CN101736368B - Noble metal ceramic composite coating inert anode for aluminum electrolysis and preparation method thereof - Google Patents
Noble metal ceramic composite coating inert anode for aluminum electrolysis and preparation method thereof Download PDFInfo
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Abstract
The invention provides a noble metal ceramic composite coating inert anode for aluminum electrolysis and a preparation method thereof, and relates to the field of molten salt electrolysis of nonferrous metals and the technology for preparing metal ceramic composite materials. The inert anode consists of an alloy substrate, an oxide film on the surface of the alloy and a noble metal-alumina composite layer on the outer layer, wherein the noble metal-alumina composite layer has a structure of noble metal coated alumina particles. The noble metal ceramic composite coating inert anode has perfect inert anode characteristics of noble metal, can eliminate CO2 pollution and protect environment because the electrode surface only undergoes reaction of separating out oxygen in the aluminum electrolysis process, has the characteristics of metal ceramic composite materials, such as abrasion resistance, brushing resistance, thermal shock resistance, counterdiffusion prevention between the noble metals and the alloy substrate, and has the characteristics of having long service life, saving energy, simplifying industrial operation and the like. The novel noble metal ceramic composite coating inert anode can save a large amount of noble metals relatively to noble metal coating inert electrodes, thus has industrial practicality.
Description
Technical field
The present invention relates to non-ferrous metal fused salt electrolysis field and ceramic-metal composite technology of preparing, particularly low-temperature aluminum electrolysis inert anode and technology of preparing thereof.
Background technology
The anode of existing Hall-H é roult electrolysis of aluminum adopts carbon materials.The reaction of carbon annode is: Al
2O
3+ 3/2C → 2Al+3/2CO
2, cause carbon annode to be fallen by mass consumption, the carbon anode that ton aluminium consumes surpasses 400kg, makes aluminium electrolytic industry become high carbon-based industry.Economically, need the huge carbon annode factory of investment construction, improved production cost.On technology, because the continuous consumption of carbon anode can cause the pole span instability, need complicated mechanical devices to adjust pole span, make aluminum electrolysis process complicated; Also cause forming the carbon slag in the electrolyzer, the consumption that increases villiaumite influences the steady running of electrolyzer.In environment protection, produce a large amount of CO in the electrolytic reaction process
2With a spot of CO, and carcinogenic CF
nMaterial, major polluting atmosphere environment needs to be equipped with and builds huge system for cleaning fume, causes the production cost of electrolysis of aluminum to improve.
For above-mentioned reasons, since aluminium electrolytic industry was born, people were developing inert anode always, to replace general carbon anode (being active anode) now, thought that this is a revolution of aluminium electrolytic industry.The inert anode that aluminium electrolytic industry adopts is meant the anode that those do not consume or trace consumes at present general sodium aluminum fluoride-alumina molten salt electrolysis, the inert anode reaction of electrolysis of aluminum is: Al
2O
3→ 2Al+3/2O
2The important meaning of development inert anode is: electrode does not consume in the electrolytic process, need not additional carbon element source mill, has reduced production cost; Electrode does not consume, and pole span is stable, is easy to control, and the anode change number of times is few, and labour intensity reduces; Can adopt higher anodic current density, the electrolyzer production capacity is increased; The anode product is an oxygen, has avoided environmental pollution, and oxygen can also estimate that the oxygen that reclaims may be 3% of primary aluminum value of the product as byproduct.The aluminium ingot production cost can reduce about 30%.
Since the eighties in 20th century, the research of inert anode mainly concentrates on (volume such as Liu Yexiang, modern aluminum electrolysis, metallurgical industry press, 2008) on metal oxide anode, alloy anode and the sintering metal anode.Yet, up to the present still do not have a tame enterprise to adopt inert anode to carry out the industrialization Aluminium Electrolysis in the world.This is because metal oxide anode, alloy anode and sintering metal anode all are that to have certain anti-sodium aluminum fluoride-alumina molten salt corrosive nature be prerequisite for the oxide compound that relies on oxide compound or electrode surface to form.But except gold and precious metal such as platinum, all oxide compounds all have certain solubleness at sodium aluminum fluoride-alumina molten salt, cause the corrosion of electrode can not satisfy the requirement of industrial aluminum amount of electrolyte.Said as Donald R.Sadoway, the inert anode research of electrolysis of aluminum remains human challenge to extreme material.He thinks that maximum chance of success is to drop to minimum to existing experience.(Donald?R.Sadoway，Inert?Anodes?for?the?Hall-Héroult?Cell：The?UltimateMaterials?Challenge，JOM，May?2001，34-35)。
Precious metals such as gold and platinum are the ideal inert anode materials.Because precious metal costs an arm and a leg, can not be directly as inert anode in industry.But it is to utilize the precious metal characteristic to make an approach likely of inert anode that precious metal is prepared as coating.(patent publication No.: CN 1612776A), employing SCX sputtering technology is at alloy silk surface-coated precious metal such as platinum, as the noble electrode of electrolysis of aluminum " to be used for the noble-metal coated inert anodes that aluminium is produced " in patent of invention.This electrode can keep structural integrity keep 17h in 900 ℃ molten fluoride after.But the noble electrode of this noble metal-coating does not obtain industrial application, shows that still there are some shortcomings in this technology.For example, noble-metal coated is on alloy substrate, mutual diffusion will take place in the precious metal of alloy substrate and surface-coated under the high-temperature work environment of electrolysis of aluminum, formation contains the alloy layer of precious metal, selective oxidation can take place in more active metallic element in this alloy layer, be dissolved in the fused salt, come out to enter in the aluminium product in cathodic reduction; The layer of precious metal of Tu Fuing only is 1～10 μ m than minimal thickness in addition, is easy to be worn, produce scuffing, causes the high speed corrosion of alloy substrate.General view is at present, and precious metal materials such as gold and platinum can still not be suitable for industrial aluminum production (Qiu Zhuxian, prebaked cell aluminium metallurgy, metallurgical industry press, 2005) the laboratory planted agent as inert anode.Therefore, precious metal is prepared as coating, utilizes the inert anode that the manufacturing of precious metal characteristic can industrial application also to need new research thinking and technological approaches.
Summary of the invention
The object of the invention is to propose a kind of novel noble metal ceramic composite coating inert anode of electrolysis of aluminum and preparation method thereof that is used for.This inert anode has the desirable inert anode characteristic of precious metal, excellent mechanical property, and permanent work-ing life and lower comprehensive cost are with a wide range of applications in aluminium electrolytic industry.
The present invention is achieved by the following technical solutions:
A kind of noble metal ceramic composite coating inert anode that is used for electrolysis of aluminum is made of the sull and the outer field precious metal-aluminum oxide composite bed of alloy substrate, alloy surface.
The alloy substrate of described inert anode is 10～25% for Cr content, and the ferrous alloy of ree content 0～0.5% or nickel-base alloy adopt casting or mechanical workout moulding;
The content of precious metal is 5%～30% in described precious metal-aluminum oxide composite bed, described precious metal is Au, or Au-Pt alloy, or Au-Pd alloy or Au-Rh alloy, the content of Pt or Pd is 0%～40% in the alloy, the content of Rh is 0%～10%, and the thickness of described precious metal-aluminum oxide composite bed is 10～100 μ m.
Described precious metal-aluminum oxide composite bed has precious metal coated aluminum oxide particulate structure, the grain size of the alumina particle that is adopted is 10nm～100 μ m, and the mass ratio of micron order aluminum oxide and alumina in Nano level is 9: 1～5: 5 in precious metal-aluminum oxide composite bed; The content of precious metal is 5%～30% (mass percent) in precious metal-aluminum oxide composite bed; The thickness of precious metal-aluminum oxide composite bed is 10～100 μ m.
The preparation method who is used for the noble metal ceramic composite coating inert anode of electrolysis of aluminum, the preparation of the outer field precious metal of described inert anode-aluminum oxide composite bed may further comprise the steps:
1) alumina particle and noble metal powder are mixed back ball milling 1～10h in high energy ball mill, obtain precious metal coated aluminum oxide particulate powder;
2) by in air preoxidation at alloy substrate surface preparation sull;
3) at surperficial electrophoresis one deck paint film of the above-mentioned sull that makes; Precious metal coated aluminum oxide particulate powder is applied on the paint film, and exerting pressure makes paint film stick to the sull surface to precious metal coated aluminum oxide granular powder equably, forms lacquer-precious metal-oxide compound compound coating;
4) adopt the hot-pressing processing device, the alloy substrate that the surface has been coated lacquer-precious metal-oxide compound compound coating is imbedded in the mould of the hot-pressing processing device that aluminum oxide micro-sphere is housed, apply the pressure of 20～100MPa by the pressure head of described hot-pressing processing device, the temperature of the stove of described hot-pressing processing device is controlled at 900～1200 ℃, handle 1h～10h, paint film is burnt, precious metal coated aluminum oxide granular powder is sintered into fine and close precious metal-aluminum oxide composite bed, and keeps precious metal coated aluminum oxide particulate structure;
5) alloy substrate that will form fine and close precious metal-aluminum oxide composite bed soaks 10min～60min in 1～10% the NaOH aqueous solution, and aluminum oxide and other impurity of surface attachment are removed in washing.
The sull on the alloy substrate surface of described inert anode is to adopt physico-chemical processes such as surface microporeization, shot-peening, sandblast to carry out surface coarsening the ferrous alloy that contains rare earth of machine-shaping or nickel-base alloy; After the cleaning, preoxidation 1～10h obtains the electroconductive oxide film in 800～1000 ℃ air.
The sull on the matrix alloy surface of described inert anode is to adopt physico-chemical processes such as surface microporeization, shot-peening, sandblast to carry out surface coarsening the ferrous alloy that does not contain rare earth of machine-shaping or nickel-base alloy; After the cleaning, the surface apply rare earth oxide film that thickness is 10～200nm or zirconia film then in 800～1000 ℃ air preoxidation 1～10h obtain the electroconductive oxide film.Add rare earth in the alloy or apply rare earth oxide film that thickness is 10～200nm on the surface or zirconia film can change the growth mechanism of the oxide film that alloy surface preoxidation generates, new oxide compound forms at the interface of alloy and oxide film, can improve the bonding force of oxide film and matrix alloy.
The structure of the precious metal-aluminum oxide composite bed that is obtained by this method makes electrode have excellent conducting performance, its precious metal is coating nano-alumina powder, the mixture of precious metal clad nano grade aluminum oxide powder is coating the micron order alumina particle again, the coating of this precious metal coated aluminum oxide grain pattern in a single day precious metal on surface is damaged, the alumina particle that exposes will be dissolved in the fused salt, then expose following precious metal, therefore can make the surface of noble metal ceramic composite coating inert anode remain precious metal, make electrode have the desirable inert anode characteristic of precious metal, the reaction of precipitated oxygen only takes place in electrode surface in aluminium electrolysis process.
Beneficial effect of the present invention is:
1. precious metal of the present invention-aluminum oxide composite bed, its precious metal coated aluminum oxide particulate structure makes electrode have excellent conducting performance.
2. precious metal coated aluminum oxide particulate structure of the present invention makes coating have the mechanical property that is different from precious metal fully, shows the characteristic of ceramic-metal composite, as wear-resistingly, anti-wash away, anti-thermal shock etc.
3. precious metal coated aluminum oxide particulate structure of the present invention can reduce the content of precious metal in the coating in a large number, can significantly lower the manufacturing cost of novel noble electrode.
4. the sull of alloy surface of the present invention can prevent precious metal and matrix alloy generation mutual diffusion, makes coating structure keep stable.
Description of drawings
Fig. 1 is the structural representation that is used for the noble metal ceramic composite coating inert anode of electrolysis of aluminum;
Fig. 2 is a hot-pressing processing apparatus structure synoptic diagram;
Wherein
| 1. |
5. |
| 2. sull | 6. |
| 3. lacquer-precious metal-oxide compound |
7. |
| 4. aluminum oxide micro-sphere |
Embodiment
Fig. 1 is the structural representation that is used for the noble metal ceramic composite coating inert anode of electrolysis of aluminum, inert anode is made of the sull and the outer field precious metal-aluminum oxide composite bed of alloy substrate, alloy surface, precious metal-aluminum oxide composite bed has precious metal coated aluminum oxide particulate structure, and wherein alumina particle is divided into micron order and nano level.
Fig. 2 is a hot-pressing processing apparatus structure synoptic diagram, as shown in the figure: adopt the hot-pressing processing device, the alloy substrate 1 that the surface has been coated lacquer-precious metal-oxide compound compound coating 3 is imbedded in the mould 5 that aluminum oxide micro-sphere 4 is housed, apply the pressure of 20～100MPa by pressure head 6, the temperature of stove 7 is controlled at 900～1200 ℃, handle 1～10h, paint film is burnt, precious metal coated aluminum oxide granular powder is sintered into fine and close precious metal-aluminum oxide composite bed, and keeps precious metal coated aluminum oxide particulate structure.
Embodiment 1:
With Au powder, median size is that aluminum oxide powder, the median size of 5 μ m is the aluminum oxide powder of 80nm, and their mass ratio is 20: 60: 20, and high-energy ball milling 6h obtains the composite granule of Au coated aluminum oxide.The Fe-20%Cr-0.5%Ce alloy is processed into diameter 10mm, length 500mm sample; The surface is through sandblasting; Preoxidation 5h obtains the Cr of the doped Ce of electroconductibility in 900 ℃ air then
2O
3Film; Adopt ability cathode electrophoresis deposition one deck urethane paint film then; Au coated aluminum oxide particulate powder is applied on the paint film, and exerting pressure makes paint film stick to sample surfaces to Au coated aluminum oxide granular powder equably.Adopt hot-pressing processing device as shown in Figure 2, the alloy substrate 1 that the surface has been coated lacquer-Au-oxide compound compound coating 3 is imbedded in the mould 5 that aluminum oxide micro-sphere 4 is housed, apply the pressure of 80MPa by pressure head 6, the temperature of stove 7 is controlled at 900 ℃, handle 3h, paint film is burnt, and Au coated aluminum oxide granular powder is sintered into fine and close Au-aluminum oxide composite bed, and keeps Au coated aluminum oxide particulate structure.Soak 10～60min in 5% the NaOH aqueous solution, aluminum oxide and other impurity that sample surfaces adheres to are removed in washing.The thickness of the Au coated aluminum oxide composite bed that obtains is 20 μ m.
As anode, plumbago crucible is a negative electrode with this electrode, and electrolyte ingredient is AlF
3, K
3AlF
6And Na
3AlF
6And electrolysis raw material A l
2O
3The concrete composition quality per-cent of ionogen is as follows under the different electrolysis temperatures: 700 ℃ is 30%AlF
3, 35%K
3AlF
6, 35%Na
3AlF; 800 ℃ is 26%AlF
3, 29.6%K
3AlF
6, 44.4%Na
3AlF
6900 ℃ are 24%AlF down
3, 7.6%K
3AlF
6, 68.4%Na
3AlF
6All add the aluminum oxide powder that accounts for ionogen total mass 8% in each ionogen.Anodic current density is 0.8mA/cm
2, temperature is controlled at 700 ℃, 800 ℃ and 900 ℃ respectively, electrolysis 6h.Test the Au content in fused salt and the product aluminium after electrolysis finishes respectively, measuring accuracy is 10
-6G/g does not all detect Au.
Embodiment 2:
With Au powder, Pt powder, median size is that aluminum oxide powder, the median size of 5 μ m is the aluminum oxide powder of 80nm, and their mass ratio is 16: 4: 60: 20, and high-energy ball milling 6h obtains the composite granule of Au-20%Pt coated aluminum oxide.The Fe-20%Cr-0.5%Ce alloy is processed into diameter 10mm, length 500mm sample; The surface is through sandblasting; Preoxidation 5h obtains the Cr of the doped Ce of electroconductibility in 900 ℃ air then
2O
3Film; Adopt ability cathode electrophoresis deposition one deck urethane paint film then; Au-20%Pt coated aluminum oxide particulate powder is applied on the paint film, and exerting pressure makes paint film stick to sample surfaces to Au-20%Pt coated aluminum oxide granular powder equably.Adopt hot-pressing processing device as shown in Figure 2, the alloy substrate 1 that the surface has been coated lacquer-Au-20%Pt-oxide compound compound coating 3 is imbedded in the mould 5 that aluminum oxide micro-sphere 4 is housed, apply the pressure of 80MPa by pressure head 6, the temperature of stove 7 is controlled at 1100 ℃, handle 3h, paint film is burnt, and Au-20%Pt coated aluminum oxide granular powder is sintered into fine and close Au-20%Pt-aluminum oxide composite bed, and keeps Au-20%Pt coated aluminum oxide particulate structure.Soak 10～60min in 5% the NaOH aqueous solution, aluminum oxide and other impurity that sample surfaces adheres to are removed in washing.The Au-20%Pt that obtains coats Al
2O
3The thickness of composite bed is 20 μ m.
As anode, plumbago crucible is a negative electrode with this electrode, and electrolyte ingredient is AlF
3, K
3AlF
6And Na
3AlF
6And electrolysis raw material A l
2O
3The concrete composition quality per-cent of ionogen is as follows under the different electrolysis temperatures: 700 ℃ is 30%AlF
3, 35%K
3AlF
6, 35%Na
3AlF
6, 800 ℃ be 26%AlF
3, 29.6%K
3AlF
6, 44.4%Na
3AlF
6900 ℃ are 24%AlF down
3, 7.6%K
3AlF
6, 68.4%Na
3AlF
6All add the aluminum oxide powder that accounts for total mass 8% in each ionogen.Anodic current density is 0.8mA/cm
2, temperature is controlled at 700 ℃, 800 ℃ and 900 ℃ respectively, electrolysis 6h.Test Au and Pt content in fused salt and the product aluminium after electrolysis finishes respectively, measuring accuracy is 10
-6G/g does not all detect Au and Pt.
Embodiment 3:
With Au powder, Pd powder, median size is that aluminum oxide powder, the median size of 5 μ m is the aluminum oxide powder of 80nm, and their mass ratio is 16: 4: 60: 20, and high-energy ball milling 6h obtains the composite granule of Au-20%Pd coated aluminum oxide.The Ni-20%Cr-0.5%Ce alloy is processed into diameter 10mm, length 500mm sample; The surface is through sandblasting; Preoxidation 5h obtains the Cr of the doped Ce of electroconductibility in 900 ℃ air then
2O
3Film; Adopt ability cathode electrophoresis deposition one deck urethane paint film then; Golden coated aluminum oxide particulate powder is applied on the paint film, and exerting pressure makes paint film stick to sample surfaces to Au-20%Pd coated aluminum oxide granular powder equably.Adopt hot-pressing processing device as shown in Figure 2, the alloy substrate 1 that the surface has been coated lacquer-Au-20%Pd-oxide compound compound coating 3 is imbedded in the mould 5 that aluminum oxide micro-sphere 4 is housed, apply the pressure of 80MPa by pressure head 6, the temperature of stove 7 is controlled at 900 ℃, handle 3h, paint film is burnt, and Au-20%Pd coated aluminum oxide granular powder is sintered into fine and close Au-20%Pd-aluminum oxide composite bed, and keeps Au-20%Pd coated aluminum oxide particulate structure.Soak 10～60min in 5% the NaOH aqueous solution, aluminum oxide and other impurity that sample surfaces adheres to are removed in washing.The Au-20%Pd that obtains coats Al
2O
3The thickness of composite bed is 20 μ m.
As anode, plumbago crucible is a negative electrode with this electrode, and electrolyte ingredient is AlF
3, K
3AlF
6And Na
3AlF
6And electrolysis raw material A l
2O
3The concrete composition quality per-cent of ionogen is as follows under the different electrolysis temperatures: 700 ℃ is 30%AlF
3, ω (K
3AlF
6)=35%, 35%Na
3AlF
6800 ℃ is 26%AlF
3, 29.6%K
3AlF
6, 44.4%Na
3AlF
6900 ℃ are 24%AlF down
3, 7.6%K
3AlF
6, 68.4%Na
3AlF
6All add the aluminum oxide powder that accounts for ionogen total amount 8% in each ionogen.Anodic current density is 0.8mA/cm
2, temperature is controlled at 700 ℃, 800 ℃ and 900 ℃ respectively, electrolysis 6h.Test Au and Pd content in fused salt and the product aluminium after electrolysis finishes respectively, measuring accuracy is 10
-6G/g does not all detect Au and Pd.
Embodiment 4:
With Au powder, Rh powder, median size is that aluminum oxide powder, the median size of 5 μ m is the aluminum oxide powder of 80nm, and their mass ratio is 19: 1: 60: 20, and high-energy ball milling 6h obtains the composite granule of Au-5%Rh coated aluminum oxide.The Ni-20%Cr-0.5%Ce alloy is processed into diameter 1 0mm, length 500mm sample; The surface is through sandblasting; Preoxidation 5h obtains the Cr of the doped Ce of electroconductibility in 900 ℃ air then
2O
3Film; Adopt ability cathode electrophoresis deposition one deck urethane paint film then; Au-5%Rh coated aluminum oxide particulate powder is applied on the paint film, and exerting pressure makes paint film stick to sample surfaces to Au-5%Rh coated aluminum oxide granular powder equably.Adopt hot-pressing processing device as shown in Figure 2, the alloy substrate 1 that the surface has been coated lacquer-Au-5%Rh-oxide compound compound coating 3 is imbedded in the mould 5 that aluminum oxide micro-sphere 4 is housed, apply the pressure of 80MPa by pressure head 6, the temperature of stove 7 is controlled at 1100 ℃, handle 3h, paint film is burnt, and golden coated aluminum oxide granular powder is sintered into fine and close Au-5%Rh-aluminum oxide composite bed, and keeps Au-20%Rh coated aluminum oxide particulate structure.Soak 10～60min in 5% the NaOH aqueous solution, aluminum oxide and other impurity that sample surfaces adheres to are removed in washing.The Au-5%Rh that obtains coats Al
2O
3The thickness of composite bed is 30 μ m.
As anode, plumbago crucible is a negative electrode with this electrode, and electrolyte ingredient is AlF
3, K
3AlF
6And Na
3AlF
6And electrolysis raw material A l
2O
3The concrete composition quality per-cent of ionogen is as follows under the different electrolysis temperatures: 700 ℃ is 30%AlF
3, 35%K
3AlF
6, 35%Na
3AlF
6800 ℃ is 26%AlF
3, 29.6%K
3AlF
6, 44.4%Na
3AlF
6900 ℃ are 24%AlF down
3, 7.6%K
3AlF
6, 68.4%Na
3AlF
6All add the aluminum oxide powder that accounts for ionogen total mass 8% in each ionogen.Anodic current density is 0.8mA/cm
2, temperature is controlled at 700 ℃, 800 ℃ and 900 ℃ respectively, electrolysis 6h.Test Au and Rh content in fused salt and the product aluminium after electrolysis finishes respectively, measuring accuracy is 10
-6G/g does not all detect Au and Rh.
Embodiment 5:
With Au powder, Pt powder, median size is that aluminum oxide powder, the median size of 5 μ m is the aluminum oxide powder of 80nm, and their mass ratio is 8: 2: 70: 20, and high-energy ball milling 6h obtains the composite granule of Au-20%Pt coated aluminum oxide.The 1Cr18Ni9Ti alloy is processed into diameter 10mm, length 500mm sample; The surface is through sandblasting; In 0.2M cerous nitrate ethanolic soln, be negative electrode with the alloy sample, graphite rod is an anode, and interpole gap is 10mm, applies voltage 20V, and electrolysis 30 seconds is handled 30min at 300 ℃ afterwards and is obtained CeO
2Film, the Cr of the doped Ce of preoxidation 5h acquisition electroconductibility in 900 ℃ air then
2O
3Film; Adopt ability cathode electrophoresis deposition one deck urethane paint film; Golden coated aluminum oxide particulate powder is applied on the paint film, and exerting pressure makes paint film stick to sample surfaces to Au-20%Pt coated aluminum oxide granular powder equably.Adopt hot-pressing processing device as shown in Figure 2, the alloy substrate 1 that the surface has been coated lacquer-Au-20%Pt-oxide compound compound coating 3 is imbedded in the mould 5 that aluminum oxide micro-sphere 4 is housed, apply the pressure of 80MPa by pressure head 6, the temperature of stove 7 is controlled at 1000 ℃, handle 3h, paint film is burnt, and golden coated aluminum oxide granular powder is sintered into fine and close Au-20%Pt-aluminum oxide composite bed, and keeps Au-20%Pt coated aluminum oxide particulate structure.Soak 10～60min in 5% the NaOH aqueous solution, aluminum oxide and other impurity that sample surfaces adheres to are removed in washing.The Au-20%Pt that obtains coats Al
2O
3The thickness of composite bed is 30 μ m.
As anode, plumbago crucible is a negative electrode with this electrode, and electrolyte ingredient is AlF
3, K
3AlF
6And Na
3AlF
6And electrolysis raw material A l
2O
3The concrete composition quality per-cent of ionogen is as follows under the different electrolysis temperatures: 700 ℃ is 30%AlF
3, 35%K
3AlF
6, 35%Na
3AlF
6800 ℃ is 26%AlF
3, 29.6%K
3AlF
6, 44.4%Na
3AlF
6900 ℃ are 24%AlF down
3, 7.6%K
3AlF
6, 68.4%Na
3AlF
6All add the aluminum oxide powder that accounts for ionogen total mass 8% in each ionogen.Anodic current density is 0.8mA/cm
2, temperature is controlled at 700 ℃, 800 ℃ and 900 ℃ respectively, electrolysis 6h.Test Au and Pt content in fused salt and the product aluminium after electrolysis finishes respectively, measuring accuracy is 10
-6G/g does not all detect Au and Pt.
Embodiment 6:
With Au powder, median size is that aluminum oxide powder, the median size of 5 μ m is the aluminum oxide powder of 80nm, and their mass ratio was respectively 10: 65: 25 and 50: 35: 15, and high-energy ball milling 6h obtains the composite granule of the golden coated aluminum oxide of different noble metal cermet ratios.The Fe-20%Cr-0.5%Ce alloy is processed into diameter 10mm, length 500mm sample; The surface is through sandblasting; Preoxidation 5h obtains the Cr of the doped Ce of electroconductibility in 900 ℃ air then
2O
3Film; Adopt ability cathode electrophoresis deposition one deck urethane paint film then; Divide three layers to be applied on the paint film Au coated aluminum oxide particulate powder of different precious metals, aluminum oxide quality ratio, the content height of Au in the Au coated aluminum oxide granular powder that bottom adopted, massfraction is 50%; The content of Au is low in the Au coated aluminum oxide granular powder that adopt in the middle layer, and massfraction is 10%; And outermost layer adopts pure Au granular powder.Exert pressure and make paint film stick to sample surfaces to Au coated aluminum oxide granular powder equably.Adopt hot-pressing processing device as shown in Figure 2, the alloy substrate 1 that the surface has been coated lacquer-Au-oxide compound gradient composite coating 3 is imbedded in the mould 5 that aluminum oxide micro-sphere 4 is housed, apply the pressure of 80MPa by pressure head 6, the temperature of stove 7 is controlled at 900 ℃, handle 3h, paint film is burnt, and Au coated aluminum oxide granular powder is sintered into fine and close Au-aluminum oxide gradient composite bed, and keeps Au coated aluminum oxide particulate structure.Soak 10～60min in 5% the NaOH aqueous solution, aluminum oxide and other impurity that sample surfaces adheres to are removed in washing.The thickness of the Au coated aluminum oxide gradient composite bed that obtains is 40 μ m.
As anode, plumbago crucible is a negative electrode with this electrode, and electrolyte ingredient is AlF
3, K
3AlF
6And Na
3AlF
6And electrolysis raw material A l
2O
3The concrete composition quality per-cent of ionogen is as follows under the different electrolysis temperatures: 700 ℃ is 30%AlF
3, 35%K
3AlF
6, 35%Na
3AlF
6800 ℃ is 26%AlF
3, 29.6%K
3AlF
6, 44.4%Na
3AlF
6900 ℃ are 24%AlF down
3, 7.6%K
3AlF
6, 68.4%Na
3AlF
6All add the aluminum oxide powder that accounts for ionogen total mass 8% in each ionogen.Anodic current density is 0.8mA/cm
2, temperature is controlled at 700 ℃, 800 ℃ and 900 ℃ respectively, electrolysis 6h.Test the Au content in fused salt and the product aluminium after electrolysis finishes respectively, measuring accuracy is 10
-6G/g does not all detect Au.
Claims (5)
1. be used for the noble metal ceramic composite coating inert anode of electrolysis of aluminum, it is characterized in that: described inert anode is made of the sull and the outer field precious metal-aluminum oxide composite bed on alloy substrate, alloy substrate surface;
The alloy substrate of described inert anode is 10～25% for Cr content, and the ferrous alloy of ree content 0～0.5% or nickel-base alloy adopt casting or mechanical workout moulding;
Described precious metal-aluminum oxide composite bed has precious metal coated aluminum oxide particulate structure, wherein, precious metal in the outer field precious metal of inert anode-aluminum oxide composite bed is Au, Au-Pt alloy, Au-Pd alloy or Au-Rh alloy, the mass percentage content of Pt, Pd is respectively 0～40% in the alloy, and the mass percentage content of Rh is 0～10%;
The grain size of described alumina particle is 10nm～100 μ m, and the mass ratio of micron order aluminum oxide and alumina in Nano level is 9: 1～5: 5 in described precious metal-aluminum oxide composite bed, and the content of precious metal is 5%～30% in precious metal-aluminum oxide composite bed;
The thickness of described precious metal-aluminum oxide composite bed is 10～100 μ m.
2. be used for the preparation method of the noble metal ceramic composite coating inert anode of electrolysis of aluminum, it is characterized in that: the preparation of the outer field precious metal of described inert anode-aluminum oxide composite bed may further comprise the steps:
1) alumina particle and noble metal powder are mixed back ball milling 1～10h in high energy ball mill, obtain precious metal coated aluminum oxide particulate powder;
2) by in air preoxidation at alloy substrate surface preparation sull;
3) at surperficial electrophoresis one deck paint film of the above-mentioned sull that makes; Precious metal coated aluminum oxide particulate powder is applied on the paint film, and exerting pressure makes paint film stick to the sull surface to precious metal coated aluminum oxide granular powder equably, forms lacquer-precious metal-oxide compound compound coating;
4) adopt the hot-pressing processing device, the alloy substrate that the surface has been coated lacquer-precious metal-oxide compound compound coating is imbedded in the mould of the hot-pressing processing device that aluminum oxide micro-sphere is housed, apply the pressure of 20～100MPa by the pressure head of described hot-pressing processing device, the temperature of the stove of described hot-pressing processing device is controlled at 900～1200 ℃, handle 1h～10h, paint film is burnt, precious metal coated aluminum oxide granular powder is sintered into fine and close precious metal-aluminum oxide composite bed, and keeps precious metal coated aluminum oxide particulate structure;
5) alloy substrate that will form fine and close precious metal-aluminum oxide composite bed soaks 10min～60min in 1～10% the NaOH aqueous solution, and aluminum oxide and other impurity of surface attachment are removed in washing.
3. inert anode preparation method according to claim 2 is characterized in that: described step 2), the sull on preparation alloy substrate surface is to adopt preoxidation 1～10h acquisition in 800～1000 ℃ air.
4. the preparation method of inert anode according to claim 2, it is characterized in that: described step 2), the sull on preparation alloy substrate surface be after the alloy substrate surface applies rare earth oxide film that thickness is 10～200nm or zirconia film in 800～1000 ℃ air preoxidation 1～10h obtain.
5. according to the preparation method of any one described inert anode in the claim 2 to 4, it is characterized in that:
With precious metal powder and alumina powder ball milling 1～10h in high energy ball mill of multiple mass ratio, obtain the precious metal coated aluminum oxide particulate powder of multiple mass ratio in the described step 1);
Described step 2) the precious metal coated aluminum oxide particulate powder branch multilayer with described multiple mass ratio in is applied on the paint film, forms precious metal-oxide compound gradient composite coating; Make the noble metal ceramic composite coating inert anode of gradient-structure.
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| CN101942677A (en) * | 2010-09-30 | 2011-01-12 | 中南大学 | Heat-insulating coating material for aluminum electrolytic inert anode and use thereof |
| CN101935853A (en) * | 2010-10-11 | 2011-01-05 | 济南澳海炭素有限公司 | Alloy oxygen evolving anode for aluminum electrolysis |
| 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 |
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| CN106756719A (en) * | 2016-12-01 | 2017-05-31 | 郴州市泰益表面涂层技术有限公司 | A kind of coupling coating with high-intensity high-tenacity and preparation method thereof |
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