50wt%Cu, 50wt%NiFe 2O 4NiFe by skin 4 and bottom 9 2O 4/ Cu cermet coating is respectively through 9 NiFe 2O 4/ Cu gradient metal ceramic layer carries out the transition to the NiFe of core 5 2O 4/ Cu cermet, the metal Cu content of adjacent gradient layer respectively differs 5wt%.
The sidepiece gradient layer of material adopts the centrifugal process moulding, and bottom gradient disk adopts the lay-up method moulding, and pole shape core 5 cermets adopt compression molding, and each several part adopts isostatic cool pressing method monolithic molding after the moulding respectively; Pole shape functionally gradient material (FGM) green compact after the moulding in 1250 ℃ of sintering 2 hours, obtain a kind of pole shape NiFe under the control sintering atmosphere 2O 4/ Cu gradient function cermet material.The gained material has good electrical conductivity, heat-shock resistance, mechanical behavior under high temperature, anti-fluoride salt and nascent oxygen corrosive performance, and core 5 can well be connected with the anode rod iron after simple and easy processing.
Embodiment 2:
Fig. 2 has described a kind of tabular NiFe 2O 4The gradient-structure of-NiO/Cu-Ni gradient function cermet material, the NiFe that it adopts 35wt%NiO to mix 2O 4Be ceramic phase, the Cu-Ni alloy is Metal Phase; Be designed to 9 gradient layers, sidepiece gradient layer 1,2,3 and the taper angle theta of 6,7,8 of bottom gradient synusia be 45 degree; The ceramic phase NiFe of skin 4 and bottom 9 2O 4-NiO content is 90wt%, and Metal Phase Cu-Ni alloy content is 10wt%, and wherein the content of Ni in alloy is 20wt%; Core 5 is for containing the NiFe of 90wt%Ni 2O 4-NiO/Ni cermet; NiFe by skin 4 and bottom 9 2O 4-NiO/Cu-Ni cermet coating is respectively through 7 NiFe 2O 4-NiO/Cu-Ni gradient metal ceramic layer carries out the transition to the NiFe of core 5 2O 4-NiO/Ni cermet; The Metal Phase Cu-Ni alloy content of adjacent gradient layer respectively differs 10wt%; Ni content in the Metal Phase alloy respectively differs 10wt%.
Sidepiece gradient layer 1,2,3 adopts the powder slurry casting moulding, and bottom gradient synusia 6,7,8 adopts the lay-up method moulding, and core 5 sintering metals adopt compression molding, and each several part adopts isostatic cool pressing method monolithic molding after the moulding respectively.Gradient plate green compact after the moulding in 1350 ℃ of sintering 3 hours, obtain a kind of tabular NiFe under the control sintering atmosphere 2O 4-NiO/Cu-Ni gradient function cermet material.The gained material has good electrical conductivity, heat-shock resistance, mechanical behavior under high temperature, anti-fluoride salt and nascent oxygen corrosive performance, and core can be welded to connect with the anode rod iron.
Embodiment 3:
Fig. 3 has described a kind of cup-shaped NiFe 2O 4The gradient-structure of-NiO/Cu-Ni gradient function cermet material, its cup 8 is NiFe 2O 4-NiO/Cu-Ni cermet material, wherein ceramic phase is the NiFe that 35wt%NiO mixes 2O 4Metal Phase is the Cu-Ni alloy that contains 15wt%Ni, and Metal Phase content is 10wt%; The NiFe that composition changes vertically in gradient 2O 4-NiO/Ni gradient function cermet links to each other contact rod 1 with cup 8; NiFe 2O 4-NiO/Ni gradient function cermet is designed to 9 gradient layers; Bottom 7 ceramic phase NiFe 2O 4The content of-NiO is 90wt%; The content of Metal Phase Ni is 10wt%; The ceramic phase NiFe of top layer 2 2O 4The content of-NiO is 10wt%; The content of Metal Phase Ni is 90wt%; By bottom 7 cermet coatings through 7 NiFe 2O 4-NiO/Ni gradient metal ceramic layer carries out the transition to top layer 2 cermet coatings, and the Metal Phase Ni content of adjacent gradient layer respectively differs 10wt%.
The sintering metal cup adopts the powder slurry casting moulding, and gradient function sintering metal rod adopts the lay-up method moulding, and two portions adopt isostatic cool pressing method monolithic molding after the moulding respectively.Cup-shaped gradient function cermet green compact after the moulding in 1300 ℃ of sintering 3 hours, obtain a kind of cup-shaped NiFe under the control sintering atmosphere 2O 4-NiO/Cu-Ni gradient function cermet material.The gained material has good electrical conductivity, heat-shock resistance, mechanical behavior under high temperature, anti-fluoride salt and nascent oxygen corrosive performance, and the superiors of gradient rod can be welded to connect with the anode rod iron.
Fig. 4 and Fig. 5 show that the core 5 gradient function sintering metal rods of prepared cup-shaped cermet material have the ideal gradient-structure.

Claims (8)

1. ceramet material with gradient function for electrolyzing Al, it is characterized in that: its layer of structure is at least two-layer; Its ceramic phase adopts spinelle type composite oxides (AB 2O 4) pottery, wherein
A is Ni, Mg, Co, Zn, Cu, at least a among Li and the Fe;
B can be Fe, Al, Co, Mn, at least a among Cr and the Ge;
Metallographic phase is Cu, Ni, Co, Cr, Fe, Ag, Pt, binary or multicomponent alloy that single metal such as Au or these metallic elements are formed.
2. used for aluminium electrolysis gradient function cermet material according to claim 1, it is characterized in that: the corner of pole shape function-graded material is designed to right angle or arc, its composition radially and axially changes in gradient, promptly by outer 4 and bottom 9 to core 5, the metallographic phase concentration gradients increases, the ceramic phase concentration gradients reduces, and the core 5 that metallographic phase content is the highest possesses good processing properties and welding property, between sidepiece gradient layer 1,2,3 and the bottom gradient layer 6,7,8 taper angle theta is arranged.
3. used for aluminium electrolysis gradient function cermet material according to claim 1 is characterized in that: tabular function-graded material be shaped as cubes, its radial section is designed to the Polygons of arbitrary shape, its edge is designed to right angle or arc; Its composition radially and axially changes in gradient, by outer 4 and bottom 9 to core 5; The metallographic phase concentration gradients increases, and the ceramic phase concentration gradients reduces, and the core 5 that metallographic phase content is the highest has good processing properties and welding property, between sidepiece gradient layer 1,2,3 and the bottom gradient layer 6,7,8 taper angle theta is arranged.
4. used for aluminium electrolysis gradient function cermet material according to claim 1 is characterized in that: the cup 8 of cup-shaped function-graded material is cermet material; Cup 8 is designed to right cylinder or cubes, and cup 8 inwall axial sections are designed to difform " U " shape; Realize that by a gradient function sintering metal guide rod sintering metal cup 8 is connected with the gradient of metal conductive bar 1; Gradient function sintering metal guide rod is from bottom 7 to top layer 2, and the metallographic phase concentration gradients increases, and the ceramic phase concentration gradients reduces, and top layer 2 possesses good processing properties and welding property; Each gradient layer size optic cup body 8 size of gradient guide rod are adjusted, and that its axial slices is is trapezoidal, rectangle and other arbitrary shape; In addition, slit filled conductive material or binding agent between cup 8 and the gradient guide rod are to strengthen conductivity and the switching performance between cup 8 and the guide rod.
5. used for aluminium electrolysis gradient function cermet material according to claim 1, it is characterized in that: pole shape and cup-shaped gradient function cermet material can cooperate with carbon anode/cathode or inertia wettability negative electrode, are used for existing aluminium cell or stream guidance type aluminum reduction cell; Tabular gradient function cermet material can cooperate with inertia wettability negative electrode, is used for novel vertical aluminium cell.
6. ceramet material with gradient function for electrolyzing Al according to claim 1 is characterized in that: pole shape NiFe 2O 4The gradient-structure of/Cu gradient function cermet material, it is with NiFe 2O 4Be ceramic phase, Cu is Metal Phase; Be designed to 11 gradient layers, sidepiece gradient layer 1,2,3 and bottom gradient layer 6,7,8 disks between taper angle theta be 45 degree; The Metal Phase Cu content of skin 4 and bottom 9 is 5wt%, ceramic phase NiFe 2O 4Content is 95wt%; Core 5 cermets contain 50wt%Cu, 50wt%NiFe 2O 4NiFe by skin 4 and bottom 9 2O 4/ Cu cermet coating is respectively through 9 NiFe 2O 4/ Cu gradient metal ceramic layer carries out the transition to the NiFe of core 5 2O 4/ Cu cermet, the metal Cu content of adjacent gradient layer respectively differs 5wt%.
7. ceramet material with gradient function for electrolyzing Al according to claim 1 is characterized in that: tabular NiFe 2O 4The gradient-structure of-NiO/Cu-Ni gradient function cermet material, the NiFe that it adopts 35wt%NiO to mix 2O 4Be ceramic phase, the Cu-Ni alloy is Metal Phase; Be designed to 9 gradient layers, sidepiece gradient layer 1,2,3 and the taper angle theta of 6,7,8 of bottom gradient synusia be 45 degree; The ceramic phase NiFe of skin 4 and bottom 9 2O 4-NiO content is 90wt%, and Metal Phase Cu-Ni alloy content is 10wt%, and wherein the content of Ni in alloy is 20wt%; Core 5 is for containing the NiFe of 90wt%Ni 2O 4-NiO/Ni cermet; NiFe by skin 4 and bottom 9 2O 4-NiO/Cu-Ni cermet coating is respectively through 7 NiFe 2O 4-NiO/Cu-Ni gradient metal ceramic layer carries out the transition to the NiFe of core 5 2O 4-NiO/Ni cermet; The Metal Phase Cu-Ni alloy content of adjacent gradient layer respectively differs 10wt%; Ni content in the Metal Phase alloy respectively differs 10wt%.
8. ceramet material with gradient function for electrolyzing Al according to claim 1 is characterized in that: a kind of cup-shaped NiFe 2O 4The gradient-structure of-NiO/Cu-Ni gradient function cermet material, its cup 8 is NiFe 2O 4-NiO/Cu-Ni cermet material, wherein ceramic phase is the NiFe that 35wt%NiO mixes 2O 4Metal Phase is the Cu-Ni alloy that contains 15wt%Ni, and Metal Phase content is 10wt%; The NiFe that composition changes vertically in gradient 2O 4-NiO/Ni gradient function cermet links to each other contact rod 1 with cup 8; NiFe 2O 4-NiO/Ni gradient function cermet is designed to 9 gradient layers; Bottom 7 ceramic phase NiFe 2O 4The content of-NiO is 90wt%; The content of Metal Phase Ni is 10wt%; The ceramic phase NiFe of top layer 2 2O 4The content of-NiO is 10wt%; The content of Metal Phase Ni is 90wt%; By bottom 7 cermet coatings through 7 NiFe 2O 4-NiO/Ni gradient metal ceramic layer carries out the transition to top layer 2 cermet coatings, and the Metal Phase Ni content of adjacent gradient layer respectively differs 10wt%.
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Cited By (10)

* Cited by examiner, † Cited by third party
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CN102557668A (en) * 2011-10-31 2012-07-11 深圳光启高等理工研究院 Preparation method of non-uniform ceramic dielectric substrate
CN103668343A (en) * 2013-12-03 2014-03-26 中南大学 Method for improving conductivity of inert anode surface compact layer of metal ceramic
CN104060298A (en) * 2014-06-27 2014-09-24 中国铝业股份有限公司 Ceramic alloy inert anode with equipotential plane and preparation method thereof
CN106488998A (en) * 2014-06-26 2017-03-08 力拓艾尔坎国际有限公司 For preparing electrode material of inert anode and application thereof
CN110252156A (en) * 2019-07-09 2019-09-20 湖南中天元环境工程有限公司 A kind of metal composite ceramal film and preparation method thereof
CN110252157A (en) * 2019-07-09 2019-09-20 湖南中天元环境工程有限公司 A kind of reinforced metal composite ceramic film and preparation method thereof
CN111962100A (en) * 2020-07-06 2020-11-20 中国铝业股份有限公司 Gradient inert anode material and preparation method thereof
CN113136519A (en) * 2021-04-26 2021-07-20 中建材科创新技术研究院(山东)有限公司 Wear-resistant and corrosion-resistant iron-based composite material and preparation method and application thereof
CN113186568A (en) * 2021-04-30 2021-07-30 中南大学 Gradient metal ceramic inert anode material for aluminum electrolysis
CN113430582A (en) * 2021-05-25 2021-09-24 西部金属材料股份有限公司 Metal ceramic inert anode with gradient net-shaped metal phase structure and connecting method of metal ceramic inert anode and metal conducting rod

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102557668A (en) * 2011-10-31 2012-07-11 深圳光启高等理工研究院 Preparation method of non-uniform ceramic dielectric substrate
CN103668343A (en) * 2013-12-03 2014-03-26 中南大学 Method for improving conductivity of inert anode surface compact layer of metal ceramic
CN103668343B (en) * 2013-12-03 2016-08-17 中南大学 A kind of method improving conductivity of inert anode surface compact layer of metal ceramic
CN106488998A (en) * 2014-06-26 2017-03-08 力拓艾尔坎国际有限公司 For preparing electrode material of inert anode and application thereof
CN106488998B (en) * 2014-06-26 2018-12-21 力拓艾尔坎国际有限公司 It is used to prepare the electrode material and application thereof of inert anode
CN104060298A (en) * 2014-06-27 2014-09-24 中国铝业股份有限公司 Ceramic alloy inert anode with equipotential plane and preparation method thereof
CN110252156B (en) * 2019-07-09 2022-04-05 湖南中天元环境工程有限公司 Metal composite ceramic membrane and preparation method thereof
CN110252156A (en) * 2019-07-09 2019-09-20 湖南中天元环境工程有限公司 A kind of metal composite ceramal film and preparation method thereof
CN110252157A (en) * 2019-07-09 2019-09-20 湖南中天元环境工程有限公司 A kind of reinforced metal composite ceramic film and preparation method thereof
CN111962100A (en) * 2020-07-06 2020-11-20 中国铝业股份有限公司 Gradient inert anode material and preparation method thereof
CN113136519B (en) * 2021-04-26 2022-02-18 中建材科创新技术研究院(山东)有限公司 Wear-resistant and corrosion-resistant iron-based composite material and preparation method and application thereof
CN113136519A (en) * 2021-04-26 2021-07-20 中建材科创新技术研究院(山东)有限公司 Wear-resistant and corrosion-resistant iron-based composite material and preparation method and application thereof
CN113186568A (en) * 2021-04-30 2021-07-30 中南大学 Gradient metal ceramic inert anode material for aluminum electrolysis
CN113186568B (en) * 2021-04-30 2022-09-23 中南大学 Gradient metal ceramic inert anode material for aluminum electrolysis
CN113430582A (en) * 2021-05-25 2021-09-24 西部金属材料股份有限公司 Metal ceramic inert anode with gradient net-shaped metal phase structure and connecting method of metal ceramic inert anode and metal conducting rod
CN113430582B (en) * 2021-05-25 2022-06-03 西部金属材料股份有限公司 Metal ceramic inert anode with gradient net-shaped metal phase structure and connecting method of metal ceramic inert anode and metal conducting rod

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