CN1038132A - The wide temperature high-speed oxidation technique of aluminum or aluminum alloy - Google Patents
The wide temperature high-speed oxidation technique of aluminum or aluminum alloy Download PDFInfo
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- CN1038132A CN1038132A CN 88105586 CN88105586A CN1038132A CN 1038132 A CN1038132 A CN 1038132A CN 88105586 CN88105586 CN 88105586 CN 88105586 A CN88105586 A CN 88105586A CN 1038132 A CN1038132 A CN 1038132A
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- China
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- grams per
- per liters
- high speed
- additive
- temperature range
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- 230000003647 oxidation Effects 0.000 title claims abstract description 31
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 31
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 21
- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 title claims description 39
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000654 additive Substances 0.000 claims abstract description 18
- 230000000996 additive effect Effects 0.000 claims abstract description 18
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000004411 aluminium Substances 0.000 claims abstract description 14
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 10
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims abstract description 7
- 229940095064 tartrate Drugs 0.000 claims abstract description 7
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000004327 boric acid Substances 0.000 claims abstract description 4
- 239000004094 surface-active agent Substances 0.000 claims abstract 5
- 239000000243 solution Substances 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 239000010406 cathode material Substances 0.000 claims description 6
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 claims description 6
- 239000012530 fluid Substances 0.000 claims description 6
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 claims description 6
- 238000005498 polishing Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 2
- DBAMUTGXJAWDEA-UHFFFAOYSA-N Butynol Chemical compound CCC#CO DBAMUTGXJAWDEA-UHFFFAOYSA-N 0.000 claims description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 238000007259 addition reaction Methods 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 239000003945 anionic surfactant Substances 0.000 claims description 2
- 238000005238 degreasing Methods 0.000 claims description 2
- ALVPFGSHPUPROW-UHFFFAOYSA-N dipropyl disulfide Chemical compound CCCSSCCC ALVPFGSHPUPROW-UHFFFAOYSA-N 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- 150000002940 palladium Chemical class 0.000 claims description 2
- 230000001737 promoting effect Effects 0.000 claims description 2
- 229960004418 trolamine Drugs 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 2
- 240000008564 Boehmeria nivea Species 0.000 claims 1
- 101150034459 Parpbp gene Proteins 0.000 claims 1
- 241000382353 Pupa Species 0.000 claims 1
- 229910052770 Uranium Inorganic materials 0.000 claims 1
- 238000005868 electrolysis reaction Methods 0.000 claims 1
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 9
- 239000000203 mixture Substances 0.000 abstract description 5
- 238000007743 anodising Methods 0.000 abstract description 3
- 239000001117 sulphuric acid Substances 0.000 abstract description 3
- 235000011149 sulphuric acid Nutrition 0.000 abstract description 3
- 229910045601 alloy Inorganic materials 0.000 abstract description 2
- 239000000956 alloy Substances 0.000 abstract description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract 1
- 239000002253 acid Substances 0.000 abstract 1
- 229910052717 sulfur Inorganic materials 0.000 abstract 1
- 239000011593 sulfur Substances 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000004512 die casting Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 241000080590 Niso Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- HKIQCRMZWJSHBZ-UHFFFAOYSA-L dihydroxy(dioxo)chromium phosphoric acid sulfuric acid Chemical compound OP(O)(O)=O.OS(O)(=O)=O.O[Cr](O)(=O)=O HKIQCRMZWJSHBZ-UHFFFAOYSA-L 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Electrolytic Production Of Metals (AREA)
Abstract
The invention provides the technology of the high film forming speed of wide operating temperature range of the sulphuric acid anodizing of a kind of aluminium and aluminum alloy surface.The main sulfur acid of the composition of electrolytic solution also has a spot of oxalic acid, boric acid, tartrate and aniorfic surfactant etc., adopt simultaneously and be accelerated into film additive and widen the temperature range additive, making operating temperature range is 0～50 ℃, and film forming speed reaches 1.2 microns/square decimeter.This technology is fitted the surperficial anodic oxidation treatment of fine aluminium, particularly aluminium alloy and aluminium diecast alloy goods.
Description
The present invention relates to a kind of wide temperature high-speed oxidation technique of aluminum or aluminum alloy high-speed oxidation technique, particularly a kind of aluminum alloy die casting.
Aluminum products are immersed in the electrolytic solution energising continuously, make the aluminum products surface form oxide film with the technology that reaches protection aluminum products widespread usage.Used chromic acid electrolytic solution in the past, its advantage is that oxide thickness can reach 4～5 microns, and fine and close, and its oxide film etch resistant properties is better.But because chromic acid price height, and chromic toxicity caused serious pollution problem, just replaced chromic acid with sulfuric acid more or less in some cases.
Under the sulphuric acid anodizing processing condition of routine, when the current density of employing 1 peace/square decimeter was carried out oxide treatment, its film forming speed was 0.2～0.25 micron/minute.Japan's aluminium production technology research proposes a kind of new aluminium and aluminium alloy high speed anode oxidation process, and the film forming speed of sulphuric acid anodizing is increased to 0.4～0.5 micron/minute.Its electrolytic solution and process conditions are: free sulfuric acid 200～220 grams per liters, aluminium permissible level＜20 grams per liter (Al
+++), additive (NiSO
4) 8 ± 2 grams per liters, 22～24 ℃ of solution temperatures, current density 1.5～2 peace/square decimeters.If sulfuric acid content increases to 300 grams per liters, when current density was 2 peace/square decimeters, the highest film forming speed was 1 micron/minute.But the temperature range of this high speed anode oxidation process is little, and film forming speed is also undesirable.
Purpose of the present invention is providing a kind of wide temperature high-speed oxidation technique of aluminum or aluminum alloy, reduces energy consumption and reduces cost to reach.
Oxidizing process flow process provided by the invention comprises: oil removing, hot water wash, electropolishing, high speed anodic oxidation and painted.Characteristics are that the electrolytic solution and the process conditions of oxidation is: sulfuric acid H
2SO
4150～320 grams per liters, Tai-Ace S 150 Al
2(SO
4)
318H
2O 0～8 grams per liter, oxalic acid C
2O
4H
20～25 grams per liter, boric acid H
3BO
30～50 grams per liter, tartrate C
4O
6H
60～50 grams per liter, anionic table promoting agent 0.01～0.02 grams per liter, be accelerated into film additive 5～12 grams per liters, widen temperature range additive 2～5 grams per liters, 5～50 ℃ of solution temperatures, current density 1～5 peace/square decimeter, cathode material aluminium or lead.The film forming speed of this technology can reach 1～1.2 micron/minute.
This process using negatively charged ion chemistry deoiling method comes wetting product surface, and goods were both degreased, and reaches again matrix surface is not corroded, and also plays the wetting ability effect simultaneously.Anion surfactant is 5～8 milliliters/liter in the used degreasing fluid, and solution temperature is 60～80 ℃, till required time is the greasy dirt Ex-all.
The aluminium alloy polishing fluid of this process using phosphoric acid-sulfuric acid-chromic acid type, low, the easy grasp of this solution cost can play the leveling effect, can play polishing action again, is the better prescription of current aluminium alloy polishing fluid.Its polishing fluid and process conditions are: phosphoric acid H
3PO
460～70%, sulfuric acid H
2SO
415～20%, chromic acid CrO
35～8%, water H
2O 3～5%, 70～110 ℃ of temperature, current density 15～20 peace/square decimeters, time 1～3.Or: phosphoric acid H
3PO
460%, chromic acid CrO
320%, water H
2O 20%, 65～75 ℃ of temperature, current density 5～10 peace/square decimeters, 3 minutes time.
The film additive that is accelerated into that this technology adopted plays film forming (Al by cobalt salt (0.5g), palladium salt (0.2g), nickel salt (8g) composition in oxidising process
2O
3) characteristics such as speed is fast, thicknesses of layers is even, absorption reinforcement, micropore increase.
The temperature range additive antianode oxidation of widening that this technology is adopted plays the sheltering effect, is carried out addition reaction respectively and is formed by thiocarbamide (1g), monoethanolamine (10g), propyl disulfide (0.2g), xitix (2g), oxalate (15g), tartrate (30g), trolamine (12g), propylene oxide (20g), epoxy chloropropane (20g) 1,4 butynol organism such as (15g).Can play the temperature range effect of widening.
We have successively done practical examination to the Al-alloy products of the first-class Si of containing of core Door lock casing, handle, door bolt in the lockmaking industry, Cu, Mn, Mg.Concrete technical process is: aluminum alloy die casting → correction → mechanical polishing → oil removing → hot water wash → electropolishing → high speed anodic oxidation → painted → sealing → check → finished product.The electrolytic solution of the oxidation of adopting and process conditions have following four kinds of examples:
Now the sample of the high-speed oxidation technique that the sample of the practical examination of this technology and Japanese aluminium production technology research are proposed carries out performance test and contrasts as follows:
Comprehensive above-mentioned situation, the wide temperature high-speed oxidation technique that the present invention proposes has following advantage:
1. can obtain oxidation film layer careful, that white is transparent in 0～50 ℃ of wide temperature range, be suitable for wide geographic area and use, energy savings reduces consuming.
2. film forming speed is fast, and makes rete be transparent, easily dyes various dark, light-coloured prods, is beneficial to the needs of all kinds of specialty decor products.
3. solution composition comprises and adds an agent composition, forms simply, and cost is low, and material source is extensive.
4. be suitable for the application of fine aluminium, particularly aluminium alloy and pack alloy goods.
5. do not have in process of production waste gas and produce, the waste water composition simply is easy to process, and is conducive to environmental protection, avoids polluting.
Claims (9)
1, a kind of aluminum or aluminum alloy high speed anode oxidation process, technical process comprises oil removing, hot water wash, electropolishing, high speed anodic oxidation, painted, it is characterized in that the electrolysis night of oxidation and process conditions are: sulfuric acid H
2SO
4150～320 grams per liters, Tai-Ace S 150 Al
2(SO
4)
318H
2O0～8 grams per liters, oxalic acid C
2O
4H
20～25 grams per liter, boric acid H
3BO
30～50 grams per liter, tartrate C
4O
6H
60～50 grams per liter, aniorfic surfactant 0.01～0.02 grams per liter, be accelerated into film additive 5～12 grams per liters, widen temperature range additive 2～5 grams per liters, 5～50 ℃ of solution temperatures, current density 1～5 peace/square decimeter, cathode material aluminium or lead.
2, high speed anode oxidation process according to claim 1 is characterized in that the electrolytic solution of oxidation and process conditions are: sulfuric acid H
2SO
4150～180 grams per liters, Tai-Ace S 150 Al
2(SO
4)
318H
2O 5～8 grams per liters, tartrate C
4O
6H
69～11 grams per liters, aniorfic surfactant 0.01～0.02 grams per liter, be accelerated into film additive 5～8 grams per liters, widen temperature range additive 3～5 grams per liters, 10～40 ℃ of solution temperatures, current density 1～3 peace/square decimeter, cathode material aluminium or lead.
3, high speed anode oxidation process according to claim 1 is characterized in that the electrolytic solution of oxidation and process conditions are: sulfuric acid HSO 280～320 grams per liters, Tai-Ace S 150 Al
2(SO
4)
318H
2O 5～8 grams per liters, be accelerated into film additive 8～12 grams per liters, widen temperature range additive 2～3 grams per liters, aniorfic surfactant 0.01～0.02 grams per liter, solution temperature 10～30, current density 3～5 peace/square decimeters, cathode material aluminium or lead, pneumatic blending.
4, high speed anode oxidation process according to claim 1 is characterized in that the electrolytic solution of oxidation and process conditions are: sulfuric acid H
2SO
4160～220 grams per liters, oxalic acid C
2O
4H
220～25 grams per liters, tartrate C
4O
6H
630～50 grams per liters, be accelerated into film additive 5～8 grams per liters, widen temperature range additive 3～5 grams per liters, aniorfic surfactant 0.01～0.02 grams per liter, 5～50 ℃ of solution temperatures, current density 3～6 peace/square decimeters, cathode material aluminium or lead, pneumatic blending.
5, high speed anode oxidation process according to claim 1 is characterized in that the electrolytic solution of oxidation and process conditions are: sulfuric acid H
2SO
4200～250 grams per liters, oxalic acid C
2O
4H
418～22 grams per liters, boric acid H
3BO
330～50 grams per liters, be accelerated into film additive 5～8 grams per liters, widen temperature range additive 2～3 grams per liters, anionic table promoting agent 0.01～0.02 grams per liter, 10～35 ℃ of solution temperatures, current density 1～2 peace/square decimeter, cathode material aluminium or lead.
6, according to claim 1,2,3,4 or 5 described high speed anode oxidation process, the drooping plan of its an ancient small-mouthed wine vessel is bragged the uranium pari and is supported ぬ and press and smooth the bad dark ramie danger of pupa .5g), palladium salt (0.2g) and nickel salt (8g) form.
7,, it is characterized in that widening the temperature range additive and carry out addition reaction and form by thiocarbamide (1g), propyl disulfide (0.2g), xitix (2g), oxalate (15g), tartrate (30g), monoethanolamine (10g), trolamine (12g), propylene oxide (20g), epoxy chloropropane (20g) 1,4 butynol (15g) organism according to claim 1,2,3,4 or 5 described high speed anode oxidation process.
8, high speed anode oxidation process according to claim 1 is characterized in that degreasing fluid and process conditions that oil removing is used are: 60～80 ℃ of 5～8 milliliters/temperature of anion surfactant.
9, high speed anode oxidation process according to claim 1 is characterized in that polishing fluid and process conditions that electropolishing is used are: phosphoric acid H
3PO
460～70%, sulfuric acid H
2SO
415～20%, chromic acid 5～8%, water HO 3～5%, 70～110 ℃ of temperature, current density 15～20 peace/square decimeters, 1～3 minute time.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88105586 CN1038132A (en) | 1988-09-28 | 1988-09-28 | The wide temperature high-speed oxidation technique of aluminum or aluminum alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88105586 CN1038132A (en) | 1988-09-28 | 1988-09-28 | The wide temperature high-speed oxidation technique of aluminum or aluminum alloy |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1038132A true CN1038132A (en) | 1989-12-20 |
Family
ID=4833765
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 88105586 Pending CN1038132A (en) | 1988-09-28 | 1988-09-28 | The wide temperature high-speed oxidation technique of aluminum or aluminum alloy |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1038132A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008064538A1 (en) * | 2006-12-01 | 2008-06-05 | Taishan City Kam Kiu Aluminium Extrusion Co., Ltd | Environment friendlly method for treating the surface of an aluminum product before spary coating |
| CN100462483C (en) * | 2006-12-21 | 2009-02-18 | 上海交通大学 | Preparation method of anti-corrosion coating on the surface of aluminum matrix composite material |
| CN102605405A (en) * | 2011-12-20 | 2012-07-25 | 中国航空工业集团公司北京航空材料研究院 | Anodization method for improving protection performance of aluminum and aluminum alloy |
| CN106193334A (en) * | 2016-09-23 | 2016-12-07 | 沈阳建筑大学 | Assembling type steel structure beam through mortise and tenon type node structure and assemble method |
| CN106637339A (en) * | 2017-01-12 | 2017-05-10 | 玉林师范学院 | Preparation process of aluminum alloy having high bonding strength anode oxide film |
| CN111519750A (en) * | 2020-04-01 | 2020-08-11 | 福莱美熙展览展示（上海）有限公司 | Rapid assembly system and assembly method thereof |
| CN114016107A (en) * | 2021-11-08 | 2022-02-08 | 佛山科学技术学院 | Environmentally friendly and wide temperature aluminum alloy anodic oxidation electrolyte and its preparation method and application |
-
1988
- 1988-09-28 CN CN 88105586 patent/CN1038132A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008064538A1 (en) * | 2006-12-01 | 2008-06-05 | Taishan City Kam Kiu Aluminium Extrusion Co., Ltd | Environment friendlly method for treating the surface of an aluminum product before spary coating |
| CN100462483C (en) * | 2006-12-21 | 2009-02-18 | 上海交通大学 | Preparation method of anti-corrosion coating on the surface of aluminum matrix composite material |
| CN102605405A (en) * | 2011-12-20 | 2012-07-25 | 中国航空工业集团公司北京航空材料研究院 | Anodization method for improving protection performance of aluminum and aluminum alloy |
| CN106193334A (en) * | 2016-09-23 | 2016-12-07 | 沈阳建筑大学 | Assembling type steel structure beam through mortise and tenon type node structure and assemble method |
| CN106193334B (en) * | 2016-09-23 | 2018-06-29 | 沈阳建筑大学 | Assembling type steel structure beam penetrates through mortise and tenon type node structure and assemble method |
| CN106637339A (en) * | 2017-01-12 | 2017-05-10 | 玉林师范学院 | Preparation process of aluminum alloy having high bonding strength anode oxide film |
| CN111519750A (en) * | 2020-04-01 | 2020-08-11 | 福莱美熙展览展示（上海）有限公司 | Rapid assembly system and assembly method thereof |
| CN111519750B (en) * | 2020-04-01 | 2021-06-11 | 福莱美熙展览展示（上海）有限公司 | Rapid assembly system and assembly method thereof |
| CN114016107A (en) * | 2021-11-08 | 2022-02-08 | 佛山科学技术学院 | Environmentally friendly and wide temperature aluminum alloy anodic oxidation electrolyte and its preparation method and application |
| CN114016107B (en) * | 2021-11-08 | 2023-03-14 | 佛山科学技术学院 | Environment-friendly wide-temperature aluminum alloy anodic oxidation electrolyte and preparation method and application thereof |
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