CN116752195A - TiB for aluminum electrolysis 2 Alloy composite cathode material and normal pressure sintering method thereof - Google Patents
TiB for aluminum electrolysis 2 Alloy composite cathode material and normal pressure sintering method thereof Download PDFInfo
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- CN116752195A CN116752195A CN202310782547.0A CN202310782547A CN116752195A CN 116752195 A CN116752195 A CN 116752195A CN 202310782547 A CN202310782547 A CN 202310782547A CN 116752195 A CN116752195 A CN 116752195A
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 51
- 239000000956 alloy Substances 0.000 title claims abstract description 51
- 238000005245 sintering Methods 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 38
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 36
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000010406 cathode material Substances 0.000 title claims abstract description 33
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 29
- 239000000843 powder Substances 0.000 claims abstract description 68
- 238000000498 ball milling Methods 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 21
- 238000000462 isostatic pressing Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000005303 weighing Methods 0.000 claims abstract description 9
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 6
- 238000005551 mechanical alloying Methods 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- 238000003825 pressing Methods 0.000 claims description 18
- 239000011812 mixed powder Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 10
- 239000012300 argon atmosphere Substances 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 229910000831 Steel Inorganic materials 0.000 claims description 5
- 239000010959 steel Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910009043 WC-Co Inorganic materials 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000004886 process control Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000005363 electrowinning Methods 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000002490 spark plasma sintering Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- PUAQLLVFLMYYJJ-UHFFFAOYSA-N 2-aminopropiophenone Chemical compound CC(N)C(=O)C1=CC=CC=C1 PUAQLLVFLMYYJJ-UHFFFAOYSA-N 0.000 description 2
- 229910002555 FeNi Inorganic materials 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000002905 metal composite material Substances 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 229910000967 As alloy Inorganic materials 0.000 description 1
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 206010053759 Growth retardation Diseases 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 229910033181 TiB2 Inorganic materials 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910002110 ceramic alloy Inorganic materials 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 231100000001 growth retardation Toxicity 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/06—Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
- C25C3/08—Cell construction, e.g. bottoms, walls, cathodes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
- B22F1/142—Thermal or thermo-mechanical treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/02—Compacting only
- B22F3/04—Compacting only by applying fluid pressure, e.g. by cold isostatic pressing [CIP]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/1003—Use of special medium during sintering, e.g. sintering aid
- B22F3/1007—Atmosphere
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/1017—Multiple heating or additional steps
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/005—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides comprising a particular metallic binder
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/14—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on borides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
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- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
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- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Fluid Mechanics (AREA)
- Thermal Sciences (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention discloses TiB for aluminum electrolysis 2 Alloy composite cathode material and normal pressure sintering method thereof, which relates to the technical field of aluminum electrowinning, and is especially suitable for cathode material for low-temperature aluminum electrolysis with inert anode and temperature of 750-900 ℃; tiB of the invention 2 The alloy composite cathode material comprises 91-96% TiB 2 1-3% of WC and 3-8% of alloy, wherein the alloy consists of three to four of Ti, fe, ni, al and Co; the preparation method comprises the following steps: weighing TiB 2 Powder, alloy powder, co powder and nano WC powder, powder mixing, mechanical alloying ball milling, rubber isostatic pressing and normal pressure sintering; the alloy powder is used as the sintering aid and the nano WC powder is used as the grain growth retarder, and the rubber isostatic pressing technology is used for obtaining the high-density pressed compact, so that the normal-pressure sintering temperature is low, the grain size of the material is small, the manufacturing cost is low, and the use requirement of low-temperature aluminum electrolysis is met.
Description
Technical Field
The invention relates to a TiB for aluminum electrolysis 2 Alloy composite cathode material and normal pressure sintering method thereof, which is especially suitable for cathode material for low temperature aluminum electrolysis cell with inert anode and electrolysis temperature lower than 900 ℃.
Background
The existing Hall-Heroult aluminum electrolysis process adopts consumable carbonThe anode consumes about 450 kg of carbon material and discharges about CO per ton of electrolytic aluminum 2 The gas was 1.5 tons and also discharged strong greenhouse gas fluorocarbon (CF 4 、C 2 F 6 )、SO 2 Contaminants such as gas and dust; the carcinogenic aromatic compounds (PAH) and SO are also discharged in the production process of the prebaked carbon anode 2 Contaminants such as dust; in addition, in the current aluminum electrolysis process, the prebaked anode carbon blocks need to be replaced every month, so that the electrolysis production is unstable, the labor intensity, the personal risk of workers facing high-temperature melt and the unorganized discharge of fluoride are increased.
The novel electrolysis process of carbon-free inert anode and the wettable cathode can be used for successfully solving the problems, oxygen is separated out from the inert anode in the electrolysis process, the production efficiency can be improved, and the inert anode technology is a key technology for energy conservation, carbon reduction and pollution reduction which needs to be overcome in the nonferrous metal smelting industry.
Aluminum electrolysis using inert anodes must use TiB simultaneously 2 The base material serves as a cathode material for two reasons:
1) Using TiB 2 The base material as cathode enables low temperature aluminum electrolysis technology using KF salts because of TiB 2 The base material has strong K permeation resistance, and the existing graphite cathode has weak K permeation resistance and is burst;
2) TiB 2 the base material has very good wetting effect on the aluminium liquid, while the existing graphite material does not wet the aluminium liquid.
TiB 2 The chemical stability can resist the high temperature corrosion of aluminum electrolyte, the conductivity is high, the aluminum liquid has good wettability and the like, and the material is considered as a candidate material of an excellent inert cathode. However, pure TiB 2 The melting point is as high as 2890 ℃, the sintering temperature of the powder is high, and grains grow rapidly during sintering to seriously reduce the mechanical property and thermal shock property of the material, so that the pure TiB 2 The cathode preparation difficulty is extremely high;
TiB published at present 2 the-C composite material adopts a hot-press sintering method or TiB 2 The metal composite material is sintered by Spark Plasma Sintering (SPS) or hot pressing sintering method, and the sintered and formed material is also required to be formedThe high machining cost of the cathode is very high;
TiB, on the other hand 2 The service life of the C composite material as an aluminum electrolysis cathode is not verified by long-time test data, and whether the cathode aluminum precipitation and TiB in the long-time aluminum electrolysis process can be carried out 2 Carbon element of-C composite material chemically reacts to destroy TiB 2 The properties of the-C composite are unknown;
patent CN 112609098 A,CN 112626403A, CN 110819867A, CN 111218599B and CN 111004956A propose TiB 2 Metal composite material, tiB 2 The content is 77-88%, the content of metal Fe, co, ni, cr, mn, WC and the like is 12-23%, and an SPS sintering method is adopted, but the SPS sintering method cannot prepare a large-size cathode yet;
patent CN 114105649A proposes a titanium diboride-based ceramic composite material comprising at least TiB 2 FeNi and Ti3 Al, the content of which is TiB 2 93% -98.8%, 1% -6% FeNi and 0.2% -1% Ti3 Al, and the manufacturing cost of the cathode is very high by adopting a hot press sintering method.
Disclosure of Invention
In order to overcome the defect of high manufacturing cost of the cathode, the invention provides a TiB for aluminum electrolysis 2 Alloy composite cathode materials, in particular for aluminium electrolysis at low temperatures, using inert anodes and with electrolysis temperatures below 900 ℃. TiB (TiB) 2 The alloy composite cathode material comprises 91-96% TiB 2 1-3% of WC and 3-8% of alloy, wherein the alloy consists of three to four of Ti, fe, ni, al and Co; the invention adopts two to three metal alloy powders of Ti, fe, ni and Al and Co powder as sintering additive, and nano WC powder as mixed powder of grain growth retardation additive, co and nano WC can also come from the ball milling process of the powder.
The invention provides TiB for aluminum electrolysis 2 -an atmospheric sintering process of an alloy composite cathode material comprising the steps of:
weighing raw materials:
weighing TiB according to a preset mass percentage 2 Powder, alloy powder, co powder and nano WC, powder;
further, the TiB 2 The mass ratio of the powder to the alloy powder to the Co powder to the nano WC powder is 91-96%, 3-6%, 0-2% and 1-2% respectively.
Mixing powder:
TiB is prepared 2 The powder, the alloy powder, the Co powder and the nano WC powder are put into a V-shaped mixer for mixing, and the mixing time is 3-5 hours.
Mechanical alloying ball milling:
the mixed powder is put into a stirring type sand mill for wet ball milling,
further, the wet ball milling process uses absolute ethyl alcohol and argon atmosphere,
further, the ball material of wet ball milling is WC-Co hard alloy
Further, the ball-milling process is carried out by adopting a wet ball-milling process with a ball-material ratio of 5:1, a rotating speed of 250-300 r/min and a ball-milling time of 20-30 h.
And (3) powder drying:
placing the mixed powder after ball milling into a vacuum drying oven for drying;
further, the vacuum drying process is carried out at the temperature of 70-90 ℃ and the vacuum degree of-0.06 MPa to-0.1 MPa for 8-12 h;
and (3) pressing:
firstly, placing the dried mixed powder into a steel mould for pre-pressing;
further, the pre-pressing pressure of the mixed powder steel mould is 80-120MPa;
placing the pre-pressed blank into a rubber die sleeve, and performing rubber isostatic pressing;
further, the pressing pressure of the isostatic pressing of the rubber is 300-400Mpa, and the pressure maintaining time is 1-2 minutes.
And (3) sintering:
sintering the pressed compact in an argon atmosphere furnace to obtain TiB 2 -an alloy composite;
further, sintering is carried out in an argon atmosphere furnace according to one of the following two systems:
system 1, sintering with a single temperature zone:
further, the sintering temperature in the single temperature zone is 160-1700 ℃ and the sintering time is 1-8 hours.
System 2, sintering by adopting a double temperature zone:
further, sintering is performed for 0.5 to 1 hour at a temperature of 1650 to 1700 ℃, then cooling is performed to 1500 to 1550 ℃, and sintering is performed for 4 to 9 hours at a temperature of 1500 to 1550 ℃.
Advantageous effects
The invention introduces three to four of Ti, fe, ni, co and Al metals as alloy additives, and introduces Al into alloy powder, and the alloy powder is mixed with TiB in the mechanical alloying ball milling process 2 The oxide film on the surface reacts, which is favorable for removing the oxide film layer and eliminating the harm of promoting the rapid growth of crystal grains in the sintering process of the oxide film; the rubber isostatic pressing technology is used, the pressed compact density is high, ti, fe, ni and Co alloy is used as sintering auxiliary agent and is in liquid state in the sintering process, and the TiB is filled in 2 In the gaps of the interface, tiB is improved 2 The sintering performance of the interface is improved, so that the density of the ceramic alloy is improved. Simultaneous WC nano-relative TiB 2 Grain encapsulation limits TiB 2 The abnormal growth of the crystal grains improves the mechanical property of the ceramic material. TiB prepared by the invention 2 The alloy composite cathode material has the following advantages:
1) The cathode material with large size can be prepared, and the preparation cost is relatively low by adopting normal pressure sintering;
2) The relative density of the material is up to more than 95%, the crystal grains are small, and the cathode material has excellent thermal shock resistance and high conductivity;
3) The service life of the cathode can be longer, and although the cathode exchanges alloy elements with aluminum liquid in the low-temperature aluminum electrolysis service environment, the alloy proportion in the material is lower than 9 percent, and even part of alloy elements exchange with aluminum in the long-time service process, tiB 2 The mechanical strength of the framework is still higher, and the cathode meets the service condition requirement of low-temperature aluminum electrolysis.
Description of the embodiments
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The technical requirements of the raw material powder of each embodiment in the invention are as follows:
TiB 2 the purity of the powder is more than or equal to 99.7 percent, and the grain diameter is less than or equal to 6 microns;
the purity of the alloy powder is more than or equal to 99.9 percent, and the granularity is less than or equal to 50 microns;
the purity of Co powder is more than or equal to 99.9 percent, and the granularity is less than or equal to 50 microns;
the particle size of nano WC is less than 200 nm.
Example 1
TiB for aluminum electrolysis 2 -alloy composite cathode material and normal pressure sintering method thereof, comprising the steps of:
weighing powder raw material, tiB 2 91% of powder, 6% of 70Ti20Fe10Al alloy powder, 2% of Co powder and 1% of nano WC powder; mixing powder for 3 hours, ball milling the mixed powder by using absolute ethyl alcohol and argon atmosphere, wherein the ball milling material is WC-Co hard alloy, the ball material ratio is 5:1, the rotating speed is 250r/min, and the ball milling time is 30 hours; drying the mixed powder at 90 deg.C under vacuum degree of-0.09 Mpa for 10 hr; pre-pressing the mixed powder in a steel mould, wherein the pressing pressure is 100Mpa, and then performing rubber isostatic pressing on the pre-pressed blank, wherein the pressing pressure is 320Mpa and the pressure maintaining time is 1 minute; the green compacts were sintered in an argon atmosphere at a sintering temperature of 1600 ℃ for 8 hours. The relative density of the obtained cathode material is higher than 96%, and the grain size is smaller than 10 microns.
Example 2
TiB for aluminum electrolysis 2 -alloy composite cathode material and normal pressure sintering method thereof, comprising the steps of:
weighing powder raw material, tiB 2 92% of powder, 5% of 84Ti16Al alloy powder, 1% of Co powder and 2% of nano WC powder; mixing powder for 3 hours, then performing wet ball milling, wherein the grinding ball material is WC-Co hard alloy, the ball material ratio is 5:1, the rotating speed is 300r/min, and the ball milling time is 20 hours; mixingDrying the powder at 90deg.C under vacuum degree of-0.09 Mpa for 10 hr; pre-pressing the mixed powder, wherein the pressing pressure is 110Mpa, performing rubber isostatic pressing on the pre-pressed blank, and maintaining the pressure for 1 minute, wherein the pressing pressure is 380 Mpa; the compacts were sintered at 1700 ℃ for 0.5 hours, then cooled to 1500 ℃ and sintered at 1500 ℃ for 9 hours. The relative density of the obtained cathode material is higher than 95 percent, and the grain size is smaller than 9 microns.
Example 3
TiB for aluminum electrolysis 2 -alloy composite cathode material and normal pressure sintering method thereof, comprising the steps of:
weighing powder raw material, tiB 2 96% of powder, 3% of 80Ti10Ni10Al alloy powder and 1% of nano WC powder; mixing powder for 3 hours, ball milling by a wet method, wherein the process comprises the steps of ball-material ratio of 5:1, rotating speed of 250r/min and ball milling time of 30 hours; drying the mixed powder at 90 deg.C under vacuum degree of-0.09 Mpa for 10 hr; pre-pressing the mixed powder, wherein the pressing pressure is 100Mpa, performing rubber isostatic pressing on the pre-pressed blank, and maintaining the pressure for 1 minute, wherein the pressing pressure is 350 Mpa; the compacts were sintered for 1 hour at a temperature of 1650 ℃, then cooled to 1500 ℃ and sintered for 9 hours at a temperature of 1500 ℃. The relative density of the obtained cathode material is higher than 97%, and the grain size is smaller than 10 microns.
Example 4
TiB for aluminum electrolysis 2 -alloy composite cathode material and normal pressure sintering method thereof, comprising the steps of:
weighing powder raw material, tiB 2 91% of powder, 6% of 70Ti20Fe10Al alloy powder, 2% of Co powder and 1% of nano WC powder; mixing powder for 3 hours, ball milling by a wet method, wherein the process comprises the steps of ball-material ratio of 5:1, rotating speed of 250r/min and ball milling time of 24 hours; drying the mixed powder at 90 deg.C under vacuum degree of-0.09 Mpa for 10 hr; pre-pressing the mixed powder, wherein the pressing pressure is 100Mpa, then performing rubber isostatic pressing on the pre-pressed blank, and maintaining the pressure for 1 minute, wherein the pressing pressure is 400 Mpa; the compacts were sintered in an argon atmosphere at a temperature of 1700 ℃ for 1 hour. The relative density of the obtained cathode material is higher than 96%, and the grain size is smaller than 8 microns.
Finally, it should be noted that: the above embodiments are only for illustrating the present invention and not for limiting the technical solution described in the present invention; thus, while the invention has been described in detail with reference to the various embodiments described above, it will be understood by those skilled in the art that the invention may be modified or equivalents; all technical solutions and modifications thereof that do not depart from the spirit and scope of the present invention are intended to be included in the scope of the appended claims.
Claims (8)
1. TiB for aluminum electrolysis 2 -alloy composite cathode material, characterized in that the TiB 2 The alloy composite cathode material comprises 91-96% TiB 2 1-3% WC and 3-8% alloy consisting of three to four of Ti, fe, ni, al and Co.
2. The TiB for aluminum electrolysis according to claim 1 2 -alloy composite cathode material, characterized in that the TiB 2 -the relative density of the alloy composite cathode material is higher than 96% and the grain size is smaller than 10 microns.
3. A TiB according to claims 1-2 2 -an alloy composite cathode material atmospheric sintering method, characterized in that the preparation method comprises the following steps:
1) Weighing the raw materials: weighing TiB according to a preset mass percentage 2 Powder, alloy powder, co powder and nano WC powder, wherein the TiB 2 The Co powder and the nano WC powder are respectively prepared from the following components in percentage by mass: 91-96%, 3-6%, 0-2% and 1-2%;
2) Mixing powder: placing the raw material powder into a V-shaped mixer for powder mixing;
3) Mechanical alloying ball milling: carrying out wet ball milling on the raw material mixed powder in an argon atmosphere by using absolute ethyl alcohol;
4) And (3) drying: placing the ball-milling mixed powder into a vacuum drying oven for drying;
5) And (3) forming: pre-pressing the mixed powder in a steel mould, and then performing rubber isostatic pressing on a pre-pressed blank;
6) Sintering: sintering the pressed compact to obtain the TiB 2 -an alloy composite cathode material.
4. A TiB according to claim 3 2 -an alloy composite cathode material atmospheric sintering method, characterized in that the TiB 2 The purity of the powder is more than or equal to 99.7 percent, and the grain diameter is less than or equal to 6 microns; the alloy powder consists of two to three metals of Ti, fe, ni and Al, the purity is more than or equal to 99.9 percent, and the granularity is less than or equal to 50 microns; the purity of the Co powder is more than or equal to 99.9 percent, and the granularity is less than or equal to 50 microns; the nano WC has a particle size of less than 200 nanometers.
5. A TiB according to claim 3 2 The normal-pressure sintering method of the alloy composite cathode material is characterized in that the mechanical alloying ball milling is wet ball milling, absolute ethyl alcohol and argon atmosphere are used as a ball milling process control agent, the ball milling material of the wet ball milling is WC-Co hard alloy, the ball material ratio is 5:1, the rotating speed is 250-300 r/min, and the ball milling time is 20-30 h.
6. A TiB according to claim 3 2 The normal pressure sintering method of the alloy composite cathode material is characterized in that the drying temperature of the ball milling drying step is 70-90 ℃, the vacuum degree is minus 0.06MPa to minus 0.1MPa, and the drying time is 8-12 h.
7. A TiB according to claim 3 2 -an alloy composite cathode material normal pressure sintering method, which is characterized in that the pre-pressing pressure of the steel mould is 80-120Mpa; the isostatic pressure of the rubber is 300-400Mpa, and the pressure maintaining time is 1-2 minutes.
8. A TiB according to claim 3 2 -an alloy composite cathode material atmospheric sintering method, characterized in that in the sintering step, the argon atmosphere atmospheric sintering can be one of the following two regimes:
1) Sintering for 1-8 hours at 1600-1700 ℃;
2) Sintering at 1650-1700 deg.c for 0.5-1 hr, cooling to 1500-1550 deg.c and final sintering at 1500-1550 deg.c for 4-9 hr.
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