CN101724861B - TiB2-C composite material for aluminum electrolytic bath and preparation method thereof - Google Patents
TiB2-C composite material for aluminum electrolytic bath and preparation method thereof Download PDFInfo
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- CN101724861B CN101724861B CN2009102433891A CN200910243389A CN101724861B CN 101724861 B CN101724861 B CN 101724861B CN 2009102433891 A CN2009102433891 A CN 2009102433891A CN 200910243389 A CN200910243389 A CN 200910243389A CN 101724861 B CN101724861 B CN 101724861B
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- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 42
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000002131 composite material Substances 0.000 title abstract description 7
- 238000005245 sintering Methods 0.000 claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000654 additive Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 21
- 230000000996 additive effect Effects 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 16
- 239000010439 graphite Substances 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 238000000465 moulding Methods 0.000 claims abstract description 6
- 239000011159 matrix material Substances 0.000 claims description 43
- 239000000843 powder Substances 0.000 claims description 17
- 238000005238 degreasing Methods 0.000 claims description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- -1 polyoxyethylene Polymers 0.000 claims description 10
- 238000003825 pressing Methods 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 9
- 238000005056 compaction Methods 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 7
- 239000004698 Polyethylene Substances 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- 229910021382 natural graphite Inorganic materials 0.000 claims description 5
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 5
- 150000002910 rare earth metals Chemical class 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical group CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 4
- 239000000428 dust Substances 0.000 claims description 4
- 235000011187 glycerol Nutrition 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 3
- 239000004925 Acrylic resin Substances 0.000 claims description 3
- 229920000178 Acrylic resin Polymers 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical class N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 108010010803 Gelatin Proteins 0.000 claims description 3
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000005642 Oleic acid Substances 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 3
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910002091 carbon monoxide Inorganic materials 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
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 125000004494 ethyl ester group Chemical group 0.000 claims description 3
- 235000021323 fish oil Nutrition 0.000 claims description 3
- 229920000159 gelatin Polymers 0.000 claims description 3
- 239000008273 gelatin Substances 0.000 claims description 3
- 235000019322 gelatine Nutrition 0.000 claims description 3
- 235000011852 gelatine desserts Nutrition 0.000 claims description 3
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 3
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 3
- 229940071676 hydroxypropylcellulose Drugs 0.000 claims description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 3
- 229920005575 poly(amic acid) Polymers 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 10
- 239000007788 liquid Substances 0.000 abstract description 6
- 238000009736 wetting Methods 0.000 abstract description 4
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 abstract description 2
- 229910033181 TiB2 Inorganic materials 0.000 abstract description 2
- 230000035939 shock Effects 0.000 abstract 1
- 239000004411 aluminium Substances 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 238000005868 electrolysis reaction Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000010936 titanium Substances 0.000 description 5
- 239000010406 cathode material Substances 0.000 description 4
- 238000000280 densification Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000002457 bidirectional effect Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000011204 carbon fibre-reinforced silicon carbide Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004320 controlled atmosphere Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000001272 pressureless sintering Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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Abstract
The invention discloses TiB2-C composite material for aluminum electrolytic bath and preparation method thereof and relates to a cathode suitable for a noble electrode aluminum electrolytic bath, in particular to a preparation method of a TiB2-C wettable cathode. The TiB2-C composite material is characterized by comprising TiB2, graphite C, a metal additive agent X and an inorganic additive agent M. In a preparation process of the material, the TiB2-C composite material having relatively higher compactness and good wetting property with aluminum liquid is obtained through adjusting a molding process, sintering atmosphere and sintering temperature. The material has the properties of high strength, high wettability with the aluminum liquid, high thermal shock resistance, and the like.
Description
Technical field
A kind of aluminum electrolyzing cell used TiB
2-C matrix material and preparation method thereof relates to a kind of noble electrode cathode of aluminium electrolytic bath that is applicable to, refers more particularly to TiB
2The preparation method of-C wettability negative electrode.
Background technology
TiB
2Owing to have excellent conductivity, easily wetting, good corrosion-resistant and antioxidant property, become the preferred material of making used for aluminium electrolysis wettability inert cathode by molten metals such as aluminium.
Patent US4377463 has introduced a kind of TiB
2-graphite-asphalt high-temperature sintering technology, wherein dividing temperature section controlled atmosphere is the key of material densification.Patent US4439382, US4465581 and US45026669 have introduced TiO
2-refinery coke-binding agent-B
2O
3/ H
3BO
3The high temperature sintering technology of system.Wherein patent US45026669 also relates to a kind of TiB
2" mushroom " structure of-C matrix material.Patent US4812280, US4929328, US6534428 and US4859124 have introduced TiB
2The hot pressing and sintering technique of material.Wherein add reactive metal Fe, Ni, Co or Si
3N
4, adopt heat pressing process can significantly reduce TiB
2The sintering temperature of densification.Patent US5543370 and US4275026 have introduced TiB
2-B
4The pressureless sintering densification technology of C/SiC matrix material.Patent CN101158047A and CN101158048A have introduced a kind of by vibratory compaction, directly the production method of the greying wettability cathode carbon pieces of synthetic titanium diboride layer.Patent CN1203216C, CN1245538C and CN1245537C have introduced a kind of preparation method of electrolysis of aluminum titanium boride cathode material with gradient function coating.
By above patent as can be known, at present, the wettable negative electrode of using in Aluminium Electrolysis is mainly by coating paint-on technique, TiB
2Vibratory compaction of-C particle and heat pressing process obtain.The TiB that adopts the coating paint-on technique to obtain
2-C negative electrode often needs electric heating device for baking dreg solidified coating, and with brush or fur Cylinder coating brush TiB
2Coating is to TiB
2The coating applied pressure is limited, causes TiB
2Coating is not ideal enough to the wettability of aluminium electrolytic cell cathode charcoal liner, does not reach moistening effect fully, thereby makes TiB
2Coating and carbon anode/cathode bonding are insecure.The TiB that adopts the vibratory compaction technology to obtain
2-C surface recombination negative electrode is a heterogeneous material, only can realize TiB
2The mechanical bond of functional layer and carbon basal body layer, and TiB
2The cohesive strength of layer and corrosion-resistant, abrasion resistance properties, there are in various degree problem and because such vibratory compaction TiB with the wettability of aluminium liquid etc.
2-C composite cathode is a heterogeneous material, and negative electrode only has one side to be rich TiB
2Layer can't satisfy the needs of aluminum electrolysis process.And the TiB that adopts heat pressing process to prepare
2Though/C composite cathode material can satisfy the technical requirements of efficient green novel aluminum electrolysis process substantially; but because its making and tooling cost are especially expensive; and there is obvious defects in this technology at aspects such as realizing material maximization, abnormally-structured design, can't accomplish scale production.
Goal of the invention
Purpose of the present invention is exactly the deficiency that exists at above-mentioned prior art, provide a kind of can be wetting with aluminium liquid height, refractory melts ionogen and oozes erosion and the erosion of aluminium liquid, high conduction and low-cost, can effectively realize cryogenic activating sintering, the aluminum electrolyzing cell used TiB of the material that homogenizes
2-C matrix material and preparation method thereof.
The objective of the invention is to be achieved through the following technical solutions.
A kind of aluminum electrolyzing cell used TiB
2-C matrix material is characterized in that described TiB
2-C matrix material comprises TiB
2, graphite C, metal additive X, inorganic additives M.
A kind of aluminum electrolyzing cell used TiB of the present invention
2-C matrix material is characterized in that described TiB
2The TiB of-C matrix material
2Weight percentage is 30%～90%, TiB
2Purity is greater than 98%, and the weight percent content of described graphite C is 0.1%～60%, and its graphite C is at least a in natural graphite, the synthetic graphite, and graphite C purity is greater than 99%.
A kind of aluminum electrolyzing cell used TiB of the present invention
2-C matrix material is characterized in that described TiB
2The metal additive X of-C matrix material is at least a in Ni, Ti, Al, Co, Fe and the rare earth metal, and weight percentage is 0.1%～10%; Non-metallic additive is B, BN, AlN, B
4C, Y
2O
3, at least a among TiN, the TiC, weight percentage is 0.1%～10%.
A kind of aluminum electrolyzing cell used TiB
2The preparation method of-C matrix material is characterized in that its preparation process may further comprise the steps:
1) batch mixing
With metal-powder X, TiB
2, graphite C powder, non-metallic additive M and dispersion agent, binding agent mix and pinch or ball milling mixes, oven dry is handled; Wherein, X is for to be selected from the metal of Ni, Ti, Al, Co, Fe and rare earth and their combination at least, and M is selected from B, BN, AlN, B at least
4C, Y
2O
3, the nonmetallic compound of TiN, TiC and their combination;
2) moulding, degreasing
Mixing raw material is carried out pressure forming make TiB
2-C matrix material green compact, and skimming treatment under inert atmosphere;
3) sintering
Degreasing blank is carried out sintering under protectiveness inert atmosphere or vacuum.
A kind of aluminum electrolyzing cell used TiB of the present invention
2The preparation method of-C matrix material, the TiB when it is characterized in that batch mixing
2The grain diameter of raw material is 1 μ m～10mm; The grain diameter of graphite C raw material is 1 μ m～100 μ m.
A kind of aluminum electrolyzing cell used TiB of the present invention
2The preparation method of-C matrix material, it is characterized in that its dispersion agent is at least a in the adjacent dioctyl phthalate of water, alcohol, benzene, oleic acid, ammonia salts solution, polyacrylamide solution, fish oil, o-butyl-2 salt, polyacrylic ester, the poly amic acid, adding weight percentage is 0.1～3.0%; Used binding agent is at least a in polyvinyl alcohol, glycerine, carboxymethyl cellulose, hydroxy propyl cellulose, acrylic resin solution, sulfite solution, gelatin, polyoxyethylene glycol, polyethylene butyl ester, polyethylene ethyl ester, polyvinyl alcohol, the polyacrylic acid, and adding weight percentage is 0.1～5.0%.
A kind of aluminum electrolyzing cell used TiB of the present invention
2The preparation method of-C matrix material is characterized in that the oven dry processing of batch mixing process is carried out under 100～150 ℃.
A kind of aluminum electrolyzing cell used TiB of the present invention
2The preparation method of-C matrix material is characterized in that its pressure forming obtains TiB
2The process of-C matrix material green compact adopts mold pressing or cast-isostatic cool pressing method or vibratory compaction, and pressure is 100MPa～400MPa.
A kind of aluminum electrolyzing cell used TiB of the present invention
2The preparation method of-C matrix material is characterized in that its skimming treatment temperature is 300 ℃～900 ℃; The inert atmosphere that adopts in the skimming treatment process is at least a from N
2, Ar, CO
2, H
2Or their combination, degreasing time is 6h～72h, the atmosphere Control for Oxygen Content is at 10～50ppm.
A kind of aluminum electrolyzing cell used TiB of the present invention
2The preparation method of-C matrix material, the atmosphere that it is characterized in that its sintering process are at least a from vacuum, N
2, Ar, CO
2, H
2Or their combination; Sintering time is 10h～24h, O in the sintering atmosphere
2Content is controlled to be 1ppm～10ppm, and sintering temperature is 1200 ℃～1800 ℃, and wherein preferred temperature is 1550 ℃～1750 ℃; Sintering process adopts the carbon dust landfill to carry out.
A kind of aluminum electrolyzing cell used TiB of the present invention
2-C matrix material, functional with aluminum-liquid wetting, the electric conductivity height, wear-resistant; Under atmospheric low-temperature, can realize the densification sintering of material, can realize TiB
2The homogeneous moulding of-C cathode material, manufacturing cost is far below heat pressing process.
Description of drawings
Fig. 1 is the process flow sheet of the inventive method.
Embodiment
A kind of aluminum electrolyzing cell used TiB
2-C matrix material, its matrix material comprises TiB
2, X graphite C, metal additive X, inorganic additives M; TiB wherein
2The TiB of-C matrix material
2Weight percentage is 30%～90%, and the weight percent content of described graphite C is 0.1%～60%, and its graphite C is at least a in natural graphite, the synthetic graphite; Metal additive X is at least a in Ni, Ti, Al, Co, Fe and the rare earth metal, and weight percentage is 0.1%～10%; Non-metallic additive is B, BN, AlN, B
4C, Y
2O
3, at least a among TiN, the TiC, weight percentage is 0.1%～10%.
A kind of aluminum electrolyzing cell used TiB of the present invention
2The step of the preparation process of-C matrix material comprises:
(1) with TiB
2Powder, Graphite Powder 99, metal additive, inorganic non-metallic additive are prepared burden by proportioning, wherein, and TiB
2Weight percentage is 30%～90%, and the Graphite Powder 99 weight percentage is 0.1～60%, and metal additive X weight percentage accounts for 0.1%～10%, and inorganic non-metallic additive M weight percentage is 0.1%～10%;
(2) above-mentioned powder adding dispersion agent and binding agent are carried out ball mill mixing, wherein used dispersion agent can be water, alcohol, the adjacent dioctyl phthalate of benzene, oleic acid, ammonia salts solution, polyacrylamide solution, fish oil, o-butyl-2 salt, polyacrylic ester, at least a in the poly amic acid accounts for 0.1～3.0% of ingredients by weight percentage composition total amount; Used binding agent is a polyvinyl alcohol, glycerine, carboxymethyl cellulose, hydroxy propyl cellulose, acrylic resin solution, sulfite solution, gelatin, polyoxyethylene glycol, polyethylene butyl ester, the polyethylene ethyl ester, polyvinyl alcohol, at least a in the polyacrylic acid accounts for 0.1～5.0% of ingredients by weight percentage composition total amount;
(3) with above-mentioned raw materials after 100～150 ℃ down oven dry removes fluid additive, adopt mold pressing or cast-isostatic cool pressing method or vibratory compaction to obtain TiB at 100～400MPa compacted under
2-C matrix material green compact;
(4) will make TiB
2-C matrix material green compact are 300～900 ℃ of following degreasings, and wherein degreasing atmosphere keeps oxygen level at 10～50ppm;
(5) will make TiB
2-C matrix material green compact are under 1200～1800 ℃ and control sintering atmosphere sintering green compact, obtain TiB
2-C matrix material.
With the TiB that makes
2-C matrix material carries out mechanical workout, can make used for aluminium electrolysis TiB
2-C composite cathode material.
Embodiment 1
With the 55wt.% granularity is the technical pure TiB of 1 μ m
2Powder, 5wt.% granularity are the technical pure TiB of 10mm
2Particle, 30wt.% granularity are graphous graphite powder, 5wt.% metal Ti powder, 4.9wt.% metal A l powder, the 0.1wt.%Y of 1 μ m
2O
3Powder places planetary ball mill, is that dispersion agent and 0.1wt.%PVA carry out ball milling mixing 300min in the ball-milling medium of binding agent containing the 3.0wt.% industrial spirit, and 100 ℃ of dry 24h down adopt bidirectional pressed moulding to obtain TiB under 400MPa pressure
2-C matrix material green compact place electric furnace with green compact, and (Ar) carries out degreasing in the inertia protective atmosphere, and skimming temp is 900 ℃, and degreasing time is 6h, and oxygen level is 50ppm in the atmosphere; Rise to 1550 ℃ with the temperature rise rate of 100 ℃/h then under the protection of high-purity Ar and carry out sintering, soaking time is 8h, and oxygen level is 10ppm in the sintering atmosphere, obtains density and is about 85% sample.
Embodiment 2
With technical pure TiB
2Powder, graphous graphite powder, metal Ti powder, boron powder respectively according to 60%, 20%, 10% and 10% (mass percent) proportioning in kneading machine, containing the 2.0wt.% industrial spirit is that dispersion agent and 5.0wt.% glycerine are to mix 300min in the medium of binding agent, dry 24h under 150 ℃ adopts vibratory compaction to obtain TiB under 100MPa pressure
2-C matrix material green compact place electric furnace with green compact, adopt the carbon dust landfill to carry out sintering under 1800 ℃, wherein 30 ℃～900 ℃ interval degreasings, and degreasing time is 72h, oxygen level is 10ppm in the atmosphere; Heat-up rate at 900～1800 ℃ of interval 100 ℃/h of employing heats up, and is incubated 8 hours down in 1800 ℃, and oxygen level is 1ppm in the atmosphere, obtains density and is about 90% sample.
Embodiment 3
With the 30wt.% granularity is 5 μ m TiB
2Powder, 60wt.% granularity are natural graphite powder, 0.1wt.% metal Ni, the 5wt.%B of 100 μ m
4C, the 4.9wt.%BN powder places planetary ball mill, containing the adjacent dioctyl phthalate of 0.1wt.% benzene is that dispersion agent and 2.0wt.%PVA carry out ball milling mixings 300min in the ball-milling medium of binding agent, 100 ℃ of dry 24h down, and the employing bidirectional pressed moulding obtains TiB under 400MPa pressure
2-C matrix material green compact place electric furnace with green compact, (Ar+H in the inertia protective atmosphere
2) carrying out degreasing, skimming temp is 600 ℃, and degreasing time is 24h, and oxygen level is 10ppm in the atmosphere; Temperature rise rate with 100 ℃/h rises to 1600 ℃ under the protection of high-purity Ar then, insulation 1h, and oxygen level is 10ppm in the atmosphere, at this moment, vacuumizes and continues to be warming up to 1750 ℃ and carry out sintering, soaking time is 10h,, obtain density and be about 91% sample.
Embodiment 4
With the 80wt.% granularity is 1 μ m TiB
2Powder, 10wt.% granularity are 5mm TiB
2Particle, 0.1% granularity are that natural graphite powder, 4wt.%TiC powder, the 5.9wt.%AlN powder of 1 μ m places kneading machine, containing the 2.0wt.% industrial spirit is that dispersion agent and 5.0wt.% polyoxyethylene glycol are to mix 180min in the medium of caking agent, dry 24h under 120 ℃ adopts vibratory compaction to obtain TiB at 200MPa pressure
2-C matrix material green compact place electric furnace with green compact, adopt the carbon dust landfill to carry out sintering under 1200 ℃, and skimming temp is 600 ℃, and degreasing time is 60h, and oxygen level is 10～50ppm in the atmosphere; Under vacuum state, adopt the heat-up rate of 100 ℃/h to heat up in 900～1200 ℃ of intervals, and be incubated 8 hours down, obtain density and be about 80% sample in 1200 ℃.
Claims (5)
1. aluminum electrolyzing cell used TiB
2-C matrix material is characterized in that described TiB
2-C matrix material comprises TiB
2, graphite C, metal additive X, inorganic additives M; Described TiB
2The TiB of-C matrix material
2Weight percentage is 30%～90%, TiB
2Purity is greater than 98%, and the weight percent content of described graphite C is 0.1%～60%, and its graphite C is at least a in natural graphite, the synthetic graphite, and graphite C purity is greater than 99%; Described TiB
2The metal additive X of-C matrix material is at least a in Ni, Ti, Al, Co, Fe and the rare earth metal, and weight percentage is 0.1%～10%; Inorganic additives M is B, BN, A1N, B
4C, Y
2O
3, at least a among TiN, the TiC, weight percentage is 0.1%～10%.
2. aluminum electrolyzing cell used TiB
2The preparation method of-C matrix material is characterized in that its preparation process may further comprise the steps:
1) batch mixing
With metal-powder X, TiB
2, graphite C powder, non-metallic additive M and dispersion agent, binding agent mix and pinch or ball milling mixes, oven dry is handled; Wherein, X is for to be selected from the metal of Ni, Ti, Al, Co, Fe and rare earth and their combination at least, and M is selected from B, BN, A1N, B at least
4C, Y
2O
3, the nonmetallic compound of TiN, TiC and their combination; Oven dry is handled and is carried out under 100～150 ℃;
2) moulding, degreasing;
Mixing raw material is carried out pressure forming make TiB
2-C matrix material green compact, its pressure forming process adopts mold pressing or cast-isostatic cool pressing method or vibratory compaction, and pressure is 100MPa～400MPa; And skimming treatment under inert atmosphere, its skimming treatment temperature is 300 ℃～900 ℃; The inert atmosphere that adopts in the skimming treatment process is at least a from N
2, Ar, CO
2, H
2Or their combination, degreasing time is 6h～72h, the atmosphere Control for Oxygen Content is at 10～50ppm;
3) sintering
Degreasing blank is carried out sintering under protectiveness inert atmosphere or vacuum; The atmosphere of its sintering process is vacuum or at least a from N
2, Ar, C0
2, H
2Or their combination; Sintering time is 10h～24h, O in the sintering atmosphere
2Content is controlled to be 1ppm～10ppm, and sintering temperature is 1200 ℃～1800 ℃; Sintering process adopts the carbon dust landfill to carry out.
3. a kind of aluminum electrolyzing cell used TiB according to claim 2
2The preparation method of-C matrix material, the TiB when it is characterized in that batch mixing
2The grain diameter of raw material is 1 μ m～10mm; The grain diameter of graphite C raw material is 1 μ m～100 μ m.
4. a kind of aluminum electrolyzing cell used TiB according to claim 2
2The preparation method of-C matrix material, it is characterized in that its dispersion agent is at least a in the adjacent dioctyl phthalate of water, alcohol, benzene, oleic acid, ammonia salts solution, polyacrylamide solution, fish oil, o-butyl-2 salt, polyacrylic ester, the poly amic acid, adding weight percentage is 0.1%～3.0%; Used binding agent is at least a in polyvinyl alcohol, glycerine, carboxymethyl cellulose, hydroxy propyl cellulose, acrylic resin solution, sulfite solution, gelatin, polyoxyethylene glycol, polyethylene butyl ester, polyethylene ethyl ester, polyvinyl alcohol, the polyacrylic acid, and adding weight percentage is 0.1%～5.0%.
5. a kind of aluminum electrolyzing cell used TiB according to claim 2
2The preparation method of-C matrix material is characterized in that its sintering temperature is 1550 ℃～1750 ℃.
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| RU2540953C2 (en) * | 2009-07-28 | 2015-02-10 | Алкоа Инк. | Composition for obtaining wetted cathode at aluminium melting |
| CN102744410A (en) * | 2012-04-27 | 2012-10-24 | 中国铝业股份有限公司 | Method for preparing TiB2 layer of cathode for aluminum electrolytic bath |
| CN103304239A (en) * | 2013-06-27 | 2013-09-18 | 中国铝业股份有限公司 | TiB2-based metal ceramic material for aluminium cell and preparation method of material |
| RU2660448C2 (en) * | 2015-04-23 | 2018-07-06 | Общество с ограниченной ответственностью "Объединенная Компания РУСАЛ Инженерно-технологический центр" | Electrode of aluminum electrolytic cell (options) |
| CN105821459B (en) * | 2016-03-29 | 2018-06-26 | 常州大学 | A kind of method for preparing boride coating in stainless steel surface |
| CN109943865A (en) * | 2019-04-28 | 2019-06-28 | 镇江慧诚新材料科技有限公司 | A kind of oxygen aluminium coproduction cathode for electrolyzing material and preparation method thereof |
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