CN103194101B - A kind of titanium boride base coating composite material used for aluminium electrolysis and preparation method thereof, coating method - Google Patents
A kind of titanium boride base coating composite material used for aluminium electrolysis and preparation method thereof, coating method Download PDFInfo
- Publication number
- CN103194101B CN103194101B CN201310101483.XA CN201310101483A CN103194101B CN 103194101 B CN103194101 B CN 103194101B CN 201310101483 A CN201310101483 A CN 201310101483A CN 103194101 B CN103194101 B CN 103194101B
- Authority
- CN
- China
- Prior art keywords
- titanium boride
- composite material
- aluminium electrolysis
- coating
- oxide
- 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.)
- Active
Links
- 239000010936 titanium Substances 0.000 title claims abstract description 58
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 58
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000000576 coating method Methods 0.000 title claims abstract description 50
- 239000011248 coating agent Substances 0.000 title claims abstract description 43
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 31
- 239000004411 aluminium Substances 0.000 title claims abstract description 30
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000010439 graphite Substances 0.000 claims abstract description 35
- 239000000463 material Substances 0.000 claims abstract description 31
- 238000005245 sintering Methods 0.000 claims abstract description 28
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 27
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 20
- 239000011246 composite particle Substances 0.000 claims abstract description 19
- 239000000758 substrate Substances 0.000 claims abstract description 15
- 229920005989 resin Polymers 0.000 claims abstract description 14
- 239000011347 resin Substances 0.000 claims abstract description 14
- 239000000428 dust Substances 0.000 claims abstract description 8
- 239000000654 additive Substances 0.000 claims abstract description 7
- 230000000996 additive effect Effects 0.000 claims abstract description 7
- 239000003292 glue Substances 0.000 claims abstract description 7
- 239000012745 toughening agent Substances 0.000 claims abstract description 7
- 238000007711 solidification Methods 0.000 claims abstract description 6
- 230000008023 solidification Effects 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 240000003936 Plumbago auriculata Species 0.000 claims abstract 2
- 238000004898 kneading Methods 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000001354 calcination Methods 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 229940043232 butyl acetate Drugs 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- 239000000835 fiber Substances 0.000 claims description 6
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- 229920003987 resole Polymers 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 6
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 claims description 5
- 239000003830 anthracite Substances 0.000 claims description 5
- 239000000571 coke Substances 0.000 claims description 5
- 239000003822 epoxy resin Substances 0.000 claims description 5
- 229920000647 polyepoxide Polymers 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- 239000010980 sapphire Substances 0.000 claims description 4
- 229910052594 sapphire Inorganic materials 0.000 claims description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 3
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- 229920006122 polyamide resin Polymers 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 3
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 3
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 2
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 2
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 claims description 2
- ZETYUTMSJWMKNQ-UHFFFAOYSA-N n,n',n'-trimethylhexane-1,6-diamine Chemical compound CNCCCCCCN(C)C ZETYUTMSJWMKNQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002002 slurry Substances 0.000 abstract description 21
- 239000011261 inert gas Substances 0.000 abstract description 7
- 239000011159 matrix material Substances 0.000 abstract description 7
- 230000003628 erosive effect Effects 0.000 abstract description 5
- 230000021615 conjugation Effects 0.000 abstract description 2
- 239000002245 particle Substances 0.000 description 9
- 241000209456 Plumbago Species 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000013467 fragmentation Methods 0.000 description 5
- 238000006062 fragmentation reaction Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 description 1
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 1
- -1 aluminium Chemical class 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910001610 cryolite Inorganic materials 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Landscapes
- Ceramic Products (AREA)
Abstract
The invention discloses a kind of titanium boride base coating composite material used for aluminium electrolysis and preparation method thereof, coating method, described matrix material is made up of following raw material by weight percentage: titanium boride-oxide composite particle: 55% ~ 70%; Carbonaceous additive: 8% ~ 15%; Organic resin glue: 15% ~ 30%; Toughener: 0.5% ~ 2%.Described coating method comprises the following steps: graphite substrate material is put into coating die by (1), then pours in mould by the slurry obtained; (2) body material of slurry will be coated with at 15 DEG C ~ 35 DEG C solidification treatment 24h ~ 48h, and then at 80 DEG C ~ 150 DEG C solidification treatment 12h ~ 24h; (3) body material step (2) being coated with slurry is placed in plumbago crucible, landfill graphite carbon dust, then carries out charing sintering in inert gas atmosphere or in vacuum; Described charing sintering temperature is 850 ~ 1050 DEG C, and charing sintering time is 80h ~ 120h.One of the present invention titanium boride used for aluminium electrolysis base coating composite material and matrix conjugation high, tensile strength can reach 8-10MPa; Coating structure is fine and close, erosion resistibility is strong.
Description
technical fieldthe present invention relates to electrochemical field, be specifically related to one and be applicable to noble electrode negative electrode titanium boride used for aluminium electrolysis based composites and technology of preparing thereof.
Background technology
Cathode material in aluminum electrolyzation technology not only will carry electric action, also to bear the chemical erosion of high temperature cryolite melts and the physics erosion of aluminium liquid, aluminium cell of the prior art generally all adopts carbonaceous cathodes material, the electrolyte-resistant penetrating quality poor due to it and not good with aluminium liquid wetting, the efficient stable having had a strong impact on electrolyzer runs.Titanium boride is owing to having excellent conductivity, easily being soaked by molten metals such as aluminium, and excellent corrosion-resistant and high-temperature oxidation resistance, therefore becomes the preferred material manufacturing wettability inert cathode used for aluminium electrolysis.Patent CN1537975 introduces titanium boride/aluminum oxide cathode and forms the component of coating, wherein adopts TiB in this coating
2/ Al
2o
3matrix material replaces pure TiB
2component, have impact on the conductivity of coating.Patent CN101914786 describes a kind of technology of preparing and paint-on technique of coating paste, and this technology can realize coating being uniformly distributed on carbon base body surface, but coat-thickness is thinner, is difficult to tolerate aluminium liquid for a long time and washes away.At present, the wettable cathode material applied in Aluminium Electrolysis obtains primarily of coating paint-on technique, vibratory compaction and heat pressing process.And it is the most conventional in Aluminium Electrolysis based on the coating paint-on technique of manual application mode.Patent US5651874, CN1448542, CN1405358 and CN1537974 describe a kind of preparation method of electrolysis of aluminum titanium boride-C cathode material coating, the method is that thermosetting resin etc. is mixed with into high thick thickener with powders of titanium boride, is painted on aluminium cell carbon cathode surface by hand.Patent US6436250B1, US5728466 describe sol-gel processing and prepare titanium boride-MO coating technology (MO represents metal oxide), substantially increase the bonding force of electroconductibility and coating and matrix.But employing manual brushing method is carried out constructing and be there is certain deficiency, as: (1) productivity is low, labour intensity is large; (2) coat-thickness heterogeneity, surface irregularity, unfairness; (3) brush applied coating is thicker, and make the heat-shock impact when electrolyzer electrical roasting, startup large, coefficient of thermal expansion mismatch causes thermal stresses uneven, finally causes early stage the coming off of coating.
Summary of the invention
Object of the present invention is exactly the deficiency existed for prior art, there is provided one to solve and between carbon basal body, possess good thermal expansion matching, anti-sodium potassium expands, resistance to fused electrolyte wetting with aluminium liquid height oozes and lose and the erosion of aluminium liquid, high connductivity and low cost, easy working titanium boride base coating composite material used for aluminium electrolysis, and the present invention will provide the preparation method of this matrix material and the coating method with this material simultaneously.
The object of the invention is to be achieved through the following technical solutions:
A kind of titanium boride base coating composite material used for aluminium electrolysis, is made up of following raw material by weight percentage:
Titanium boride-oxide composite particle: 55% ~ 70%; Carbonaceous additive: 8% ~ 15%; Organic resin glue: 15% ~ 30%; Toughener: 0.5% ~ 2%.
Described titanium boride-oxide composite particle, is mixed by 60% ~ 90% titanium boride and 10% ~ 40% oxide sol by weight percentage, and described oxide sol solid content is 5% ~ 30%.
Described oxide sol is at least one in alumina sol, magnesium oxide colloidal sol, titanium oxide sol, zinc oxide colloidal sol or silica sol.
Carbonaceous additive is at least one in graphite, refinery coke or electric calcined anthracite.
Described organic resin glue is made up of binding agent, dispersion agent, solidifying agent; The mass percentage of each component is respectively binding agent 35% ~ 58%, dispersion agent 40% ~ 64%, solidifying agent 1% ~ 5%.
Described binding agent is at least one in pitch, furane resin, resol, epoxy resin or furfuryl resin; Dispersion agent is at least one in acetone, butanone, ethanol or butylacetate; Solidifying agent is at least one in tosic acid, polyamide resin, m-xylene diamine, hexamethylenetetramine, trimethylhexamethylenediamine, diethyl amino propylamine, quadrol or diethylenetriamine.
Described toughener is at least one in carbon fiber, silicon carbide fiber, sapphire whisker, Zirconium oxide fibre or titanium carbide.
Prepare the method for above-mentioned titanium boride base coating composite material, comprise the following steps:
First prepare titanium boride-oxide composite particle, by the proportioning of above-mentioned titanium boride and oxide sol, titanium boride and oxide sol are stirred, after 700 ~ 1000 DEG C of calcinings, broken mistake 100-150 mesh sieve obtains;
By the proportioning raw materials of above-mentioned titanium boride base coating composite material, titanium boride-oxide composite particle, carbonaceous additive, organic resin glue, toughener are carried out kneading stirring, obtain applying slurry; Kneading temperature is 15 DEG C ~ 35 DEG C, and in air, relative humidity is 30% ~ 90%, and the kneading time is 2 ~ 6h.
With the coating method of above-mentioned titanium boride base coating composite material, comprise the following steps:
(1) apply, graphite substrate material is put into coating die, the distance at graphite substrate material upper surface and mould edge suitable for reading, and graphite substrate material surrounded surface is consistent with the gap size between mold wall, then pours in mould by slurry obtained above;
(2) solidify, will the body material of slurry be coated with at 15 DEG C ~ 35 DEG C solidification treatment 24h ~ 48h, and then at 80 DEG C ~ 150 DEG C solidification treatment 12h ~ 24h;
(3) charing sintering, is placed in plumbago crucible by the body material that step (2) is coated with slurry, landfill graphite carbon dust, then carries out charing sintering in inert gas atmosphere or in vacuum; Described charing sintering temperature is 850 ~ 1050 DEG C, and charing sintering time is 80h ~ 120h.
Rare gas element described in step (3) is that Ar is or/and N
2; O in described inert gas atmosphere or in vacuum
2content controls as 10ppm ~ 50ppm; Described vacuum is 10
-1pa.
The present invention compared with prior art, has following obvious advantage:
One of the present invention titanium boride base used for aluminium electrolysis coating composite material, titanium boride composition profiles is reasonable, void content is low, effectively prevents electrolytical infiltration, and can form uniform aluminium liquid film on surface; Coated material and matrix conjugation high, tensile strength can reach 8-10MPa; Coating structure is fine and close, erosion resistibility is strong.Due to the sintering aid added, effectively reduce the sintering temperature of matrix material, manufacturing cost is far below heat pressing process.
Adopt mould pilot brush to be coated with process in the present invention, make coating processes to realize automatization, coat-thickness is controlled, homogeneous, effectively controls the planeness of coatingsurface, smooth finish.
Embodiment
Embodiment 1
First the titanium oxide sol (also directly can buy from market) that solid content is 5% is prepared, then 70% titanium boride (median size 5 ~ 10 μm) and 30% titanium oxide sol are uniformly mixed, calcination processing is carried out again at 700 DEG C, then after calcining, 100-150 sieve is crossed in material fragmentation, obtains titanium boride-titanium composite particles powder.By 55% titanium boride-titanium composite particles, 8% Graphite Powder 99 (particle diameter is 10-150), 5% refinery coke (40-50 μm), 7% furane resin, 3.5% epoxy resin, 10% ethanol, 5.2% butanone, 4% butylacetate, 0.3% polyamide resin, 1% sapphire whisker, 1% titanium carbide are placed in kneading pot and stir, kneading temperature is 15 DEG C, in air, relative humidity is 30%, the kneading time is 5h, obtains applying slurry.Slurry after kneading is coated on graphite substrate material surface, and coating operates according to the following steps: loaded in coating die by coated body material, one of body material facing to mould openings, remaining four are provided with gap between face and mould.Body material this one side facing to mould openings and the distance at mould mouth edge, and remaining four gap width between face and mould, be coat-thickness.Slurry obtained above is poured into, until slurry is concordant with mould mouth edge in mould.After slurry is poured into, usable sheet is scraped along mould mouth edge, to ensure that slurry is concordant with mould mouth edge, within 2-5 minute, gets final product the demoulding.Graphite substrate material after the demoulding is isothermal curing 24h at 20 DEG C, then isothermal curing 12h at 80 DEG C, be placed in plumbago crucible again and put into electric furnace, landfill graphite carbon dust, then in rare gas element Ar atmosphere, carry out charing sintering, charing sintering temperature is 900 DEG C, and charing sintering time is 80h, and the oxygen level in inert gas atmosphere is 50ppm.
Obtain the sample that resistivity is 29 μ Ω m.
Embodiment 2
First preparing solid content is the alumina sol of 15%, then 60% titanium boride and 40% alumina sol are uniformly mixed, finally at 1000 DEG C, carry out calcination processing, then 100-150 mesh sieve is crossed in material fragmentation after calcining and obtain titanium boride-alumina composite particle powder.By 70% titanium boride-alumina composite particle, 5% Graphite Powder 99 (particle diameter is 10-150 μm), 3% electric calcined anthracite (particle diameter is 100-150 μm), 6% pitch (150-200 μm), 4% resol, 1.6% furfuryl resin, 4% ethanol, 3% acetone, 1% butylacetate, 0.4% tosic acid, 2% carbon fiber is placed in kneading pot and stirs, kneading temperature is 25 DEG C, in air, relative humidity is 50%, the kneading time is 6h, obtains applying slurry.Slurry after kneading is coated on graphite substrate material surface, isothermal curing 48h at 25 DEG C, then isothermal curing 24h at 150 DEG C, be placed in plumbago crucible again and put into electric furnace, landfill graphite carbon dust, then carries out charing sintering in rare gas element Ar atmosphere, and charing sintering temperature is 950 DEG C, charing sintering time is 100h, and the oxygen level in inert gas atmosphere is 10ppm.
Obtain the sample that resistivity is 38 μ Ω m.
All the other are implemented as embodiment 1.
Embodiment 3
First preparing solid content is the silica sol of 30%, then 90% titanium boride and 10% silica sol are uniformly mixed, finally at 900 DEG C, carry out calcination processing, then 100-150 mesh sieve is crossed in material fragmentation after calcining and obtain titanium boride-silicon oxide composite particle powder.By 65% titanium boride-silicon oxide composite particles, 9.5% electric calcined anthracite (particle diameter is 100-150 μm), 5% pitch (particle diameter is 150-200 μm), 3% resol, 2% epoxy resin, 5.5% ethanol, 9% acetone, 0.5% quadrol, 0.5% silicon carbide fiber is placed in kneading pot and stirs, kneading temperature is 35 DEG C, in air, relative humidity is 70%, the kneading time is 2h, obtains applying slurry; Slurry after kneading is coated on graphite substrate material surface, isothermal curing 30h at 35 DEG C, then isothermal curing 12h at 90 DEG C, then is placed in plumbago crucible and puts into electric furnace, landfill graphite carbon dust, then at rare gas element N
2can be arbitrary proportion with Ar(, both are with 1:1 mixing in the present embodiment) carry out charing sintering in atmosphere, carbonizing sintering temperature is 1050 DEG C, and charing sintering time is 90h, and the oxygen level in inert gas atmosphere is 30ppm.
Obtain the sample that resistivity is 48 Ω cm.
All the other are implemented as embodiment 1.
Embodiment 4
First the magnesium oxide colloidal sol that solid content is 20% is prepared, then 80% titanium boride and 20% magnesium oxide colloidal sol are uniformly mixed, finally at 880 DEG C, carry out calcination processing, then 100-150 mesh sieve is crossed in material fragmentation after calcining and obtain titanium boride-magnesium oxide composite particle powder.By 58.5% titanium boride-magnesium oxide composite particles, 8.5% graphite (particle diameter is 10-150 μm), 6.5% refinery coke (particle diameter is 40-50 μm), 8% pitch (particle diameter is 10-150 μm), 4.5% resol, 6.5% ethanol, 3% butanone, 2.6% butylacetate, 0.4% diethylenetriamine, 1.5% Zirconium oxide fibre is placed in kneading pot and stirs, and kneading temperature is 30 DEG C, and in air, relative humidity is 70%, the kneading time is 2h, obtains applying slurry; Slurry after kneading is coated on graphite substrate material surface, isothermal curing 30h at 35 DEG C, then isothermal curing 12h at 90 DEG C, then is placed in plumbago crucible and puts into electric furnace, landfill graphite carbon dust, then at rare gas element N
2carry out charing sintering in atmosphere, charing sintering temperature is 980 DEG C, and charing sintering time is 90h, and the oxygen level in inert gas atmosphere is 20ppm.
Obtain the sample that resistivity is 26 μ Ω m.
All the other are implemented as embodiment 1.
Embodiment 5
First the zinc oxide colloidal sol that solid content is 18% is prepared, then 75% titanium boride and 25% zinc oxide colloidal sol are uniformly mixed, at 900 DEG C, carry out calcination processing again, then 100-150 mesh sieve is crossed in material fragmentation after calcining and obtain titanium boride-zinc oxide composite particle powder.By 66.8% titanium boride-zinc oxide composite particles, 8% graphite (particle diameter 10-150 μm), 3% refinery coke (40-50 μm), 3% electric calcined anthracite (100-150 μm), 5% epoxy resin, 4% resol, 4.5% ethanol, 2.5% butanone, 1.1% butylacetate, 5% m-xylene diamine, 1.2% sapphire whisker is placed in kneading pot and stirs, kneading temperature is 30 DEG C, in air, relative humidity is 50%, and the kneading time is 4h, obtains applying slurry; Slurry after kneading is coated on graphite substrate material surface, isothermal curing 30h at 30 DEG C, then isothermal curing 12h at 90 DEG C, then is placed in plumbago crucible and puts into electric furnace, landfill graphite carbon dust, then in vacuum, (vacuum tightness is 10
-1pa) carry out charing sintering in atmosphere, charing sintering temperature is 850 DEG C, and charing sintering time is 90h.
Obtain the sample that resistivity is 35 μ Ω m.
All the other are implemented as embodiment 1.
Claims (8)
1. a titanium boride base coating composite material used for aluminium electrolysis, is characterized in that being made up of following raw material by weight percentage:
Titanium boride-oxide composite particle: 55% ~ 70%; Carbonaceous additive: 8% ~ 15%; Organic resin glue: 15% ~ 30%; Toughener: 0.5% ~ 2%;
Described titanium boride-oxide composite particle, is mixed by 60% ~ 90% titanium boride and 10% ~ 40% oxide sol by weight percentage, and described oxide sol solid content is 5% ~ 30%;
Titanium boride-oxide composite particle is prepared by following steps, titanium boride and oxide sol is stirred, and after 700 ~ 1000 DEG C of calcinings, broken 100-150 mesh sieve of crossing obtains;
Titanium boride-oxide composite particle, carbonaceous additive, organic resin glue, toughener are carried out kneading stirring, obtains titanium boride base coating composite material used for aluminium electrolysis; Kneading temperature is 15 DEG C ~ 35 DEG C, and in air, relative humidity is 30% ~ 90%, and the kneading time is 2 ~ 6h.
2. one according to claim 1 titanium boride base used for aluminium electrolysis coating composite material, is characterized in that: described oxide sol is at least one in alumina sol, magnesium oxide colloidal sol, titanium oxide sol, zinc oxide colloidal sol or silica sol.
3. one according to claim 1 titanium boride base used for aluminium electrolysis coating composite material, is characterized in that: carbonaceous additive is at least one in graphite, refinery coke or electric calcined anthracite.
4. one according to claim 1 titanium boride base used for aluminium electrolysis coating composite material, is characterized in that: described organic resin glue is made up of binding agent, dispersion agent, solidifying agent; The mass percentage of each component is respectively binding agent 35% ~ 58%, dispersion agent 40% ~ 64%, solidifying agent 1% ~ 5%.
5. one according to claim 4 titanium boride base used for aluminium electrolysis coating composite material, is characterized in that: described binding agent is at least one in pitch, furane resin, resol, epoxy resin or furfuryl resin;
Dispersion agent is at least one in acetone, butanone, ethanol or butylacetate;
Solidifying agent is at least one in tosic acid, polyamide resin, m-xylene diamine, hexamethylenetetramine, trimethylhexamethylenediamine, diethyl amino propylamine, quadrol or diethylenetriamine.
6. one according to claim 1 titanium boride base used for aluminium electrolysis coating composite material, is characterized in that: toughener is at least one in carbon fiber, silicon carbide fiber, sapphire whisker, Zirconium oxide fibre or titanium carbide.
7. prepare the method for coating with titanium boride base coating composite material according to claim 1, it is characterized in that comprising the following steps:
(1) apply, graphite substrate material is put into coating die, the distance at graphite substrate material upper surface and mould edge suitable for reading, and graphite substrate material surrounded surface is consistent with the gap size between mold wall, the titanium boride base coating composite material used for aluminium electrolysis then claim 1 obtained is poured in mould;
(2) solidify, will the graphite substrate material of titanium boride base coating composite material used for aluminium electrolysis be coated with at 15 DEG C ~ 35 DEG C solidification treatment 24h ~ 48h, and then at 80 DEG C ~ 150 DEG C solidification treatment 12h ~ 24h;
(3) charing sintering, graphite substrate material step (2) being coated with titanium boride base coating composite material used for aluminium electrolysis is placed in plumbago crucible, landfill graphite carbon dust, then at Ar or/and N
2charing sintering is carried out in atmosphere or in vacuum; Described charing sintering temperature is 850 ~ 1050 DEG C, and charing sintering time is 80h ~ 120h.
8. titanium boride base coating composite material according to claim 7 prepares the method for coating, it is characterized in that: the Ar described in step (3) is or/and N
2o in atmosphere or in vacuum
2content controls as 10ppm ~ 50ppm; Described vacuum≤10
-1pa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310101483.XA CN103194101B (en) | 2013-03-27 | 2013-03-27 | A kind of titanium boride base coating composite material used for aluminium electrolysis and preparation method thereof, coating method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310101483.XA CN103194101B (en) | 2013-03-27 | 2013-03-27 | A kind of titanium boride base coating composite material used for aluminium electrolysis and preparation method thereof, coating method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103194101A CN103194101A (en) | 2013-07-10 |
| CN103194101B true CN103194101B (en) | 2016-03-09 |
Family
ID=48716924
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310101483.XA Active CN103194101B (en) | 2013-03-27 | 2013-03-27 | A kind of titanium boride base coating composite material used for aluminium electrolysis and preparation method thereof, coating method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103194101B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103468134B (en) * | 2013-08-14 | 2015-11-25 | 苏州康华净化系统工程有限公司 | A kind of waterproof antistatic aluminium alloy covered containing gum resin |
| CN103668331A (en) * | 2013-11-29 | 2014-03-26 | 云南云铝润鑫铝业有限公司 | Method for effectively prolonging service life of aluminum electrolytic tank |
| CN105086745A (en) * | 2015-07-29 | 2015-11-25 | 安徽鹏峰新型建材科技有限公司 | Anti-corrosion paint special for scaffold |
| CN105088277A (en) * | 2015-08-27 | 2015-11-25 | 江苏联合金陶特种材料科技有限公司 | Preparation of TiB2-TiB/Ti gradient composite porous material used for aluminum electrolysis |
| CN106435644A (en) * | 2016-12-05 | 2017-02-22 | 中南大学 | Tamping paste for aluminum electrolytic cell and use method of tamping paste |
| CN113185856B (en) * | 2021-04-25 | 2024-04-09 | 仲恺农业工程学院 | Preparation method and application of coating material for oil sludge cracking treatment |
| CN114134539B (en) * | 2021-11-05 | 2024-09-27 | 新疆农六师碳素有限公司 | Special coating material for aluminum carbon production line and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08169786A (en) * | 1994-12-16 | 1996-07-02 | Tokai Carbon Co Ltd | Production of oxidation resistant carbon fiber reinforced carbon composite material |
| CN1807693A (en) * | 2005-12-26 | 2006-07-26 | 石忠宁 | Aluminium electrolysis cathode with titanium diboride coating and preparation process thereof |
| CN101844926A (en) * | 2010-03-24 | 2010-09-29 | 中南大学 | Pelleting method of titanium diboride powder |
| CN101876079A (en) * | 2010-06-13 | 2010-11-03 | 中国铝业股份有限公司 | Titanium boride cathode material for aluminium electrolysis and preparation method thereof |
| CN102304725A (en) * | 2011-09-16 | 2012-01-04 | 云南云铝润鑫铝业有限公司 | Electrolytic cathode containing titanium boride-carbon coating, and preparation method thereof |
| CN102491753A (en) * | 2011-11-22 | 2012-06-13 | 中国铝业股份有限公司 | TiB2 composite cathode material for aluminum electrolysis and preparation method thereof |
-
2013
- 2013-03-27 CN CN201310101483.XA patent/CN103194101B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08169786A (en) * | 1994-12-16 | 1996-07-02 | Tokai Carbon Co Ltd | Production of oxidation resistant carbon fiber reinforced carbon composite material |
| CN1807693A (en) * | 2005-12-26 | 2006-07-26 | 石忠宁 | Aluminium electrolysis cathode with titanium diboride coating and preparation process thereof |
| CN101844926A (en) * | 2010-03-24 | 2010-09-29 | 中南大学 | Pelleting method of titanium diboride powder |
| CN101876079A (en) * | 2010-06-13 | 2010-11-03 | 中国铝业股份有限公司 | Titanium boride cathode material for aluminium electrolysis and preparation method thereof |
| CN102304725A (en) * | 2011-09-16 | 2012-01-04 | 云南云铝润鑫铝业有限公司 | Electrolytic cathode containing titanium boride-carbon coating, and preparation method thereof |
| CN102491753A (en) * | 2011-11-22 | 2012-06-13 | 中国铝业股份有限公司 | TiB2 composite cathode material for aluminum electrolysis and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103194101A (en) | 2013-07-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103194101B (en) | A kind of titanium boride base coating composite material used for aluminium electrolysis and preparation method thereof, coating method | |
| CN100465349C (en) | Aluminium electrolysis cathode with titanium diboride coating and preparation process thereof | |
| RU2125123C1 (en) | Element of electrolyzer cell, method of manufacturing the element, electrolyzer | |
| CN100491600C (en) | Method for preparing carbon block of cathode capable of being humidified | |
| CN101698945B (en) | Carbon-fiber reinforced cathode carbon block and preparation method thereof | |
| CN101876079B (en) | Titanium boride cathode material for aluminium electrolysis and preparation method thereof | |
| CN110744031B (en) | Metal ceramic wear-resistant material of three-dimensional network ceramic framework and preparation method thereof | |
| CN101158048A (en) | Graphitized wetable cathode carbon block for aluminium electrolysis bath and production method thereof | |
| CN101255568A (en) | Particle gradation functional gradient TiB2/C composite cathode for aluminium electrolysis and preparation method thereof | |
| CN102304725A (en) | Electrolytic cathode containing titanium boride-carbon coating, and preparation method thereof | |
| CN109055995B (en) | Method for preparing carbon oxide anode for electrolytic extraction of titanium | |
| CN102010206A (en) | Titanium boride composite material for aluminum electrolysis and preparation method thereof | |
| CN101165217A (en) | Humid cathode carbon block with high graphite basal body and producing method thereof | |
| CN102491753A (en) | TiB2 composite cathode material for aluminum electrolysis and preparation method thereof | |
| JPS58501172A (en) | Sintered refractory hard metal | |
| CN103643260B (en) | A kind of TiB used for aluminium electrolysis 2-C composite cathode and preparation method thereof | |
| CN110436933B (en) | TiB for aluminum electrolysis2-graphene composite cathode material and preparation method thereof | |
| CN1273284A (en) | Carbon block as cathode with compound titanium boride-carbon layer and its preparing process | |
| WO2021061014A1 (en) | Method for protecting cathode blocks of aluminium electrolyzers having prebaked anodes, protective composition and coating | |
| CN100366800C (en) | Preparation method of TiB2 composite layer cathode carbon block | |
| CN203923399U (en) | A kind of used for aluminium electrolysis TiB2-C composite cathode | |
| CN103951435A (en) | TiB2-based composite cathode material used for aluminium electrolysis and preparation method thereof | |
| CN101314857A (en) | Self-smoothing composite layer unreactive cathode block | |
| EP3247821B1 (en) | Improved method for fabricating a dense, dimensionally stable, wettable cathode substrate in situ | |
| CN102744410A (en) | Method for preparing TiB2 layer of cathode for aluminum electrolytic bath |
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 | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20170105 Address after: 100082 Beijing, Xizhimen, North Street, No. 62, No. Patentee after: Aluminum Corporation of China Limited Address before: 223005 Haikou Road, Huaian Economic Development Zone, Jiangsu, No. 9 Patentee before: Jiangsu United Ceralloy Materials Technologies Co., Ltd. |