CN103668318A - Method for preparing titanium-clad copper layered composite electrode plate by spray deposition method - Google Patents
Method for preparing titanium-clad copper layered composite electrode plate by spray deposition method Download PDFInfo
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- CN103668318A CN103668318A CN201310428292.4A CN201310428292A CN103668318A CN 103668318 A CN103668318 A CN 103668318A CN 201310428292 A CN201310428292 A CN 201310428292A CN 103668318 A CN103668318 A CN 103668318A
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- 229910052802 copper Inorganic materials 0.000 title claims abstract description 87
- 239000010949 copper Substances 0.000 title claims abstract description 87
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000009718 spray deposition Methods 0.000 title claims abstract description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 126
- 239000010936 titanium Substances 0.000 claims abstract description 125
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 124
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 238000003466 welding Methods 0.000 claims description 43
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 32
- 238000005097 cold rolling Methods 0.000 claims description 19
- 229910052786 argon Inorganic materials 0.000 claims description 18
- 238000005098 hot rolling Methods 0.000 claims description 18
- 238000000576 coating method Methods 0.000 claims description 12
- IUYOGGFTLHZHEG-UHFFFAOYSA-N copper titanium Chemical compound [Ti].[Cu] IUYOGGFTLHZHEG-UHFFFAOYSA-N 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000013049 sediment Substances 0.000 claims description 8
- 238000000889 atomisation Methods 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000001540 jet deposition Methods 0.000 claims description 6
- 238000004381 surface treatment Methods 0.000 claims description 6
- 238000007669 thermal treatment Methods 0.000 claims description 6
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 4
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 3
- 238000005096 rolling process Methods 0.000 claims description 2
- 238000005507 spraying Methods 0.000 abstract description 18
- 238000005266 casting Methods 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- 238000010891 electric arc Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 2
- 238000000605 extraction Methods 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract 1
- 239000002585 base Substances 0.000 abstract 1
- -1 ferrous metals Chemical class 0.000 abstract 1
- 239000007921 spray Substances 0.000 description 10
- 230000004927 fusion Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000007592 spray painting technique Methods 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000004699 copper complex Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a method for preparing a titanium-clad copper layered composite electrode plate by a spray deposition method, and discloses a titanium-clad copper layered composite plate for an insoluble anode and a preparation method thereof in the fields of extraction of non-ferrous metals, chlor-alkali industry and other fields. An electric arc spraying method, a melting-casting method or the spray deposition method is adopted for preparing the titanium/copper layered composite plate taking copper as an inner core and using titanium to coat an outer layer. The three methods are simple in preparation processes and easy to operate and are suitable for industrialized production, the prepared titanium/copper layered composite plate has excellent interfacial bonding property, electric conductivity and corrosion resistance, the titanium-coated anode is prepared by using the titanium/copper layered composite plate as a base plate, then the internal resistance of an electrode is reduced, the current distribution is uniform, the product purity is high, and the cell voltage is reduced by 0.1-0.8V in comparison with a traditional titanium-coated electrode, so that the effects of saving energy and reducing consumption are achieved.
Description
Patent application of the present invention is from Chinese Patent Application No.: 200910094554,1, the applying date: on June 8th, 2009, denomination of invention is: the preparation method > > division of < < titanium/titanium/copper laminated composite electrode plate comes.
Technical field
The fields such as non-ferrous metal extraction, chlorine industry that the present invention relates to are for the preparation method of insoluble anode substrate titanium/copper laminated composite plate.
Background technology
Titanium electrode extracts and chlorine industry field because its excellent solidity to corrosion and dimensional stability are widely used in non-ferrous metal, but it is substrate that traditional coated titanium electrode be take titanium or titanium alloy, there is the defects such as internal resistance is large, current efficiency is low, current research emphasis both domestic and external is mainly the research of alloy system and coating aspect, to improve the use properties of electrode, and the method is to reducing not significantly effect of electrode internal resistance.
The electroconductibility that the corrosion resisting property that the comprehensive titanium of titanium/copper stratified composite is good and copper are good, is applied to titanium electrode, can improve the electroconductibility of electrode and being uniformly distributed of electric current, thereby improves the over-all properties of electrode.
The problems such as at present, the technique of the compound comparative maturity of titanium/copper has compound, the hot rolling of blast, welding, and above-mentioned several technique exists energy consumption large, and production cost is high, and geometric accuracy is poor, and yield rate is low.
Therefore the preparation method who, develops titanium/carbon/carbon-copper composite material that a kind of preparation technology is simple, production cost is low, energy consumption is little, material use efficiency is high, dimensional precision is high is the technical barrier that current researchist faces.The inventor, through fundamental research for many years, has found a kind of preparation method of titanium/carbon/carbon-copper composite material.
Summary of the invention
The object of the invention is, for the larger problem of titanium electrode material internal resistance, provides titanium/carbon/carbon-copper composite material that a kind of preparation technology is simple, production cost is low, material use efficiency is high, dimensional precision is high, conduct electricity very well and preparation method thereof.
Titanium/titanium/copper laminated composite electrode plate of the present invention is characterised in that: adopt arc spraying on titanium or copper coin, to spray layer of copper or titanium or adopt spray deposition jet deposition layer of copper or titanium or adopt fusion casting to water cast copper at the titanium box direct injection of making on titanium or copper coin, bound edge welding after thermal treatment rolling, obtain take inner core as copper, the outer titanium copper-clad laminated composite plate being coated by titanium, wherein the thickness of titanium layer is 0.6～1.2 ㎜.
The welding of described bound edge be in argon arc welding, union-melt weld, electron-bombardment welding, plasma arc welding, electric-resistance seam-welding any.
Titanium/copper complex method comprises that adopting arc spraying, fusion casting or spray deposition to prepare inner core is copper, the outer laminated composite plate being coated by titanium.
Described arc spraying is on titanium or copper coin, to spray layer of copper or titanium; Described spray deposition is jet deposition layer of copper or titanium on titanium or copper coin; Described fusion casting is watered cast copper at the titanium box direct injection of making.
The concrete steps of described arc spraying are: by copper coin deoil, surface treatment, utilize arc-spraying machine spray coating one deck titanium, then at 500～900 ℃, carry out hot rolling, cold rolling, make titanium copper-clad composition board; Or by titanium plate deoil, surface treatment, sandblast, erosion, utilize arc-spraying machine to spray certain thickness copper layer at a face of titanium plate, gained covers copper titanium plate and at 400～850 ℃, carries out hot rolling, rear cold rolling, obtain composite board of titanium/copper, again by after copper face coated copper welding compound, two titanium copper composition board copper face superimposions, thermal treatment, by a kind of bound edge in argon arc welding, union-melt weld, electron-bombardment welding, plasma arc welding, electric-resistance seam-welding, weld, make titanium copper-clad composition board.Above-mentioned two kinds of methods make titanium copper-clad composition board after surface treatment coating, make production titanium anode plate.
The preparation process of described spray deposition is: copper coin is deoiled, and sandblast, is preheated to 300～700 ℃, sends into vacuum or argon atmospher sediment chamber, by pressure atomization double-sided deposition one deck titanium, and hot rolling at 500～900 ℃, cold rolling, make titanium copper-clad composition board; Or titanium plate is deoiled, sandblast, preheating temperature is 300～800 ℃, send into vacuum or argon atmospher sediment chamber, a face jet deposition layer of copper by pressure atomization shower nozzle at titanium plate, after at 400～850 ℃, carry out hot rolling, cold rolling, make composite board of titanium/copper, again by after copper face coated copper welding compound, two titanium copper composition board copper face superimposions, thermal treatment, by a kind of bound edge in argon arc welding, union-melt weld, electron-bombardment welding, plasma arc welding, electric-resistance seam-welding, weld, make titanium copper-clad composition board.Above-mentioned two kinds of methods make titanium copper-clad composition board after surface treatment coating, make production titanium anode plate.
The concrete steps of described fusion casting are: titanium plate is deoiled, sandblast, cleaned up, by melting, flash welding, argon arc welding, union-melt weld, electron beam welding, plasma arc welding or resistance welding, be prepared into titanium box, be preheated to 300～800 ℃, by the copper Implanted Titanium box of 1100～1300 ℃ of molten states, at 300～800 ℃ of temperature, carry out hot rolling subsequently, cold rolling, be prepared into titanium copper-clad composition board.
Described spraying or copper layer thickness are that 0.5～1.0 ㎜, titanium layer thickness are 0.8～1.2 ㎜.
Described titanium can be pure titanium or titanium alloy, and copper can be fine copper or copper alloy.
Titanium/copper compounding technology of the present invention comprises that adopting arc spraying, fusion casting or spray deposition to prepare inner core is copper, the outer titanium/copper laminated composite plate being coated by titanium, is specifically described as follows:
(1) to prepare titanium/copper (titanium copper-clad) composition board step as follows in electric arc spraying:
By titanium plate deoil, sandblast, utilize the thick copper layer of arc-spraying machine spraying one deck 0.5～1.0 ㎜, gained covers copper titanium plate and at 300～800 ℃, carries out hot rolling, cold rolling afterwards, make titanium copper composition board, electric arc spraying process parameter is arc voltage 32～42V, working current 160～200A, air pressure 0.3～0.9MPa, spray distance 80～200 ㎜.
Copper coin is deoiled, sandblast, cleaned up, utilize the thick titanium layer of arc-spraying machine double-face spray painting one deck 0.8～1.2 ㎜, at 500～900 ℃, carry out hot rolling, cold rolling afterwards, make titanium copper-clad composition board, electric arc spraying process parameter is arc voltage 32～42V, working current 160～200A, air pressure 0.3～0.9MPa, spray distance 80～200 ㎜.
(2) to prepare titanium/copper (titanium copper-clad) composition board step as follows for jet deposition:
Titanium plate is deoiled, sandblast, cleaned up, and preheating temperature is 400～800 ℃, sends into vacuum or argon atmospher sediment chamber, by pressure atomization shower nozzle deposition one deck 0.5～1.0 ㎜ copper layer, carries out hot rolling at 300～800 ℃, rear cold rolling, makes composite board of titanium/copper.
By copper coin deoil, sandblast, cleaning, preheating temperature is 300～800 ℃, sends into vacuum or argon atmospher sediment chamber, by pressure atomization shower nozzle double-sided deposition 0.8～1.2 ㎜ titanium layer, carries out hot rolling at 300～800 ℃, rear cold rolling, makes titanium copper-clad composition board.
In aforesaid method (1) and (2), titanium plate thickness is 0.8～1.2 ㎜, and copper plate thickness is 0.6～1.5 ㎜.
Obtained titanium copper composition board in aforesaid method (1) and (2), copper face coated copper welding compound, rear two titanium copper composition board copper face superimposions, thermal treatment, by a kind of bound edge in argon arc welding, union-melt weld, electron-bombardment welding, plasma arc welding, electric-resistance seam-welding, weld, make titanium copper-clad composition board.
(3) to prepare titanium copper-clad matrix material step as follows for fusion casting:
Titanium plate is deoiled, sandblast, cleaned up, by melting, flash welding, argon arc welding, union-melt weld, electron beam welding, plasma arc welding, resistance welding, be prepared into titanium box, be preheated to 300～800 ℃, by the copper Implanted Titanium box of 1100～1300 ℃ of molten states, at 300～800 ℃ of temperature, carry out hot rolling subsequently, cold rolling, be prepared into titanium copper-clad composition board.
Described titanium copper-clad composition board, is and prepares titanium electrode substrate used thereof, carries out surface treatment, coating, makes production titanium anode plate.
Above-mentioned all titaniums, copper, can be fine copper, pure titanium, or copper alloy, titanium alloy.
Preparation technology of the present invention is simple, easy to operate, adapting to industrialization produces, prepared titanium/copper laminated composite plate interfacial bonding property, electroconductibility, corrosion resistance excellent, with it as the prepared coating titanium anode of substrate, make electrode internal resistance reduction, distribution of current is even, product purity is high, bath voltage is compared with conventional coatings titanium electrode and is reduced by 0.1～0.8V, thereby reaches energy-saving and cost-reducing effect.
Accompanying drawing explanation
In Fig. 1, (a) is composite board of titanium/copper part sectioned view and (b) for compound section figure.
In Fig. 2, (a) is titanium copper-clad composite plate structure schematic diagram and (b) for part sectioned view.
Fig. 3 is titanium box structural representation.
Embodiment
With example, further illustrate flesh and blood of the present invention below, but content of the present invention is not limited to this.
Embodiment 3 deoils 120 * 120 * 0.8 ㎜ titanium plate surface, sandblast, clean up, and puts into argon atmospher sediment chamber, is preheated to 500 ℃ of copper layers that spray deposition 0.6 ㎜ is thick, at 500 ℃ of temperature, carry out hot rolling, rear cold rolling, make titanium copper composition board, copper face applies layer of copper welding compound, stack applies certain pressure, in 600 ℃ of process furnace, is incubated 60 minutes, cold rolling, with argon arc welding bound edge, weld, make titanium copper-clad composition board, coatings applications, bath voltage reduces 0.2V.
Embodiment 4 deoils 100 * 100 * 1.0 ㎜ copper coin surfaces, sandblast, clean up, and puts into argon atmospher sediment chamber, is preheated to 700 ℃ of thick titanium layers of two-sided spray deposition 1.0 ㎜, at 900 ℃ of temperature, carry out hot rolling, rear cold rolling, make titanium copper-clad composition board, coatings applications, bath voltage reduces 0.4V.
Embodiment 5 deoils the thick titanium plate surface of 0.8 ㎜, sandblast, clean up, by argon arc welding, be prepared into the titanium box that physical dimension is 120 * 120 * 6 ㎜, be preheated to 500 ℃, 1200 ℃ of molten state copper are injected to box, after carry out the hot rolling of 600 ℃, cold rolling, be prepared into titanium copper-clad composition board, coatings applications, bath voltage reduces 0.3V.
Claims (3)
1. a spray deposition is prepared the method for titanium bag titanium/copper laminated composite electrode plate, it is characterized in that adopting spray deposition jet deposition layer of copper or titanium on titanium or copper coin, bound edge welding after thermal treatment rolling, obtaining inner core is copper, the outer titanium copper-clad laminated composite plate being coated by titanium; Preparation process is:
Copper coin is deoiled, and sandblast, is preheated to 300～700 ℃, sends into vacuum or argon atmospher sediment chamber, by pressure atomization double-sided deposition one deck titanium, and hot rolling at 500～900 ℃, cold rolling, make titanium copper-clad composition board;
Or titanium plate is deoiled, sandblast, preheating temperature is 300～800 ℃, sends into vacuum or argon atmospher sediment chamber, a face jet deposition layer of copper by pressure atomization shower nozzle at titanium plate, after at 400～850 ℃, carry out hot rolling, cold rolling, make the composition board of titanium copper-clad,
Again by after copper face coated copper welding compound, two titanium copper composition board copper face superimposions, thermal treatment, welds by a kind of bound edge in argon arc welding, union-melt weld, electron-bombardment welding, plasma arc welding, electric-resistance seam-welding, makes the composition board of titanium copper-clad;
Above-mentioned two kinds of methods make titanium copper-clad composition board after surface treatment coating, make and produce with titanium copper-clad laminated composite plate, and wherein the thickness of copper layer is 0.5～1.0 ㎜, and the thickness of titanium layer is 0.6～1.2 ㎜.
2. spray deposition according to claim 1 is prepared the method for titanium bag titanium/copper laminated composite electrode plate, it is characterized in that: described titanium layer thickness is 0.8～1.2 ㎜.
3. the preparation method of titanium/titanium/copper laminated composite electrode plate according to claim 1, is characterized in that: described titanium is pure titanium or titanium alloy, and copper is fine copper or copper alloy.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310428292.4A CN103668318B (en) | 2009-06-08 | 2009-06-08 | Spray deposition prepares the method for titanium bag titanium/copper laminated composite electrode plate |
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| CNA2009100945541A CN101575714A (en) | 2009-06-08 | 2009-06-08 | Titanium/copper laminated composite electrode plate and preparation method thereof |
| CN201310428292.4A CN103668318B (en) | 2009-06-08 | 2009-06-08 | Spray deposition prepares the method for titanium bag titanium/copper laminated composite electrode plate |
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| CNA2009100945541A Division CN101575714A (en) | 2009-06-08 | 2009-06-08 | Titanium/copper laminated composite electrode plate and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108660443A (en) * | 2018-06-04 | 2018-10-16 | 中大立信（北京）技术发展有限公司 | A kind of preparation method and its usage of stannic oxide electrode |
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Cited By (2)
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| CN108660443B (en) * | 2018-06-04 | 2020-05-22 | 中大立信（北京）技术发展有限公司 | Preparation method and application of stannic oxide electrode |
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