CN101586246B - High temperature resistant molten salt corrosion ceramet anode material and preparation method thereof - Google Patents
High temperature resistant molten salt corrosion ceramet anode material and preparation method thereof Download PDFInfo
- Publication number
- CN101586246B CN101586246B CN2009103040917A CN200910304091A CN101586246B CN 101586246 B CN101586246 B CN 101586246B CN 2009103040917 A CN2009103040917 A CN 2009103040917A CN 200910304091 A CN200910304091 A CN 200910304091A CN 101586246 B CN101586246 B CN 101586246B
- Authority
- CN
- China
- Prior art keywords
- corrosion
- high temperature
- molten salt
- temperature resistant
- anode material
- 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.)
- Expired - Fee Related
Links
Images
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The present invention provides a kind of high temperature resistant molten salt corrosion ceramet anode material and a preparation method thereof. The referred ceramet inertness anode material is composed of the following components by weight: 50% to 95% of spinelle type oxide, 1% to 30% of other oxide, 1% to 30% of metal or alloy, and 0.1% to 2% of grain boundary corrosion resistant energizing agent. The raw material is added with a given amount of +3 value lanthanide series rare-earth oxide powder, the rare-earth oxide and a ceramic matrix react with each other during a sintering process to form high temperature resistant molten salt corrosive ferrate new phase along the grain boundary, and simultaneously accelerate the elimination of communication between the grain boundary and breathing holes as well as densification of the sintering material, so as to improve the high temperature resistant molten salt corrosive performance of the material especially the grain boundary region.
Description
Technical field
The invention belongs to material science, relate to a kind of high temperature resistant molten salt corrosion ceramet anode material and preparation method thereof.
Background technology
At present, sintering metal is because of with the good thermo-chemical stability of pottery, strong corrosion resistant, oxidation-resistance and metallic substance good conduction and thermal shock resistance, and being considered to be hopeful to replace carbon anode most becomes one of inert anode material of fused salt electrolysis (as electrolytic aluminum).In high temperature fused salt electrolysis matter, because the difference of chemical composition and the existence of crystal boundary impurity or internal stress between crystal grain boundary and inside, cause easily electrolyte osmosis, material swelling, ftracture and the problem such as come off, therefore need take effective ways to strengthen or purify the crystal boundary of cermet material, improve its high temperature resistant molten salt corrosive nature.At present solution mainly contains and adjusts the material composition proportioning, reduces raw material impurity content, optimizes preparation technology and improve density, reduce porosity etc.The present invention proposes a kind of high temperature fused salt electrolysis anti-corrosion intensifying method of inert anode material, especially for spinel based cermet inert anode material, by adding the anti-corrosion hardening agent of an amount of crystal boundary, make itself and ceramic matrix that certain chemical reaction take place, and generate high temperature resistant electrolyte fused salt corrosion novel substance along crystal boundary, the generation of this material both had been conducive to eliminate crystal boundary and had been communicated with pore, improve the material sintered density, reach the purpose that improves cermet material refractory salt corrosion performance thereby can strengthen again its crystal boundary.
Summary of the invention
The purpose of this invention is to provide a kind of corrosion that can stand secular high-temperature fluorination thing fused salt, and can guarantee cermet inert anode material of inert anode smooth running in electrolysis of aluminum and preparation method thereof, solve the problem that existing used for aluminium electrolysis cermet inert anode material corrosion resistance, especially crystal boundary corrosion resistance nature have much room for improvement.
A kind of high temperature resistant molten salt corrosion ceramet anode material is made up of following mass percent component: 50%-95% spinel oxides, other oxide compound of 1%-30%, 1%-30% metallographic phase, the anti-corrosion reinforcer of 0.1%-2% crystal boundary.
Described spinel oxides is MFe
2O
4And MAl
2O
4In a kind of or their combination, M is Ni, Cu, Mn, Zn or Co; Other oxide is A
xO
yIn a kind of or their combination, x=1 or 2; Y=1,2 or 3; A is Ni, Cu, Mn, Zn or Co.
Described metallographic phase is a kind of among Fe, Ni, Cu, Co, the Ag or their alloy.
The anti-corrosion hardening agent of described crystal boundary is La
2O
3, Y
2O
3, Yb
2O
3And other+a kind of in the 3 valency lanthanide rare earth oxides or their combination, and particle size range is 2-5 μ m.
Its preparation technology carries out as follows:
(1) synthetic: by synthetic MFe
2O
4Or MAl
2O
4The spinelle stoichiometric proportion takes by weighing MO and Fe
2O
3Or Al
2O
3After add again a certain amount of A
xO
yOxide and an amount of dispersant carry out batch mixing 1-4h, and batch mixing is evenly rear 80-120 ℃ of lower the oven dry and the synthetic MFe of calcining under 1000-1400 ℃ of air atmosphere
2O
4Or MAl
2O
4Spinel oxides and A
xO
yMixture;
(2) batch mixing: with above-mentioned ceramic phase, metal and anti-corrosion reinforcer carry out batch mixing in proportion, described ceramic phase is made up of spinel oxides and other oxide compound, the mass percent of spinel oxides in sintering metal is 50%-95%, granularity is 2-20 μ m, the mass percent of described other oxide compound in sintering metal is 1%-30%, granularity is 1-10 μ m, the mass percent of described metallographic phase in sintering metal is 1%-30%, granularity is 5-35 μ m, the mass percent of described anti-corrosion reinforcer in sintering metal is 0.1-2%, granularity is 2-5 μ m, and adds the organic binder bond polyvinyl alcohol of compound total mass 1wt% and an amount of dispersion agent industrial spirit carries out batch mixing 1-12h;
(3) oven dry: after batch mixing is even, 80-120 ℃ of lower oven dry;
(4) moulding: compound compression molding under 100-500MPa pressure is obtained the sintering metal green compact;
(5) degreasing: with the sintering metal green compact under nitrogen atmosphere 200-600 ℃ carried out O in the nitrogen atmosphere degreasing 2-10 hour
2Dividing potential drop is 50-500ppm;
(6) densification sintering: insulation in the vacuum sintering furnace of the green compact after the degreasing under 1200-1400 ℃ of temperature was obtained cermet specimens in 2-10 hour, temperature rise rate 20-50 ℃/h wherein, O in the nitrogen atmosphere
2Dividing potential drop is 50-500ppm.
The present invention can realize the anti-corrosion reinforcement of used for aluminium electrolysis cermet inert anode material crystal boundary, adopts suitable anti-corrosion reinforcer and proper proportion and rational sintering process to solve the anti-fluorochemical high-temperature molten salt corrosion of inert anode material problem; Its technology is simple, convenient, and raw material is easy to get, and is with low cost.Cermet inert anode material of the present invention, make anti-corrosion reinforcer and ceramic matrix that certain chemical reaction take place by suitable anti-corrosion reinforcer adding proportion and agglomerant artistic skill, and generate high temperature resistant ionogen fused salt corrosion novel substance wustite cenotype along crystal boundary, the generation of this wustite had both helped eliminating crystal boundary and had been communicated with pore, improve the material sintered density, thereby can strengthen its crystal boundary again and reach the purpose that improves cermet material refractory brine corrosion performance, thereby can stand the corrosion of secular high-temperature fluorination thing fused salt, can guarantee inert anode smooth running in electrolysis of aluminum.The present invention uses the heavy industrialization of realizing cermet inert anode and is significant.
Description of drawings
Fig. 1 is 0.50Yb in the specific embodiment of the invention 1
2O
3-10Cu/ (10NiO-NiFe
2O
4) 1300 ℃ of sintered sample fractures of cermet inert anode sem photograph.(1000X)
Fig. 2 is the 0.50Yb of 1300 ℃ of sintering in the specific embodiment of the invention 1
2O
3-10Cu/ (10NiO-NiFe
2O
4) cermet inert anode is at 960 ℃ of electrolysis 10h post-etching sample corrosion layer sem photographs.(200X)
Fig. 3 is 0.50Yb in the specific embodiment of the invention 2
2O
3-3Ni-12Cu/ (10NiO-NiFe
2O
4) 1300 ℃ of sintered sample fractures of cermet inert anode sem photograph.(500X)
Fig. 4 is 0.50Yb in the specific embodiment of the invention 2
2O
3-3Ni-12Cu/ (10NiO-NiFe
2O
4) 960 ℃ of electrolysis 10h corrosion of cermet inert anode sample corrosion layer sem photograph.(500X)
Fig. 5 is 0.25Yb in the specific embodiment of the invention 3
2O
3-3Ni-12Cu/ (10NiO-NiFe
2O
4) 1300 ℃ of sintered sample fractures of cermet inert anode sem photograph.(500X)
Fig. 6 is 0.25Yb in the specific embodiment of the invention 3
2O
3-3Ni-12Cu/ (10NiO-NiFe
2O
4) 960 ℃ of electrolysis 10h corrosion of cermet inert anode sample corrosion layer sem photograph.(500X)
Fig. 7 is 1.0Y in the specific embodiment of the invention 4
2O
3-10Cu/ (10NiO-NiFe
2O
4) 1300 ℃ of sintered sample fractures of cermet inert anode sem photograph.(500X)
Fig. 8 is 1.0Y in the specific embodiment of the invention 4
2O
3-10Cu/ (10NiO-NiFe
2O
4) 960 ℃ of electrolysis 10h corrosion of cermet inert anode sample corrosion layer sem photograph.(200X)
Fig. 9 is 0.5Y in the specific embodiment of the invention 5
2O
3-10Cu/ (10NiO-NiFe
2O
4) 1300 ℃ of sintered sample fractures of cermet inert anode sem photograph.(500X)
Figure 10 is 0.5Y in the specific embodiment of the invention 5
2O
3-10Cu/ (10NiO-NiFe
2O
4) 960 ℃ of electrolysis 10h corrosion of cermet inert anode sample corrosion layer sem photograph.(500X)
Embodiment:
The invention will be further described below in conjunction with embodiment, rather than limitation of the present invention.
Embodiment 1:0.50Yb
2O
3-10Cu/ (10NiO-NiFe
2O
4) cermet inert anode
0.50Yb
2O
3-10Cu/ (10NiO-NiFe
2O
4) composition of raw materials of cermet inert anode is as shown in table 1.
Table 1 0.50Yb
2O
3-10Cu/ (10NiO-NiFe
2O
4) the composition of raw materials example of cermet inert anode
| Raw material | Quality percentage composition (%) |
| Yb 2O 3 | 0.50 |
| NiO | 8.95 |
| NiFe 2O 4 | 80.55 |
| Cu | 10.00 |
Be 61.32% and 38.68% to take by weighing respectively Fe by mass fraction
2O
3Powder and NiO powder, granularity are respectively 1.4 μ m and 4.1 μ m, after ball milling mixing 2.5h and 100 ℃ of dryings, the corundum crucible of packing into place resistance furnace under air atmosphere in 1200 ℃ of calcining 6h, obtain NiFe
2O
4The spinel ceramics powder adds NiFe then
2O
4Spinelle, NiO oxide, Cu metal and Yb
2O
3Powder is mixed together, its granularity is respectively 8.1 μ m, 4.1 μ m, 10 μ m and 3.1 μ m, take industrial alcohol as dispersant and the 1wt% polyvinyl alcohol be binding agent, ball milling 2.5h in ball grinder, behind 100 ℃ of dry 12h of mixed-powder, bidirectional pressed moulding is the green compact of d20mm * 40mm under 200MPa pressure, green compact carry out degreasing in nitrogen protective atmosphere, skimming temp is 600 ℃, and degreasing time is 10h, and oxygen content is 100ppm in the atmosphere; Rise to 1300 ℃ and be incubated 4h and carry out densification sintering with the heating rate of 20 ℃/h at last, obtain final sintered sample, its sample fractography as shown in Figure 1, the sample fracture is fine and close, Yb
2O
3Granule disperse distribution cermet.Its density, bending strength, electric conductivity, 960 ℃ of annual corrosion rates (ionogen composition 78.07%Na
3AlF
6-9.5%AlF
3-5.0%CaF
2-7.43%Al
2O
3, molecular ratio is 2.3, liquidus temperature is 947 ℃, 960 ℃ of electrolysis temperatures, 13 ℃ of superheating temperature) be respectively 95.58%, 169.6MPa, 16.59Scm
-1And 3.33cm/a.960 ℃ of electrolysis 10h of its cermet inert anode post-etching sample corrosion layer sem photograph as shown in Figure 2, the metallic corrosion layer is about 10 μ m-30 μ m, illustrates that anode has stronger high temperature resistant molten salt corrodibility.
Annual corrosion rate calculation formula (down together):
W
Loss=(W
b* C
b+ W
a* C
a) * 10
-6* 365 * 24/ (s
Anode* ρ
Anode* t)
W in the formula
LossBe defined as anode annual corrosion rate (cm/a), W
bBe ionogen total amount (g), C
bFor entering the impurity concentration (ppm) in the ionogen, W
aBe the total amount (g) of negative electrode aluminium, C
aFor entering impurity concentration (ppm) in the negative electrode aluminium liquid, S
AnodeAnode submerged surface-area (cm during for electrolysis
2), ρ
AnodeBe anodic volume density (g/cm
3), t is electrolysis time (h).
Embodiment 2:0.50Yb
2O
3-3Ni-12Cu/ (10NiO-NiFe
2O
4) cermet inert anode
0.50Yb
2O
3-3Ni-12Cu/ (10NiO-NiFe
2O
4) composition of raw materials of cermet inert anode is as shown in table 2.
Table 2 0.50Yb
2O
3-3Ni-12Cu/ (10NiO-NiFe
2O
4) the composition of raw materials example of cermet inert anode
| Raw material | Quality percentage composition (%) |
| Yb 2O 3 | 0.50 |
| NiO | 8.45 |
| NiFe 2O 4 | 76.05 |
| Cu | 12.00 |
| Ni | 3.00 |
Be 61.32% and 38.68% to take by weighing respectively and analyze pure Fe by mass fraction
2O
3Powder and analyze pure NiO powder, granularity is respectively 1.4 μ m and 4.1 μ m, and after ball milling mixings 2.5h and 100 ℃ of dryings, the corundum crucible of packing into places resistance furnace to calcine 6h in 1200 ℃ under air atmosphere, obtains NiFe
2O
4The spinel ceramics powder adds NiFe then
2O
4Spinelle, NiO oxide, Cu-Ni metal and Yb
2O
3Powder is mixed together, its granularity is respectively 8.1 μ m, 4.1 μ m, 12 μ m and 3.1 μ m, take industrial alcohol as dispersant and the 1wt% polyvinyl alcohol be binding agent, secondary ball milling 2.5h in ball grinder, after 100 ℃ of dryings of mixed-powder under 200MPa pressure bidirectional pressed moulding be the green compact of d20mm * 40mm, green compact are at N
2Carry out degreasing in the protective atmosphere, skimming temp is 600 ℃, and degreasing time is 10h, and oxygen content is 100ppm in the atmosphere; Rise to 1300 ℃ and be incubated 4h and carry out densification sintering with the heating rate of 20 ℃/h at last, obtain final sintered sample, sample fracture sem photograph as shown in Figure 3, Yb
2O
3Powder disperse distribution cermet, and the sample hole is less.(ionogen is formed 78.07%Na for density, bending strength, electric conductivity and 960 ℃ of annual corrosion rates
3AlF
6-9.5%AlF
3-5.0%CaF
2-7.43%Al
2O
3, molecular ratio is 2.3, liquidus temperature is 947 ℃, 960 ℃ of electrolysis temperatures, 13 ℃ of superheating temperature) be respectively 98.92%, 178.7MPa, 38.27Scm
-1And 0.65cm/a.960 ℃ of electrolysis 10h of its cermet inert anode corrode sample corrosion layer sem photograph as shown in Figure 4, and the metallic corrosion layer thickness is 10-20 μ m, illustrates that its high temperature resistant molten salt corrosive nature is better.
Embodiment 3:0.25Yb
2O
3-3Ni-12Cu/ (10NiO-NiFe
2O
4) cermet inert anode
0.25Yb
2O
3-3Ni-12Cu/ (10NiO-NiFe
2O
4) composition of raw materials of cermet inert anode is as shown in table 3.
Table 3 0.25Yb
2O
3-3Ni-12Cu/ (10NiO-NiFe
2O
4) the composition of raw materials example of cermet inert anode
| Raw material | Quality percentage composition (%) |
| Yb 2O 3 | 0.25 |
| NiO | 84.75 |
| NiFe 2O 4 | 76.275 |
| Cu | 12.00 |
| Ni | 3.00 |
Be 61.32% and 38.68% to take by weighing respectively and analyze pure Fe by mass fraction
2O
3Powder and analyze pure NiO powder, granularity is respectively 1.4 μ m and 4.1 μ m, and after ball milling mixings 2.5h and 100 ℃ of dryings, the corundum crucible of packing into places resistance furnace to calcine 6h in 1200 ℃ under air atmosphere, obtains NiFe
2O
4The spinel ceramics powder adds NiFe then
2O
4Spinelle, NiO oxide, Cu-Ni metal and Yb
2O
3Powder is mixed together, its granularity is respectively 8.1 μ m, 4.1 μ m, 12 μ m and 3.1 μ m, take industrial alcohol as dispersant and the 1wt% polyvinyl alcohol be binding agent, secondary ball milling 2.5h in ball grinder, after 100 ℃ of dryings of mixed-powder under 200MPa pressure bidirectional pressed moulding be the green compact of d20mm * 40mm, green compact are at N
2Carry out degreasing in the protective atmosphere, skimming temp is 600 ℃, and degreasing time is 10h, and oxygen content is 100ppm in the atmosphere; Rise to 1300 ℃ and be incubated 4h and carry out densification sintering with the heating rate of 20 ℃/h at last, obtain final sintered sample, sample fracture sem photograph as shown in Figure 5, Yb
2O
3Powder disperse distribution cermet, and the sample hole is less.(ionogen is formed 78.07%Na for density, bending strength, electric conductivity and 960 ℃ of annual corrosion rates
3AlF
6-9.5%AlF
3-5.0%CaF
2-7.43%Al
2O
3, molecular ratio is 2.3, liquidus temperature is 947 ℃, 960 ℃ of electrolysis temperatures, 13 ℃ of superheating temperature) be respectively 96.93%, 175.3MPa, 45.41Scm
-1And 0.78cm/a.960 ℃ of electrolysis 10h of its cermet inert anode corrode sample corrosion layer sem photograph as shown in Figure 6, and the metallic corrosion layer thickness is 30-50 μ m, illustrates that its high temperature resistant molten salt corrosive nature is better.
Embodiment 4:1.0Y
2O
3-10Cu/ (10NiO-NiFe
2O
4) cermet inert anode
1.0Y
2O
3-10Cu/ (10NiO-NiFe
2O
4) composition of raw materials of cermet inert anode is as shown in table 4.
Table 4 1.0Y
2O
3-10Cu/ (10NiO-NiFe
2O
4) the composition of raw materials example of cermet inert anode
| Raw material | Quality percentage composition (%) |
| Y 2O 3 | 1.0 |
| NiO | 8.90 |
| NiFe 2O 4 | 80.10 |
| Cu | 10.00 |
Be 61.32% and 38.68% to take by weighing respectively and analyze pure Fe by mass fraction
2O
3Powder and analyze pure NiO powder, granularity is respectively 1.4 μ m and 4.1 μ m, and after ball milling mixings 2.5h and 100 ℃ of dryings, the corundum crucible of packing into places resistance furnace to calcine 6h in 1200 ℃ under air atmosphere, obtains NiFe
2O
4The spinel ceramics powder adds NiFe then
2O
4Spinelle, NiO oxide, Cu-Ni metal and Y
2O
3Powder is mixed together, its granularity is respectively 8.1 μ m, 4.1 μ m, 10 μ m and 3.5 μ m, take industrial alcohol as dispersant and the 1wt% polyvinyl alcohol be binding agent, secondary ball milling 2.5h in ball grinder, after 100 ℃ of dryings of mixed-powder under 200MPa pressure bidirectional pressed moulding be the green compact of d20mm * 40mm, green compact are at N
2Carry out degreasing in the protective atmosphere, skimming temp is 600 ℃, and degreasing time is 10h, and oxygen content is 100ppm in the atmosphere; Rise to 1300 ℃ and be incubated 4h and carry out densification sintering with the heating rate of 20 ℃/h at last, obtain final sintered sample, sample fracture sem photograph as shown in Figure 7, Y
2O
3Powder disperse distribution cermet, and the sample hole is less.(ionogen is formed 78.07%Na for density, bending strength, electric conductivity and 960 ℃ of annual corrosion rates
3AlF
6-9.5%AlF
3-5.0%CaF
2-7.43%Al
2O
3, molecular ratio is 2.3, liquidus temperature is 947 ℃, 960 ℃ of electrolysis temperatures, 13 ℃ of superheating temperature) be respectively 93.28%, 165.7MPa, 17.91Scm
-1And 4.08cm/a.960 ℃ of electrolysis 10h of its cermet inert anode corrode sample corrosion layer sem photograph as shown in Figure 8, and the metallic corrosion layer thickness is 30-100 μ m, illustrates that its high temperature resistant molten salt corrosive nature is better.
Embodiment 5:0.5Y
2O
3-10Cu/ (10NiO-NiFe
2O
4) cermet inert anode
0.5Y
2O
3-10Cu/ (10NiO-NiFe
2O
4) composition of raw materials of cermet inert anode is as shown in table 5.
Table 5 1.0Y
2O
3-10Cu/ (10NiO-NiFe
2O
4) the composition of raw materials example of cermet inert anode
| Raw material | Quality percentage composition (%) |
| Y 2O 3 | 0.5 |
| NiO | 8.95 |
| NiFe 2O 4 | 80.55 |
| Cu | 10.00 |
Be 61.32% and 38.68% to take by weighing respectively and analyze pure Fe by mass fraction
2O
3Powder and analyze pure NiO powder, granularity is respectively 1.4 μ m and 4.1 μ m, and after ball milling mixings 2.5h and 100 ℃ of dryings, the corundum crucible of packing into places resistance furnace to calcine 6h in 1200 ℃ under air atmosphere, obtains NiFe
2O
4The spinel ceramics powder adds NiFe then
2O
4Spinelle, NiO oxide, Cu-Ni metal and Y
2O
3Powder is mixed together, its granularity is respectively 8.1 μ m, 4.1 μ m, 10 μ m and 3.5 μ m, take industrial alcohol as dispersant and the 1wt% polyvinyl alcohol be binding agent, secondary ball milling 2.5h in ball grinder, after 100 ℃ of dryings of mixed-powder under 200MPa pressure bidirectional pressed moulding be the green compact of d20mm * 40mm, green compact are at N
2Carry out degreasing in the protective atmosphere, skimming temp is 600 ℃, and degreasing time is 10h, and oxygen content is 100ppm in the atmosphere; Rise to 1300 ℃ and be incubated 4h and carry out densification sintering with the heating rate of 20 ℃/h at last, obtain final sintered sample, sample fracture sem photograph as shown in Figure 9, Y
2O
3Powder disperse distribution cermet, and the sample hole is less.(ionogen is formed 78.07%Na for density, bending strength, electric conductivity and 960 ℃ of annual corrosion rates
3AlF
6-9.5%AlF
3-5.0%CaF
2-7.43%Al
2O
3, molecular ratio is 2.3, liquidus temperature is 947 ℃, 960 ℃ of electrolysis temperatures, 13 ℃ of superheating temperature) be respectively 92.56%, 156.3MPa, 17.57Scm
-1And 5.03cm/a.960 ℃ of electrolysis 10h of its cermet inert anode corrode sample corrosion layer sem photograph as shown in figure 10, and the metallic corrosion layer thickness is 30-50 μ m, illustrates that its high temperature resistant molten salt corrosive nature is better.
Claims (6)
1. high temperature resistant molten salt corrosion ceramet anode material, it is characterized in that: described cermet inert anode material is made up of following mass percent component: the 50%-95% spinel oxides, other oxide of 1%-30%, the 1%-30% Metal Phase, the anti-corrosion hardening agent of 0.1%-2% crystal boundary; Described other oxide is A
xO
yIn a kind of or their combination, x=1 or 2; Y=1,2 or 3; A is Ni, Cu, Mn, Zn or Co; The anti-corrosion hardening agent of described crystal boundary is La
2O
3, Y
2O
3, Yb
2O
3And other+a kind of in the 3 valency lanthanide rare earth oxides or their combination, and particle size range is 2-5 μ m.
2. a kind of high temperature resistant molten salt corrosion ceramet anode material according to claim 1, it is characterized in that: described spinel oxides is MFe
2O
4And MAl
2O
4In a kind of or their combination, M is Ni, Cu, Mn, Zn or Co.
3. a kind of high temperature resistant molten salt corrosion ceramet anode material according to claim 1 is characterized in that: described metallographic phase is one or both and the above multicomponent alloy that constitutes among Fe, Ni, Cu, Co, the Ag.
4. the preparation method of the described a kind of high temperature resistant molten salt corrosion ceramet anode material of claim 1 is characterized in that,
(1) synthetic A
xO
yOther oxide and MFe
2O
4Or MAl
2O
4Spinel oxides;
(2) batch mixing: the spinel oxides that will account for cermet mass percent 50%-95%, account for other oxide of cermet mass percent 1%-30%, account for the Metal Phase of cermet mass percent 1%-30%, account for the anti-corrosion hardening agent of cermet mass percent 0.1-5%, the organic binder bond polyvinyl alcohol and the dispersant industrial alcohol that account for compound gross mass 1% carry out batch mixing 1-12h; Described other oxide is A
xO
yIn a kind of or their combination, x=1 or 2; Y=1,2 or 3; A is Ni, Cu, Mn, Zn or Co; The anti-corrosion hardening agent of described crystal boundary is La
2O
3, Y
2O
3, Yb
2O
3And other+a kind of in the 3 valency lanthanide rare earth oxides or their combination, and particle size range is 2-5 μ m;
(3) oven dry, moulding, degreasing, densification sintering obtain the sintering metal anode material.
5. the preparation method of a kind of high temperature resistant molten salt corrosion ceramet anode material according to claim 4 is characterized in that, described spinel oxides is MFe
2O
4And MAl
2O
4In a kind of or their combination, M is Ni, Cu, Mn, Zn or Co.
6. the preparation method of a kind of high temperature resistant molten salt corrosion ceramet anode material according to claim 4 is characterized in that, described metallographic phase is one or both and the above multicomponent alloy that constitutes among Fe, Ni, Cu, Co, the Ag.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009103040917A CN101586246B (en) | 2009-07-07 | 2009-07-07 | High temperature resistant molten salt corrosion ceramet anode material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009103040917A CN101586246B (en) | 2009-07-07 | 2009-07-07 | High temperature resistant molten salt corrosion ceramet anode material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101586246A CN101586246A (en) | 2009-11-25 |
| CN101586246B true CN101586246B (en) | 2011-01-05 |
Family
ID=41370669
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009103040917A Expired - Fee Related CN101586246B (en) | 2009-07-07 | 2009-07-07 | High temperature resistant molten salt corrosion ceramet anode material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101586246B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102010193A (en) * | 2010-12-15 | 2011-04-13 | 中国铝业股份有限公司 | Corrosion resistant protection material for fusedsaltelectrolysis and preparation method thereof |
| CN102226287B (en) * | 2011-06-02 | 2012-10-10 | 中南大学 | Metal phase of cermet inert anode material capable of resisting corrosion of high-temperature molten salt and preparation method and application thereof |
| CN107986799B (en) * | 2017-11-24 | 2021-01-12 | 中南大学 | Composite material for recovering flue gas waste heat of aluminum electrolysis cell and preparation method thereof |
| 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 |
| CN113215429A (en) * | 2021-04-30 | 2021-08-06 | 中南大学 | Preparation method of high-density metal ceramic inert anode material for aluminum electrolysis |
| CN113174615B (en) * | 2021-04-30 | 2024-02-13 | 中南大学 | Metal ceramic material for aluminum electrolysis inert anode and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1772961A (en) * | 2005-11-10 | 2006-05-17 | 东北大学 | Metal-base composite material inert anode for aluminium electrolysis and producing process thereof |
| CN101255577A (en) * | 2007-12-07 | 2008-09-03 | 中南大学 | Metal ceramic inert anode for molten salt electrolysis and preparation method thereof |
-
2009
- 2009-07-07 CN CN2009103040917A patent/CN101586246B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1772961A (en) * | 2005-11-10 | 2006-05-17 | 东北大学 | Metal-base composite material inert anode for aluminium electrolysis and producing process thereof |
| CN101255577A (en) * | 2007-12-07 | 2008-09-03 | 中南大学 | Metal ceramic inert anode for molten salt electrolysis and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101586246A (en) | 2009-11-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101586246B (en) | High temperature resistant molten salt corrosion ceramet anode material and preparation method thereof | |
| CN102586853B (en) | Method for improving high-temperature fused salt corrosion resistance of metal ceramic inert anode | |
| CN104087973B (en) | For manufacturing the composition of the wettable negative electrode in aluminium melting | |
| CN102173409B (en) | Preparation method for graphite carbon material | |
| CN103304239A (en) | TiB2-based metal ceramic material for aluminium cell and preparation method of material | |
| EP0783597A1 (en) | Stable anodes for aluminium production cells | |
| CN102226287B (en) | Metal phase of cermet inert anode material capable of resisting corrosion of high-temperature molten salt and preparation method and application thereof | |
| CN101724861B (en) | TiB2-C composite material for aluminum electrolytic bath and preparation method thereof | |
| CN108409315B (en) | Nickel ferrite based ceramic inert anode material for aluminum electrolysis and preparation method thereof | |
| CN107417260A (en) | The hot pressing method for preparing of magnesia ceramics | |
| CN102010193A (en) | Corrosion resistant protection material for fusedsaltelectrolysis and preparation method thereof | |
| CN103848631A (en) | Silicon nitride ceramic insulating material used for multipole magnesium electrolysis technology | |
| CN107986799B (en) | Composite material for recovering flue gas waste heat of aluminum electrolysis cell and preparation method thereof | |
| Zhang et al. | Sintering kinetics and properties of NiFe2O4‐based ceramics inert anodes doped with TiN nanoparticles | |
| CN113249755B (en) | Inert anode material and preparation method and application thereof | |
| CN104944959B (en) | A kind of TiB used for aluminium electrolysis2/ TiB composite ceramics cathode materials and preparation method thereof | |
| CN115074786B (en) | Seepage-proofing material for rare earth electrolytic tank, preparation method of seepage-proofing material and rare earth electrolytic tank | |
| CN113430577A (en) | NiFe for aluminum electrolysis2O4Inert anode material of base cermet and its prepn | |
| CN103951435A (en) | TiB2-based composite cathode material used for aluminium electrolysis and preparation method thereof | |
| JP3877630B2 (en) | Method for producing conductive ceramics | |
| CN114988410B (en) | Rare earth carbide material and preparation method and application thereof | |
| CN114570915B (en) | Preparation method of rare earth composite material | |
| CN114835497B (en) | Ceramic material for rare earth molten salt electrolytic cell and preparation method and application thereof | |
| CN117886596A (en) | Metal ceramic inert anode material with low metal phase content and preparation method thereof | |
| He | Effect of Yb 2 O 3 doping on the grain boundary of NiFe 2 O 4–10NiO-based cermets after sintering |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110105 Termination date: 20150707 |
|
| EXPY | Termination of patent right or utility model |