CN1176250C - Cathode block coated with titanium boride metal-ceramic composite material and its preparation method - Google Patents
Cathode block coated with titanium boride metal-ceramic composite material and its preparation method Download PDFInfo
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- CN1176250C CN1176250C CNB02131179XA CN02131179A CN1176250C CN 1176250 C CN1176250 C CN 1176250C CN B02131179X A CNB02131179X A CN B02131179XA CN 02131179 A CN02131179 A CN 02131179A CN 1176250 C CN1176250 C CN 1176250C
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Abstract
The present invention relates to a titanium boride ceramic-metal composite coating cathode block for an aluminium cell. A titanium boride ceramic-metal composite coating is used as a working surface of the aluminium cell. The present invention is characterized in that the weight percentage of a titanium boride ceramic-metal composite powder formulation for preparing the titanium boride ceramic-metal composite coating comprises 60 to 80% of Ti, 6 to 9% of C, 1 to 3% of Zr and 15 to 30% of B. Steps for preparing the titanium boride ceramic-metal composite coating comprise: spray and painting powder is prepared, and the granularity is between-80 and +300 meshes; carbon bottom surface pretreatment comprises roughening and preheating; plasma spray painting is carried out under the air normal pressure atmosphere, the powder is conveyed by using mixed gas of argon, nitrogen and hydrogen, and the coating thickness is 0.5 to 1.2mm; the powder is mechanically processed into products after cooled. The titanium boride ceramic-metal composite coating cathode block has the characteristics of good electric conductive performance, high heat stability, strong electrolyte erosion resisting performance, good wettability for aluminium liquid, etc.; furthermore, the service life of the aluminium cell can be effectively prolonged, the current efficiency is increased, the energy is saved, and the consumption is reduced.
Description
Technical field:
The present invention relates to a kind of aluminium electrolytic industry cathode material and preparation method thereof.Be particularly related to the preparation method of the cathode block coated with titanium boride metal-ceramic composite material of aluminium electrolyzer.
Background technology:
Fused salt electrolysis legal system aluminium is unique industry system aluminium method of system aluminium in the worldwide, and aluminium electrolytic cell cathode uses carbon materials, has three kinds at present: conventional cathode carbon piece, schungite cathode block and high graphite carbon piece.Aluminium electrolytic cell cathode is that carbon piece of being built by laying bricks or stones by bottom land and the about 20 centimetres of aluminium liquid that cover in the above constitute.The groove breakage mainly is the breakage of cathode block, and the life-span of groove was generally 4 years, and under disadvantageous situation, this time limit also can shorten.A large amount of research and production practice confirm, the damage of carbon materials is because the immersion of sodium, ionogen and the metal aluminium liquid that occurs during electrolysis makes due to the carbon piece dilatational strain.When aluminium was produced, the aluminum oxide of the adding bottom land of being everlasting generated precipitation, causes the bottom land minor insulation when serious.Because carbon cathode is poor by the aluminium wettability, this has not only aggravated the sedimentary forming process of groove, also can make cryolite melts immerse the carbon piece, makes it to expand; Leak out to cathode steel bar and cause iron-holder rising in the aluminium, the situation continued deterioration just forces and stops groove.In addition, contact with the effective of cathode block, must keep quite high aluminium liquid layer in the groove in order to guarantee molten aluminum.The subregion insulation of bottom land and the problem that the higher aluminum liquid layer brings are: electromagnetic force causes motion of aluminium liquid layer and constantly fluctuation, and for fear of aluminium and anode in short circuit, everything will make current efficiency reduce and power consumption increases.Titanium boride is that unique solubleness is very little in aluminium liquid, electric conductivity is high and can be the wetting material of aluminium.Wettability well just can directly deposit skim aluminium liquid on the cathode block surface, improve electric conductivity and corrosion resistance nature.The method that applies titanium boride at present on the aluminium cell carbon cathode is to use the vibratory compaction method, at carbon block base body last layer titanium boride-carbon composite layer.Because titanium boride-carbon composite layer contains 70% pitch, coke and Resin adhesive, easily corroded and early failure in actual use by sodium and aluminium.Document MA (metal digest) (digest number: 199907-42-0602), (digest number: (digest number: EIP98054192445 has introduced Germany scientist and successfully with plasma spraying method powders of titanium boride has been sprayed on the carbon cathode in a vacuum EI (engineering index), and test result shows that coating performance is good for EIP98054192446 and EI (engineering index).Caused the very big concern of Aluminum circle.But this method is owing to adopt vacuum plasma equipment, cost height.
Summary of the invention:
Purpose of the present invention mainly is to solve in a vacuum with plasma spraying method powders of titanium boride to be sprayed on the high problem of cost on the carbon cathode, develop under normal atmosphere atmosphere method on the carbon cathode that powders of titanium boride is sprayed on, reduced cost with the plasma spraying carbon material; Use the special-purpose titanium boride metal-ceramic composite material powder of plasma spraying under the suitable normal atmosphere atmosphere of developing simultaneously, the cathode block coated with titanium boride metal-ceramic composite material made from this powder has that resistance aluminium rate is low, Heat stability is good, electrolyte-resistant etch, to characteristic such as the wettability of aluminium liquid is good.
A kind of cathode block coated with titanium boride metal-ceramic composite material, on conventional cathode carbon piece, schungite cathode block and the high graphite cathode carbon piece with normal atmosphere atmosphere under plasma spraying method prepare coated with titanium boride metal-ceramic composite material, this layer and carbon block base body are closely linked, coated with titanium boride metal-ceramic composite material is characterized in that as the working face of electrolyzer the titanium boride metal-ceramic composite material power formulations weight percent composition for preparing coated with titanium boride metal-ceramic composite material is:
Ti:60-76.5%, C:6-9%, Zr:1-3%, B:15-30%, best group becomes: Ti:65.5-75%, C:6.2-8%, Zr:1.3-2.5%, B:16-27%.
The preparation process of preparation coated with titanium boride metal-ceramic composite material is as follows:
1, preparation spray powders, granularity is at-80～+ 300 orders;
2, carbon piece surface is given handling and is comprised roughening, give 200 ℃ of heat;
3, plasma spraying under normal atmosphere atmosphere, use argon gas, nitrogen and hydrogen gas mixture powder feeding, wherein argon gas is 10～20%, hydrogen is 5～15%, all the other are nitrogen, the total flux of mixed gas remains on 30～80 liters/minute, and coat-thickness is 0.5～1.2mm, and best coat-thickness is 0.8～1.0mm;
4, be machined as product after the cooling.
Compared with the prior art, the present invention has following characteristics:
1. prepare the special-purpose titanium boride metal-ceramic composite material powder that is used for plasma spraying carbon material under the normal atmosphere atmosphere; In 20～1000 ℃ temperature range, the thermal expansivity of coating is about 5.7 * 10
-6/ ℃ and the thermal expansivity 4 * 10 of carbon cathode
-6/ ℃ close; The coating resistance rate is 7.5 μ Ω m in the time of 900 ℃; Coat-thickness is 0.5～1mm; The bonding force of coating and carbon-based material is 5.2MPa, in conjunction with firm; Coating has good anti-sodium erosion performance, and solution loss speed is slower, is suitable for carrying out plant-scale applying.
2. compare with the vacuum plasma spray coating method, owing to do not need vacuum system, facility investment is little, and cost is low.
Embodiment:
Embodiment 1: at conventional cathode carbon piece surface preparation spraying preparation coated with titanium boride metal-ceramic composite material
Titanium boride metal-ceramic composite material power formulations weight percent is formed:
Ti:62.5%, C:8%, Zr:2.5%, B:27%, granularity is at-80～+ 300 orders.
Preparation process is as follows:
1. carbon piece surface is given handling and is comprised roughening, give 200 ℃ of heat;
2. plasma spraying under normal atmosphere atmosphere uses argon gas, nitrogen and hydrogen gas mixture powder feeding, and wherein argon gas is 10～20%, and hydrogen is 5～15%, and all the other are nitrogen, and the total flux of mixed gas remains on 30～80 liters/minute, and coat-thickness is 0.7mm;
3. be machined as product after the cooling.
Embodiment 2: at schungite cathode block surface preparation spraying preparation coated with titanium boride metal-ceramic composite material
Titanium boride metal-ceramic composite material power formulations weight percent is formed:
Ti:71.4%, C:7.6%, Zr:2%, B:19%, granularity is at-80～+ 300 orders.
Preparation process is as follows:
1. carbon piece surface is given handling and is comprised roughening, give 200 ℃ of heat;
2. plasma spraying under normal atmosphere atmosphere uses argon gas, nitrogen and hydrogen gas mixture powder feeding, and wherein argon gas is 10～20%, and hydrogen is 5～15%, and all the other are nitrogen, and the total flux of mixed gas remains on 30～80 liters/minute, and coat-thickness is 0.9mm;
3. be machined as product after the cooling.
Embodiment 3: at high graphite cathode carbon piece surface preparation spraying preparation coated with titanium boride metal-ceramic composite material titanium boride metal-ceramic composite material power formulations weight percent composition be:
Ti:76.5%, C:6.2%, Zr:1.3%, B:16%, granularity is at-80～+ 300 orders.
Preparation process is as follows:
1. carbon piece surface is given handling and is comprised roughening, give 200 ℃ of heat;
2. plasma spraying under the normal atmosphere atmosphere uses argon gas, nitrogen and hydrogen gas mixture powder feeding, and wherein argon gas is 10～20%, and hydrogen is 5～15%, and all the other are nitrogen, and the total flux of mixed gas remains on 30～80 liters of parts, and coat-thickness is 1.1mm;
3. be machined as product after the cooling.
Claims (3)
1. cathode block coated with titanium boride metal-ceramic composite material, on conventional cathode carbon piece, schungite cathode block and the high graphite cathode carbon piece with normal atmosphere atmosphere under plasma spraying method prepare coated with titanium boride metal-ceramic composite material, this layer and carbon block base body are closely linked, coated with titanium boride metal-ceramic composite material is characterized in that as the working face of electrolyzer the titanium boride metal-ceramic composite material power formulations weight percent composition for preparing coated with titanium boride metal-ceramic composite material is:
Ti：60-76.5％，C：6-9％，Zr：1-3％，B：15-30％。
2. a kind of cathode block coated with titanium boride metal-ceramic composite material as claimed in claim 1, it is characterized in that titanium boride metal-ceramic composite material power formulations weight percent consists of: Ti:65.5-75%, C:6.2-8%, Zr:1.3-2.5%, B:16-27%.
3. the preparation method of a cathode block coated with titanium boride metal-ceramic composite material, the preparation process that it is characterized in that preparing coated with titanium boride metal-ceramic composite material is as follows:
(1) preparation spray powders, granularity is at-80～+ 300 orders;
(2) carbon piece surface is given handling and is comprised roughening, give 200 ℃ of heat;
(3) plasma spraying under normal atmosphere atmosphere uses argon gas, nitrogen and hydrogen gas mixture powder feeding, and wherein argon gas is 10～20%, hydrogen is 5～15%, all the other are nitrogen, and the total flux of mixed gas remains on 30～80 liters/minute, and coat-thickness is 0.5～1.2mm;
(4) be machined as product after the cooling.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB02131179XA CN1176250C (en) | 2002-10-15 | 2002-10-15 | Cathode block coated with titanium boride metal-ceramic composite material and its preparation method |
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| CNB02131179XA CN1176250C (en) | 2002-10-15 | 2002-10-15 | Cathode block coated with titanium boride metal-ceramic composite material and its preparation method |
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| CN1405358A CN1405358A (en) | 2003-03-26 |
| CN1176250C true CN1176250C (en) | 2004-11-17 |
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| CNB02131179XA Expired - Fee Related CN1176250C (en) | 2002-10-15 | 2002-10-15 | Cathode block coated with titanium boride metal-ceramic composite material and its preparation method |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100510191C (en) * | 2006-12-08 | 2009-07-08 | 湖北工业大学 | Method of plasma spraying preparation of ternary boride-based metal ceramic coating |
| CN101555136B (en) * | 2009-05-20 | 2012-03-21 | 南京工业大学 | Titanium silicon carbide/titanium diboride-titanium carbide composite material and preparation method thereof |
| CN101921114B (en) * | 2010-09-15 | 2013-04-10 | 胡建东 | High-purity titanium boride (TiB) ceramic powder with face-centered cubic structure and preparation method thereof |
| DE102011004012A1 (en) * | 2011-02-11 | 2012-08-16 | Sgl Carbon Se | Surface profiled graphite cathode block with an abrasion resistant surface |
| CN102373488A (en) * | 2011-10-26 | 2012-03-14 | 中国铝业股份有限公司 | Method for reducing cathode drop of aluminium cell |
| CN102864404B (en) * | 2012-09-03 | 2014-01-22 | 昆明冶金研究院 | Method for preparing aluminum electrolytic cell TiB2 cathode coating by adopting plasma spraying technology |
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2002
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