CN102010193A - Corrosion resistant protection material for fusedsaltelectrolysis and preparation method thereof - Google Patents
Corrosion resistant protection material for fusedsaltelectrolysis and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 60
- 238000005260 corrosion Methods 0.000 title claims abstract description 44
- 230000007797 corrosion Effects 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000005245 sintering Methods 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 239000002270 dispersing agent Substances 0.000 claims abstract description 13
- 239000011230 binding agent Substances 0.000 claims abstract description 12
- 238000005238 degreasing Methods 0.000 claims abstract description 12
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 9
- 239000011029 spinel Substances 0.000 claims abstract description 9
- 238000000465 moulding Methods 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims description 22
- 238000005868 electrolysis reaction Methods 0.000 claims description 19
- 239000000919 ceramic Substances 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 8
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- 239000006185 dispersion Substances 0.000 claims description 5
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- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- 239000004375 Dextrin Substances 0.000 claims description 3
- 229920001353 Dextrin Polymers 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 3
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- 229910052759 nickel Inorganic materials 0.000 claims description 3
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- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 238000000748 compression moulding Methods 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
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- 238000009740 moulding (composite fabrication) Methods 0.000 claims description 2
- -1 polyoxyethylene Polymers 0.000 claims description 2
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- 239000011224 oxide ceramic Substances 0.000 abstract description 22
- 229910052574 oxide ceramic Inorganic materials 0.000 abstract description 22
- 238000003756 stirring Methods 0.000 abstract description 13
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- 229910016287 MxOy Inorganic materials 0.000 abstract 2
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- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 22
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- 229910000943 NiAl Inorganic materials 0.000 description 10
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- 230000003213 activating effect Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a corrosion resistant protection material for fusedsaltelectrolysis and a preparation method thereof. The invention is characterized in that the corrosion resistant protection material for the fusedsaltelectrolysis comprises the following components by mass percent: 75-100% of AB2O4 and 0-25% of MxOy; and the preparation method comprises the following steps: (1) synthesizing an AB2O4 spinel type oxide ceramic phase; and (2) proportionally mixing and stirring the AB2O4, MxOy, a binder and a dispersing agent, drying, molding, degreasing, and sintering to obtain the corrosion resistant protection material for the fusedsaltelectrolysis. In the material preparation process, by adjusting the factors such as material formula composition, molding technology, sintering schedule and the like, the protection material for an electrode guide bar or a temperature thermocouple with high compactness, corrosion resistance and good thermal shock resistance can be acquired.
Description
Technical field
A kind of fused salt electrolysis is with anti-corrosion protecting materials and preparation method thereof; relate to a kind of fused salt electrolysis that is used for non-ferrous metal (Al, rare earth and refractory metal etc.) with electrode guide rod or temperature thermocouple protecting materials, particularly use a kind of spinel oxides pottery protecting materials and preparation method thereof in the aluminium electrolysis process.
Background technology
Adopt the existing molten-salt electrolysis technology of carbon annode to have energy consumption height, big, the problems such as environmental pollution is serious, cost is high, production instability of carbon consumption.Can realize the less energy-consumption of electrolysis production process based on the electrolysis novel process of noble electrode, pollution-free, targets such as low cost.
The noble electrode novel process has adopted brand-new ionogen, anode, negative electrode and cell construction; wherein novel electrolytes system corrodibility and perviousness are stronger; need high temperature resistant molten salt corrosive nature better protection material that the noble electrode guide rod that immerses fully in the fused salt is effectively protected, otherwise electrolytic attack and chemical corrosion will take place and lose efficacy in guide rod in electrolytic process.Simultaneously, the measurement of temperature is one of fused salt electrolysis important parameter, and thermopair also needs the protecting materials of excellent performance.For the protecting materials that uses in the high-temperature molten salt, must possess following performance: good chemical stability is an inert to fused electrolyte or electrode at high temperature, can not react with ionogen or electrode; Have stable high-temperature performance, have enough normal temperature and high-temperature mechanics strength property, thermal shock resistance is good; Starting material are easy to get, and cost is low, and preparation technology is simple.
Summary of the invention
Purpose of the present invention for provide a kind of can resist high-temperature molten salt corrosion and have good thermal shock resistance can, the fused salt electrolysis that effectively realizes noble electrode guide rod and thermopair are subjected to good protection under the high-temperature molten salt condition is with anti-corrosion protecting materials and preparation method thereof.
A kind of corrosion resistant protection material for fusedsaltelectrolysiand is characterized in that the quality proportioning of this corrosion resistant protection material for fusedsaltelectrolysiand component is: 75%-100% AB
2O
4, 0-25%M
xO
yAB
2O
4For having the composite oxides of spinel structure, wherein A is Ni, at least a among Zn, Cu, Co or the Mn, and B is at least a among Fe or the Al; M is at least a among Ni, Ca, Cu, Ba, Y, the Ce; X=1 or 2; Y=1,2 or 3.
A kind of fused salt electrolysis is characterized in that the step of its preparation process comprises with the preparation method of anti-corrosion protecting materials:
(1) synthetic AB
2O
4The spinel oxides ceramic phase;
(2) with AB
2O
4, M
xO
Y,Binding agent and dispersant carry out mix and blend by proportioning, and oven dry, moulding, degreasing, sintering obtain corrosion resistant protection material for fusedsaltelectrolysiand.
The preparation method of a kind of corrosion resistant protection material for fusedsaltelectrolysiand of the present invention is characterized in that synthetic AB
2O
4The raw material process directly add with the oxide form of respective element A, B, addition is respectively in the corresponding oxide equivalents of elements A, B; Synthetic AB
2O
4The temperature of spinel oxides ceramic phase is 1000-1300 ℃, and synthetic atmosphere is air atmosphere.
A kind of fused salt electrolysis of the present invention is characterized in that with the preparation method of anti-corrosion protecting materials dispersion agent is water, industrial spirit, and addition is 50% ~ 70% of a raw material gross weight.
A kind of fused salt electrolysis of the present invention is with the preparation method of anti-corrosion protecting materials; it is characterized in that binding agent is at least a in polyvinyl alcohol, carboxymethyl cellulose, hydroxy propyl cellulose, polyoxyethylene glycol, dextrin, the polyacrylamide, its addition is 0.5% ~ 2% of a raw material gross weight.
A kind of fused salt electrolysis of the present invention is characterized in that with the preparation method of anti-corrosion protecting materials its molding mode is compression molding or extrusion molding, and forming pressure is 30MPa ~ 200MPa.
A kind of fused salt electrolysis of the present invention is characterized in that with the preparation method of anti-corrosion protecting materials skimming temp is 200-600 ℃, and degreasing time is 10-24h.
The preparation method of a kind of corrosion resistant protection material for fusedsaltelectrolysiand of the present invention is characterized in that AB
2O
4-M
xO
yThe sintering temperature of pottery is 1200~1400 ℃, and sintering atmosphere is air atmosphere, and sintering time is 15 ~ 30h.
A kind of corrosion resistant protection material for fusedsaltelectrolysiand of the present invention by filling a prescription preferred and the means such as pressureless sintering, can be resisted high-temperature molten salt corrosion and have the good thermal shock resistance energy, is implemented under the high-temperature molten salt condition good protection to inert electrode guide rod and thermocouple; Preparation process be sintered to air atmosphere, sintering process is easy to control, passes through M
xO
yAdding, not only can realize AB
2O
4The cryogenic activating sintering of pottery, and can crystal grain thinning, corrosion resisting property and the thermal shock resistance of material improved.
Description of drawings
Fig. 1 is CaO-NiO-NiFe in the embodiment of the invention 1
2O
4Sample section S EM figure behind 1300 ℃ of sintering of oxide ceramics protective material.
Fig. 2 is CaO-NiO-NiFe in the embodiment of the invention 1
2O
4Oxide ceramics protective material static corrosion 24h post-etching layer SEM figure.
Fig. 3 is CuO-NiO-NiFe in the embodiment of the invention 2
2O
4Sample section S EM figure behind 1300 ℃ of sintering of oxide ceramics protective material.
Fig. 4 is CuO-NiO-NiFe in the embodiment of the invention 2
2O
4Oxide ceramics protective material static corrosion 24h post-etching layer SEM figure.
Fig. 5 is BaO-Y in the embodiment of the invention 3
2O
3-NiO-NiFe
2O
4Oxide ceramics protective material static corrosion 24h post-etching layer SEM figure.
Embodiment
A kind of corrosion resistant protection material for fusedsaltelectrolysiand, the quality proportioning of this corrosion resistant protection material for fusedsaltelectrolysiand component is: 75%-100% AB
2O
4, 0-25%M
xO
yAB
2O
4For having the composite oxides of spinel structure, wherein A is Ni, at least a among Zn, Cu, Co or the Mn, and B is at least a among Fe or the Al; M is at least a among Ni, Ca, Cu, Ba, Y, the Ce; X=1 or 2; Y=1,2 or 3.
The step of its preparation process journey comprises:
(1) at first will synthesize AB
2O
4Raw material directly add with the oxide form of respective element A, B, addition is respectively in the corresponding oxide equivalents of elements A, B;
(2) by batch mixing, drying, behind 1000 ~ 1200 ℃ of lower calcining 4 ~ 6h, obtain the AB of object phase composition
2O
4Raw material;
(3) then with AB
2O
4And M
xO
y, dispersant, binding agent, press proportion ingredient batch mixing 1-4h, and in 60-100 ℃ of lower oven dry 6-12h, adopt mold pressing or extrusion modling to obtain ceramic green at 30~200 MPa compacted unders, 200-600 ℃ of lower degreasing 10-24h under air or oxygen atmosphere, sintering 15 ~ 30h under 1200~1400 ℃ and air atmosphere obtains the electrode insulation material.
Embodiment 1
CaO-NiO-NiFe
2O
4The oxide ceramics protective material
CaO-NiO-NiFe
2O
4Oxide ceramics protective material batching is as shown in table 1.
Table 1 CaO-NiO-NiFe
2O
4Oxide ceramics protective material composition proportion
Composition | Content wt % |
NiFe 2O 4 | 87.12 |
NiO | 11.88 |
CaO | 1 |
1:1 takes by weighing NiO and Fe in molar ratio
2O
3, put into the kneading pot, take water as dispersant, stir 2h.Put into 80 ℃ of oven dry of baking oven after stirring.Pulverizing is rear and put into the corundum saggar, uses Muffle furnace 1200 ℃ of calcining 6h under air atmosphere, and the rear pulverizing of cooling obtains NiFe
2O
4Ceramic phase.Add 11.88% NiO and 1% CaO in ceramic phase, binding agent made by the polyvinyl alcohol that accounts for total mass 2% and industrial spirit is made dispersion agent, ball milling 2.5h in ball grinder.Rear taking-up is through 80 ℃ of oven dry.Coldmoulding under 150MPa pressure, the two-way sample that is pressed into φ 30mm * 20mm.In retort furnace under the air atmosphere, 600 ℃ of degreasing 2h, at last at 1300 ℃ of insulation 4h, furnace cooling obtains the sample of densified sintering product.Burn till back sample section S EM figure as shown in Figure 1.It is 91.91% that test draws its relative density; Folding strength is 33MPa; The static corrosion rate is 0.67mm/a.Static corrosion 24h post-etching layer SEM figure as shown in Figure 2.
Embodiment 2
CuO-NiO-NiFe
2O
4The oxide ceramics protective material
CuO-NiO-NiFe
2O
4Oxide ceramics protective material batching is as shown in table 2.
Table 2 CuO-NiO-NiFe
2O
4Oxide ceramics protective material composition proportion
Composition | Content wt% |
NiFe 2O 4 | 80.3 |
NiO | 10.95 |
CuO | 8.75 |
1:1 takes by weighing NiO and Fe in molar ratio
2O
3, put into the kneading pot, take water as dispersant, stir 2h.Put into 80 ℃ of oven dry of baking oven after stirring.Take out and pulverize and put into the corundum saggar, use Muffle furnace 1000 ℃ of calcining 6h under air atmosphere, pulverize after the cooling, obtain ceramic phase NiFe
2O
4Add 10.95% NiO and 8.75% CuO in ceramic phase, binding agent made by the polyacrylamide that accounts for total mass 1.5% and industrial spirit is made dispersion agent, ball milling 2.5h in ball grinder.Take out behind the ball milling, through 60 ℃ of oven dry.Coldmoulding under 200MPa pressure, the two-way sample that is pressed into φ 30mm * 20mm.In retort furnace under the air atmosphere, 600 ℃ of degreasing 2h, at last at 1300 ℃ of insulation 4h, furnace cooling obtains the sample of densified sintering product.Burn till back sample section S EM figure as shown in Figure 3.It is 92.04% that test draws its relative density; Folding strength is 69.5MPa; The static corrosion rate is 0.026mm/a.Static corrosion 24h post-etching layer SEM figure as shown in Figure 4.
Embodiment 3
BaO-Y
2O
3-NiO-NiFe
2O
4The oxide ceramics protective material
BaO-Y
2O
3-NiO-NiFe
2O
4Oxide ceramics protective material batching is as shown in table 3.
Table 3 BaO-Y
2O
3-NiO-NiFe
2O
4Oxide ceramics protective material composition proportion
Composition | Content wt% |
NiFe 2O 4 | 85 |
NiO | 22 |
BaO | 2 |
Y 2O 3 | 1 |
1:1 takes by weighing NiO and Fe in molar ratio
2O
3, put into the kneading pot, take water as dispersant, stir 2h.Put into 80 ℃ of oven dry of baking oven after stirring.Take out and pulverize and put into the corundum saggar, use Muffle furnace 1200 ℃ of calcining 6h under air atmosphere, pulverize after the cooling, obtain ceramic phase NiFe
2O
4In ceramic phase, add 22%NiO, 2%BaO and 1%Y
2O
3, binding agent made by the polyvinyl alcohol that accounts for gross mass 2% and industrial alcohol is made dispersant, kneading 2h in the kneading pot.Take out behind the ball milling, through 80 ℃ of oven dry.Coldmoulding under 150MPa pressure, the two-way sample that is pressed into φ 30mm * 20mm.In retort furnace under the air atmosphere, 600 ℃ of degreasing 2h, at last at 1300 ℃ of insulation 4h, furnace cooling obtains the sample of densified sintering product.It is 89.85% that test draws its relative density; Folding strength is 81MPa; The static corrosion rate is 0.39mm/a.Static corrosion 24h post-etching layer SEM figure as shown in Figure 5.
Embodiment 4
CeO
2-NiO-NiAl
2O
4The oxide ceramics protective material
CeO
2-NiO-NiAl
2O
4Oxide ceramics protective material batching is as shown in table 4.
Table 4 CeO
2-NiO-NiAl
2O
4Oxide ceramics protective material composition proportion
Composition | Content wt% |
NiAl 2O 4 | 75 |
NiO | 24 |
CeO | 1 |
1:1 takes by weighing NiO and Al in molar ratio
2O
3, put into the kneading pot, take water as dispersant, stir 2h.Put into 80 ℃ of oven dry of baking oven after stirring.Take out and pulverize and put into the corundum saggar, use Muffle furnace 1200 ℃ of calcining 2h under air atmosphere, pulverize after the cooling, obtain ceramic phase NiAl
2O
4The NiO of adding 24% and 1% CeO in ceramic phase
2, the carboxymethyl cellulose that accounts for gross mass 2% makes binding agent and industrial alcohol is made dispersant, ball milling 2h in ball grinder.Take out behind the ball milling, through 80 ℃ of oven dry.Coldmoulding under 100MPa pressure, the two-way sample that is pressed into φ 30mm * 20mm.In retort furnace under the air atmosphere, 600 ℃ of degreasing 2h, at last at 1400 ℃ of insulation 4h, furnace cooling obtains the sample of densified sintering product.Its relative density is 92.74%.
Embodiment 5
Y
2O
3-CaO-NiO-NiAl
2O
4The oxide ceramics protective material
Y
2O
3-CaO-NiO-NiAl
2O
4Oxide ceramics protective material batching is as shown in table 5.Table 5 Y
2O
3-CaO-NiO-NiAl
2O
4Oxide ceramics protective material composition proportion
Composition | Content wt% |
NiAl 2O 4 | 83 |
NiO | 15 |
CaO | 1.5 |
Y 2O 3 | 0.5 |
1:1 takes by weighing NiO and Al in molar ratio
2O
3, put into the kneading pot, take water as dispersant, stir 2h.Put into 80 ℃ of oven dry of baking oven after stirring.Take out and pulverize and put into the corundum saggar, use Muffle furnace 1200 ℃ of calcining 2h under air atmosphere, pulverize after the cooling, obtain ceramic phase NiAl
2O
4Add 24% NiO in ceramic phase, binding agent made by the dextrin that accounts for total mass 1% and industrial spirit is made dispersion agent, ball milling 2h in ball grinder.Take out behind the ball milling, through 80 ℃ of oven dry.The sample of φ 25mm * 20mm is made in extrusion molding under 30MPa pressure.In retort furnace under the air atmosphere, 600 ℃ of degreasing 2h, at last at 1350 ℃ of insulation 4h, furnace cooling obtains the sample of densified sintering product.Sample is through 800 ℃ of rapid heat cycle circulation experiments 5 times, and the no obvious crackle in surface shows good thermal shock resistance.
Embodiment 6
NiFe
2O
4The oxide ceramics protective material
1:1 takes by weighing NiO and Fe in molar ratio
2O
3, put into the kneading pot, take water as dispersant, stir 2h.Put into 80 ℃ of oven dry of baking oven after stirring.Take out and pulverize and put into the corundum saggar, use Muffle furnace 1200 ℃ of calcining 2h under air atmosphere, pulverize after the cooling, obtain ceramic phase NiFe
2O
4Binding agent made by the polyethylene glycol that adds gross mass 1.5% in ceramic phase and industrial alcohol is made dispersant, ball milling 2h in ball grinder.Take out behind the ball milling, through 60 ℃ of oven dry.The sample of φ 25mm * 40mm is made in extrusion molding under 30MPa pressure.In retort furnace under the air atmosphere, 400 ℃ of degreasing 2h, at last at 1350 ℃ of insulation 4h, furnace cooling obtains the sample of densified sintering product.Sample is through 800 ℃ of rapid heat cycle circulation experiments 4 times, and the no obvious crackle in surface shows good thermal shock resistance.
Claims (8)
1. a corrosion resistant protection material for fusedsaltelectrolysiand is characterized in that the quality proportioning of this corrosion resistant protection material for fusedsaltelectrolysiand component is: 75%-100% AB
2O
4, 0-25%M
xO
yAB
2O
4For having the composite oxides of spinel structure, wherein A is Ni, at least a among Zn, Cu, Co or the Mn, and B is at least a among Fe or the Al; M is at least a among Ni, Ca, Cu, Ba, Y, the Ce; X=1 or 2; Y=1,2 or 3.
2. a fused salt electrolysis is characterized in that the step of its preparation process comprises with the preparation method of anti-corrosion protecting materials:
(1) synthetic AB
2O
4The spinel oxides ceramic phase;
(2) with AB
2O
4, M
xO
Y,Binding agent and dispersant carry out mix and blend by proportioning, and oven dry, moulding, degreasing, sintering obtain corrosion resistant protection material for fusedsaltelectrolysiand.
3. according to the preparation method of the described a kind of corrosion resistant protection material for fusedsaltelectrolysiand of claim, it is characterized in that synthetic AB
2O
4The raw material process directly add with the oxide form of respective element A, B, addition is respectively in the corresponding oxide equivalents of elements A, B; Synthetic AB
2O
4The temperature of spinel oxides ceramic phase is 1000-1300 ℃, and synthetic atmosphere is air atmosphere.
4. a kind of fused salt electrolysis according to claim 2 is characterized in that with the preparation method of anti-corrosion protecting materials dispersion agent is water, industrial spirit, and addition is 50 ~ 70% of a raw material gross weight.
5. a kind of fused salt electrolysis according to claim 2 is with the preparation method of anti-corrosion protecting materials; it is characterized in that binding agent is at least a in polyvinyl alcohol, carboxymethyl cellulose, hydroxy propyl cellulose, polyoxyethylene glycol, dextrin, the polyacrylamide, its addition is 0.5% ~ 2% of a raw material gross weight.
6. a kind of fused salt electrolysis according to claim 2 is characterized in that with the preparation method of anti-corrosion protecting materials its molding mode is compression molding or extrusion molding, and forming pressure is 30MPa ~ 200MPa.
7. a kind of fused salt electrolysis according to claim 2 is characterized in that with the preparation method of anti-corrosion protecting materials skimming temp is 200-600 ℃, and degreasing time is 10-24h.
8. the preparation method of a kind of corrosion resistant protection material for fusedsaltelectrolysiand according to claim 2 is characterized in that AB
2O
4-M
xO
yThe sintering temperature of pottery is 1200~1400 ℃, and sintering atmosphere is air atmosphere, and sintering time is 15 ~ 30h.
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CN104498998A (en) * | 2014-12-06 | 2015-04-08 | 中国铝业股份有限公司 | Protecting method of electrode guide rod for insulating corrosion of electrolyte atmosphere |
CN109970438A (en) * | 2019-04-28 | 2019-07-05 | 中国铝业股份有限公司 | A kind of side-wall material |
CN112458523A (en) * | 2020-11-12 | 2021-03-09 | 南通创源电化学科技有限公司 | Ceramic anode electroplating bath |
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CN113480295A (en) * | 2021-08-04 | 2021-10-08 | 中钢集团洛阳耐火材料研究院有限公司 | Ceramic crucible for nickel-based high-temperature alloy and preparation method |
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CN104498998A (en) * | 2014-12-06 | 2015-04-08 | 中国铝业股份有限公司 | Protecting method of electrode guide rod for insulating corrosion of electrolyte atmosphere |
CN109970438A (en) * | 2019-04-28 | 2019-07-05 | 中国铝业股份有限公司 | A kind of side-wall material |
CN112537956A (en) * | 2019-09-23 | 2021-03-23 | 比亚迪股份有限公司 | Black zirconia ceramic and preparation method and application thereof |
CN112458523A (en) * | 2020-11-12 | 2021-03-09 | 南通创源电化学科技有限公司 | Ceramic anode electroplating bath |
CN112458523B (en) * | 2020-11-12 | 2023-10-31 | 南通创源电化学科技有限公司 | Ceramic anode electroplating bath |
CN113480295A (en) * | 2021-08-04 | 2021-10-08 | 中钢集团洛阳耐火材料研究院有限公司 | Ceramic crucible for nickel-based high-temperature alloy and preparation method |
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