CN1412351A - Light metal alloy surface coating method - Google Patents
Light metal alloy surface coating method Download PDFInfo
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- CN1412351A CN1412351A CN02145754A CN02145754A CN1412351A CN 1412351 A CN1412351 A CN 1412351A CN 02145754 A CN02145754 A CN 02145754A CN 02145754 A CN02145754 A CN 02145754A CN 1412351 A CN1412351 A CN 1412351A
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- China
- Prior art keywords
- light metal
- metal alloy
- acid
- solution
- passivation
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- 238000000576 coating method Methods 0.000 title claims abstract description 30
- 229910001092 metal group alloy Inorganic materials 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000011248 coating agent Substances 0.000 claims abstract description 24
- 238000011282 treatment Methods 0.000 claims abstract description 13
- 238000004140 cleaning Methods 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 29
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 22
- 238000002161 passivation Methods 0.000 claims description 22
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 14
- 239000004922 lacquer Substances 0.000 claims description 14
- 239000011777 magnesium Substances 0.000 claims description 14
- 229910052749 magnesium Inorganic materials 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 12
- 238000007747 plating Methods 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- 239000011701 zinc Substances 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 8
- 238000007743 anodising Methods 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 238000009713 electroplating Methods 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 150000008043 acidic salts Chemical class 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000003973 paint Substances 0.000 claims description 2
- 150000003016 phosphoric acids Chemical class 0.000 claims description 2
- 238000010301 surface-oxidation reaction Methods 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 1
- 238000005286 illumination Methods 0.000 claims 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 3
- 238000001465 metallisation Methods 0.000 abstract 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000013532 laser treatment Methods 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 238000004512 die casting Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910000861 Mg alloy Inorganic materials 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- PAZZVPKITDJCPV-UHFFFAOYSA-N 10-hydroxyoctadecanoic acid Chemical compound CCCCCCCCC(O)CCCCCCCCC(O)=O PAZZVPKITDJCPV-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004159 Potassium persulphate Substances 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 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 description 1
- 229960002050 hydrofluoric acid Drugs 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 238000011536 re-plating Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
- C23C28/025—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only with at least one zinc-based layer
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/34—Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/20—Pretreatment
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/42—Pretreatment of metallic surfaces to be electroplated of light metals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Electrochemistry (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Electroplating Methods And Accessories (AREA)
- Chemical Treatment Of Metals (AREA)
- Laminated Bodies (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Chemically Coating (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
The invention relates to a method for coating light metal alloy surfaces, according to which a galvanic layer containing Sn is applied to a galvanic intermediate layer, following a passivating cleaning treatment and a chemical metallisation. The galvanic layer is electroconductive and can also be lacquered.
Description
Technical field
The present invention relates to the coating method of surface of light metal alloy.Light metal alloy is interpreted as and contains the alloy that determines the component of surface chemistry with aluminium or magnesium as main participation herein.
Background technology
This light metal alloy is because its proportion is little should reach high mechanical stability in various one side and receive an acclaim in the vital again application of weight of parts on the other hand.These application examples are as being used in aircraft industry, perhaps, at first be in recent years, be used in automobile making, the housing of the housing of perhaps high value equipment, especially mobile telephone, these housings are conceived to stability on the one hand, constitute the basic structure of total structure, should as far as possible little weight loading be arranged to the user on the other hand.
Yet the shortcoming of these light metal alloys is that it is easy to oxidation, makes always will worry anticorrosive problem, and will need suitable surface treatment method.Protect the problem on the surface of this light metal alloy generally also always to be not easy to the real impression that keeps corresponding component enduringly.
Study the whole bag of tricks and used the whole bag of tricks within a large range.Because these methods or can only reach technical requirements limitedly, or with high costs, or on the geometric size of the parts that are subject to processing, limited to very much, so also need now to be improved or substitute.
Summary of the invention
In view of this technical problem, the present invention proposes a kind of superior and special coating method of light metal surface flexibly.
According to the present invention, be used for surface of light metal alloy coating method and have step:
-passivation ground cleaning surface of light metal alloy,
-carry out zinciferous metallochemistry to plate
-plating middle layer
-carry out stanniferous plating
The preferred embodiments of the present invention provide in the dependent claims.
The method according to this invention is a feature with its stanniferous electrolytic coating, and described stanniferous electrolytic coating can seal the surface of light metal alloy reliably with other described coating.The component of tin preferably should be more preferably at more than 50% more than 40% in corresponding electrolytic coating.
Passivation cleaning by at first carrying out contains the metallochemistry plating of metallic zinc then at least, can reach to have the tin electroplating layer and can adhere to well.Yet also will be adopted a galvanized middle layer in order to improve, the purpose in described middle layer is that the metal level that has zinc that produces with electroless plating before the protection can not be subjected to the follow-up plating infringement that has tin (also having other).Carry out the middle layer and electroplate the technology that into can select to be conceived to stablize zinciferous metal-plated, can on this layer, carry out stanniferous plating again, needn't consider zinciferous coating again.It is significant especially adopting about 7 to 10 the electroplating technology of pH value when electroplating the middle layer.Contain the destruction that the zinc layer can be subjected to acid on the one hand, the destruction that can be subjected to alkali on the other hand, this might wish when making stanniferous electrolytic coating, and is inevitable in other words.
Described passivation cleaning, can contain handlebar surface of light metal alloy alkalescence ground degrease as first step, use a kind of solution-treated degrease then the surface, described solution is acid on the one hand, at least contain a kind of acid-salt, thereby and light metal surface carried out certain pickling, carry out passivation on the other hand by way of parenthesis to oxygenizement.Notion in this oxidation is interpreted as that generally valence electron shifts, and comprises particularly to constitute oxide compound such as aluminium sesquioxide (Al
2O
3) and constitute fluorochemical such as bifluoride magnesium (MgF
2).
When main ingredient is magnesium, at least 50% weight magnesium component of at least 80% weight especially preferably, propose: described acid solution is handled or the salts solution of acid will carry out in two steps.One the step be at first in the pH value at 3-5, preferably handle in the more weak acid solution of the order of magnitude about 4.Another step is to adopt another kind of pH value at 0.5-2 then, the preferably much better than acid of the order of magnitude about 1, and described acid also contains fluorion.In pickled surface, constitute the passivation layer that contains bifluoride magnesium.
Described weakly acid soln can contain the mixture of carboxylic acid and tetra-sodium, and carboxylic acid for example is citric acid, oxysuccinic acid, oxalic acid or lactic acid.The strong acid solution of follow-up use for example can be the mixture of phosphoric acid and fluoram.
If light metal has significant al composition on the other hand, at least 60% weight especially especially contains the al composition of 80% weight, and the processing in acid or acidic salt solution can be used in the strong oxidizing solution that pickling produces passivation layer simultaneously and carry out.Wherein said passivation layer contains aluminium sesquioxide.The suitable example of strong oxidizing solution is nitric acid, persulfuric acid (peroxomonoschwefelsaeure) or Potassium Persulphate.
Another possibility that passivation is cleaned is with containing the solution-treated (or containing such processing) that phosphoric acid contains alcohol on the other hand on the one hand.When this processing, should carry out anodizing to the surface.To this with reference to the inventor on June 1st, 2000 in first to file 01114981.2: " method of cleaning and decontaminating surface of light metal alloy ".Should be introduced among the application in first to file.Can carry out very effective degreasing and the subsidiary causticization of having carried out to the surface with described cleaning, wherein the anodizing parameters optimization (current density of anodizing, voltage or the like) very flexibly of can picking up goods.Described alcohol can be general alcohol, for example methyl alcohol, ethanol, propyl alcohol and butanols and higher acid and derivative thereof, such as Virahol or the like.Can also be glycol, polyethers and other alcohol.Can certainly use mixture.Preferred butanols and Virahol.
Mainly be the alloy of magnesium component or preferably adopt fluorion to carry out surface passivation above-mentioned, wherein fluorion is added and contain in the solution of phosphoric acid, wherein in this treatment step anode is received on the surface.This treatment step can carry out simultaneously with another step that contains alcohol, also can carry out dividually with it, and solution contains phosphoric acid, pure and mild fluorion in a back step.
Fluorion can exist also and can exist with other form with fluoram, alkali metal fluosilicate hydrochlorate, fluoric acid.
In addition, for the described fluoride treatment of using, that is to say it is the processing that was divided into for two steps on the one hand, be processing on the other hand with the combination of phosphoric acid and alcohol, if light metal does not have magnesium or has only seldom magnesium, the component of silicon preferably surpasses 0.1, especially surpass 0.5 or 1 or 2% weight in addition higher be significant.Here fluorinion concentration can be determined by silicon concentration.
Described processing with phosphoric acid and alcohol and fluorion can be preferably with alkaline cleaning step end, is about 10 or be higher than 10 alkaline aqueous solution and carry out in the pH value.
Yet the step that alkalescence is cleaned is few and more be to be unfavorable by the dominant passive surface of aluminium sesquioxide for bifluoride magnesium, is to be disadvantageous under described high pH value at least.More wish to adopt the oxidation step that carries out aluminium sesquioxide in the aqueous oxygenant.Owing to adopting fluorion, the reason of the component of silicon also has meaning.Described oxidizing aqueous dose can be over cure solution or persulfuric acid (card rosilic acid) solution.Wherein oxidation should always be carried out after fluorine is handled.On the other hand, when high magnesium component, the pH value 6 or following acidic conditions under to carry out oxidizing aqueous step also be problematic because for may damage the fluorine passivation.
Described fluorion component can be a lower limit in 0.1 or 0.3 or 0.5% weight, and 20 or 30 or 10 is in the scope of the upper limit.Anodizing current density when handling with phosphoric acid and alcohol can be at 10 or 30 or 50 peace/rice
2Be lower limit 1000 peace/rice
2In the scope for the upper limit.Suitable temperature is at 10 to 40 degrees centigrade.Phosphoric acid can account for the 30-90% volume of solution, and accounts for the 50-95 weight percent in such volumetric ratio.Preferably the rest part of described solution mainly is alcohol or is fluorochemical under situation about having.
After above-mentioned cleaning with passivation is carried out pre-treatment, the zinciferous metallochemistry plating of enumerating previously.Can also containing metal copper and/or nickel in this chemical plating outside.
Copper and/or nickel equally also can be contained in follow-up plating middle layer.The last electrolytic coating of having discussed contains tin certainly, yet can contain for example zinc, bismuth and/or plumbous to improve erosion resistance in addition.
Above-mentioned method causes stable and persistent surface of light metal alloy electrolytic coating.Because described method can be carried out with wet chemical technology and electroplating processes, thus very flexible on the part size that can take up the post of and geometrical shape, can carry out on large-scale low-cost ground in addition.Can obtain the condition of surface that metallicity is conducted electricity with aforesaid method, this needs in many application.
Characteristics of the present invention are all right coating paint layer on stanniferous electrolytic coating.Thereby obtained another degree of freedom on the surface optical configuration.Thereby for example described lacquer can be the thick and transparent diversified decorative effect that reaches.Can also have with the existing japanning machine structure that is coated with of surface lacquer device and so on for example, various optical of the parts that are subject to processing and tactile outward appearance.Yet the most important thing is that the painted surface generally is an electrical isolation, is desirable in the application facet that has.Can also improve resistance to corrosion significantly by lacquering at last.
Can draw lacquer operation thus highly beneficially, can look applicable cases and relatively freely select with two compositions.Also can adopt the lacquer of single component, although the technical feature difference in general.
If before covering lacquer, the tack that passivation can improve lacquer is significantly carried out on stanniferous electrolytic coating surface.In the anode surface oxidation of this preferred alkalescence, for example in the solution that contains phosphoric acid salt or carbonate, carry out.
Described alkaline anodic oxidation can follow-up cathode treatment be replenished, and described cathode treatment is carried out in hexavalent chromium solution, can be to carry out in the chromic acid.Yet adopting sexivalent chromium for the reason of labour hygiene and environment protection still be debatable (but whether to product itself), so can be preferably plate surface be only used alkaline cathode oxidation pre-treatment before being coated with covering.Except above-mentioned advantage, covering the surface that is coated with can also revert to metallic surface electroconductibility to the subregion afterwards.This for example is being used on certain position electrically contacting with galvanized parts and the rest part of these parts when also will keep insulating; perhaps keep certain optical surface feature, it is significant doing like this when perhaps finally need be especially well chemistry and mechanical load being had excellent protection.
According to the present invention, a kind of laser treatment has been proposed for this reason, the laser radiation part was peeled off or evaporated to described laser treatment in relatively no problem mode enamelled coating brings metallic conductivity by making it to melt then again.Component according to the tin in the surface of the present invention provides special good electrical conductivity and provides stability for the part of removing lacquer simultaneously for this reason.
What laser treatment also can help not covering lacquer in addition partly improves existing surface conductivity according to parts of the present invention.At last, if with on the surface treated of the present invention such as being provided with other with oxide compound, nitride of spraying or the like or during additional insulation layer, also can using laser treatment.
In addition preferably on surf zone, in several hrs or apply the material of the metal-like conduction of liquid within these few days, for example contain cementing agent or other ageing-resistant material made of plastic of conductive particle by laser radiation.Described particle can be a silver granuel.Irradiation can preferably be carried out at twice, with the thermal load of limiting surface, can certainly carry out with conventional device under the airy environment.Fact proved and to use the Nd:YaG laser apparatus, for example 90W power.
The layer thickness in galvanized middle layer is between 5 to 10 microns.The bed thickness of preferred stanniferous electrolytic coating is also between the 5-10 micron.
Embodiment
Shown in the accompanying drawing the die-cast part of making by magnesium alloy AZ91 can be as for example.What relate at this is the frame part 1 (so-called frame) of cover for mobile phone.Bonding another metal or be coated with the shell portion of metal on the line 2 that described frame part 1 should be shown in the figure.Wherein on the one hand importantly the frame part 1 of magnesium die casting the surface durability of good high value outward appearance is arranged.Owing to often catch and touch, and the salt that occurs thus, weak acid and moist effect, and when using all the year round because the effect of weather effect and other condition, outside surface can become ugly when coating deficiently.Thereby internal surface may produce the fault that particle causes electric component owing to corrosion.
In addition, when gummed bonding portion to have favorable conductive to connect each other also be important, produce electromagnetic shielding with this to mobile telephone.Generally speaking, should be when the magnesium die casting is had stable coating to providing good electrical conductivity for composing outstanding surf zone 2.For shown in the planar section of mounting cup 3 of mobile telephone circuitry plate also be such, described planar section is owing to want ground connection equally also should conduct electricity.Other details of frame part 1 has no relation for the understanding of the present invention.
At first frame part 1 being carried out conventional alkaline degrease is 4 citric acid and tetra-sodium processing then in pH value.Then the strong acid solution with phosphoric acid and fluoram carries out passivation under pH1.
On the surface of cleaning and passivation in this way,, on this layer, can plate the copper layer of 7 micron layers again with conventional plating coated with the transition layer that becomes with copper by zinc.
The distinctive tin electrolytic coating of the present invention in re-plating on this relatively effectively galvanized copper layer, and additionally be coated with zinc therein, be that mass ratio is 70: 30 (tin: zinc) in this example.The thickness of coating is at 8 microns.
The surface of also conducting electricity is covered the pre-treatment of lacquer with alkaline anodizing oxidation in phosphate solution.When handling, do not use sexivalent chromium.But replace commercially available binary lacquer directly is coated in sclerosis then on the surface that anodizing crosses.
Thereby make magnesium die casting 1 that qualified visual quality and technical quality be arranged, wherein can use the bright lacquer of full impregnated, thereby expose the beautiful outward appearance of metal.
Then the surface is handled with commercially available Nd:YaG laser apparatus at lines 2 that illustrate and mounting cup 3 places.This laser apparatus is a Q-switch, about 32 amperes of lamp current, and power is 90W.Shine twice on line shown in the figure and the face, wherein pointwise is carried out exactly.Can determine spacing and every used energy of point with experiment, make to obtain enough line thickness on the other hand by the lines that obtain logical Chang on the one hand.Line thickness should be not too small, to optimize the transition resistance to another shell portion.Lines should be not excessive and will be fully covered by the cementing agent of later coating on the other hand.What use in this example is 1 millimeter.In addition, the access energy of each irradiation should be unnecessarily not high, exceedingly heats than deep layer avoiding.Can also reduce the energy of each irradiation by carrying out twice irradiation.Be radiated at this with 15 watts every square millimeter at every turn.The fltting speed of laser apparatus is 400 mm/second.
Then, so can cover the silica gel of being furnished with silver granuel on metallized again surperficial 2,3, thus with carry out bonding conductively in this another shell portion that does not describe in detail.Described another shell portion is metal or metallizing equally, and bonding making has electric contact to cementing agent.Can keep electric contact to cementing agent in this way.Can be manufactured on the housing of tight electric shielding generally in this way.
Other details of laser treatment is referring to the inventor " producing the method for metallic conductivity surf zone " on the light metal alloy of coating.
Claims (20)
1. the coating method of light metal surface (1) has step:
-passivation ground cleaning surface of light metal alloy (1),
-carry out zinciferous metallochemistry to plate
-plating middle layer
-carry out stanniferous plating.
2. the method for claim 1 is characterized in that, contains in steps:
-surface of light metal alloy (1) alkalescence ground degrease, and
-with handling surface of light metal alloy (1) in acid solution or the acidic salt solution, produce passivation layer by oxygenizement simultaneously.
3. method as claimed in claim 2 is characterized in that, the light metal alloy layer has the magnesium component of 50% weight, and contains in steps in the processing of acid solution:
-in weakly acid soln, handle, then,
-in strong acid, handle, wherein contain fluorion in the strong acid solution.
4. method as claimed in claim 3 is characterized in that described weakly acid soln contains carboxylic acid and tetra-sodium.
5. as claim 3 or 4 described methods, it is characterized in that described weakly acid soln contains phosphoric acid and fluoram.
6. method as claimed in claim 2 is characterized in that described light metal alloy contains the aluminium of at least 60% weight, and the processing in acid or acidic salt solution can be carried out with strong oxidizing solution.
7. method as claimed in claim 6 is characterized in that, described strong oxidizing solution is nitric acid, persulfuric acid or persulfate solution.
8. the method for claim 1 is characterized in that, has in surface of light metal alloy (1) passivation is cleaned with the solution-treated that contains phosphoric acid and alcohol, wherein surface of light metal alloy (1) is received anode.
9. method as claimed in claim 8, it is characterized in that, light metal alloy (1) contains the magnesium of at least 50% weight, and/or contain the silicon components of 0.1% weight, and passivation step finishes with containing the treatment step that carries out in the solution of phosphoric acid and fluorion, wherein surface of light metal alloy (1) is connect anode.
10. method as claimed in claim 8 is characterized in that light metal alloy contains the aluminium of at least 60% weight, and the treatment step in adopting oxidizing aqueous dose is cleaned in passivation.
11. each the described method as above claim is characterized in that, goes back cupric and/or nickel in the metallochemistry plating except zinc.
12. each the described method as above claim is characterized in that, contains copper and/or nickel in the middle of electroplating.
13. each the described method as above claim is characterized in that electrolytic coating contains zinc, bismuth and/or lead in addition except containing tin.
14. each the described method as above claim is characterized in that coating paint layer on stanniferous electrolytic coating.
15. method as claimed in claim 14 is characterized in that, described lacquer is the lacquer operation of two compositions.
16. as claim 14 or 15 described methods, it is characterized in that, before covering lacquer, passivation carried out on stanniferous electrolytic coating surface.
17. method as claimed in claim 16 is characterized in that, Passivation Treatment contains alkaline anodizing oxidation.
18. method as claimed in claim 17 is characterized in that, the anode surface oxidation of alkalescence is carried out in the solution that contains phosphoric acid salt and/or carbonate.
19., it is characterized in that carry out cathode treatment when Passivation Treatment, described cathode treatment is carried out in containing the solution of hexavalent chromium as claim 16,17 or 18 described methods, described cathode treatment is carried out after alkaline anodizing sometimes.
20. as above claim each described method, it is characterized in that, go up in the part (2,3) of surface of light metal alloy (1) and use laser illumination, with the electroconductibility of raising surface of light metal alloy.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP01124435.7 | 2001-10-11 | ||
| EP01124435A EP1302565B1 (en) | 2001-10-11 | 2001-10-11 | Coating method for light metal alloy surfaces |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1412351A true CN1412351A (en) | 2003-04-23 |
| CN1213169C CN1213169C (en) | 2005-08-03 |
Family
ID=8178944
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021457549A Expired - Fee Related CN1213169C (en) | 2001-10-11 | 2002-10-11 | Light metal alloy surface coating method |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US20030079997A1 (en) |
| EP (1) | EP1302565B1 (en) |
| JP (1) | JP2003221683A (en) |
| KR (1) | KR100553233B1 (en) |
| CN (1) | CN1213169C (en) |
| AT (1) | ATE277207T1 (en) |
| DE (1) | DE50103781D1 (en) |
| WO (1) | WO2003033777A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101205609B (en) * | 2006-12-18 | 2010-08-11 | 比亚迪股份有限公司 | Composition for magnesium alloy surface activation |
| CN103305894A (en) * | 2012-03-09 | 2013-09-18 | 苏州汉扬精密电子有限公司 | Magnesium alloy surface treatment method |
| CN103498156A (en) * | 2013-09-27 | 2014-01-08 | 成都四威高科技产业园有限公司 | Surface coating technology of silicon carbide particle reinforced aluminium-based composite |
| CN104562004A (en) * | 2015-01-28 | 2015-04-29 | 江西富意美实业有限公司 | Aluminum-alloy temperature sensing pipe for various types of temperature controllers and preparation method thereof |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004035876A1 (en) * | 2002-10-09 | 2004-04-29 | Wolf-Dieter Franz | Method for cleaning and passivating light alloy surfaces |
| JP4736084B2 (en) * | 2005-02-23 | 2011-07-27 | オーエム産業株式会社 | Manufacturing method of product made of magnesium or magnesium alloy |
| US20070075406A1 (en) * | 2005-09-30 | 2007-04-05 | Yueh-Se Ho | Wafer-level method for metallizing source, gate and drain contact areas of semiconductor die |
| IT1393140B1 (en) * | 2009-03-17 | 2012-04-11 | Nuovo Pignone Spa | METHOD OF PRODUCTION OF A PROTECTIVE COATING FOR A COMPONENT OF A TURBOMACCHINA, THE SAME COMPONENT AND THE RELATED MACHINE |
| CN102110866B (en) * | 2009-12-24 | 2013-08-28 | 深南电路有限公司 | Manufacturing process of waveguide slot |
| EP2722930A1 (en) * | 2012-10-16 | 2014-04-23 | Delphi Technologies, Inc. | Coated contact element |
| DE102018203800B4 (en) * | 2018-03-13 | 2019-11-21 | Te Connectivity Germany Gmbh | Contact pin and arrangement for connecting electrical conductors made of copper and aluminum |
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| BE421943A (en) * | 1936-06-06 | |||
| US2871171A (en) * | 1956-05-10 | 1959-01-27 | Atkinson James Thomas Nesbitt | Method of electroplating copper on aluminum |
| US2901409A (en) * | 1956-08-03 | 1959-08-25 | Dow Chemical Co | Anodizing magnesium |
| US3767582A (en) * | 1970-02-02 | 1973-10-23 | Texas Instruments Inc | Etching composition preparatory to nickel plating |
| US3915667A (en) * | 1973-09-20 | 1975-10-28 | Westinghouse Electric Corp | Abrasion resistant coating for aluminum base alloy and method |
| FR2298619A1 (en) * | 1975-01-22 | 1976-08-20 | Pechiney Aluminium | PROCESS AND SURFACE TREATMENT OF AN ALUMINUM WIRE FOR ELECTRICAL USE |
| JPS5268832A (en) * | 1975-12-05 | 1977-06-08 | Nippon Steel Corp | Surface treatment of tin plated steel sheet |
| DE2659273C2 (en) * | 1976-12-29 | 1985-08-29 | Daimler-Benz Ag, 7000 Stuttgart | Process for the continuous processing of two-component paints |
| US4143210A (en) * | 1977-09-30 | 1979-03-06 | Whyco Chromium Company, Inc. | Multi-layer plating for improved corrosion resistance |
| JPS59208098A (en) * | 1983-05-12 | 1984-11-26 | Shimizu Shoji Kk | Improvement of adhesive strength of paint film formed by anionic electrodeposition |
| US4744872A (en) * | 1986-05-30 | 1988-05-17 | Ube Industries, Ltd. | Anodizing solution for anodic oxidation of magnesium or its alloys |
| DE3808609A1 (en) * | 1988-03-15 | 1989-09-28 | Electro Chem Eng Gmbh | METHOD OF GENERATING CORROSION AND WEAR RESISTANT PROTECTION LAYERS ON MAGNESIUM AND MAGNESIUM ALLOYS |
| AU4267096A (en) * | 1994-12-19 | 1996-07-10 | Alcan International Limited | Cleaning aluminium workpieces |
| DE19535068C2 (en) * | 1995-09-21 | 1997-08-21 | Lpkf Cad Cam Systeme Gmbh | Coating for the structured production of conductor tracks on the surface of electrically insulating substrates, method for producing the coating and of structured conductor tracks |
| DE19723980B4 (en) * | 1997-06-06 | 2005-01-27 | Fa. Alfred R. Franz | Continuous, computer-controlled process for the production of black-chromed, surface-defect-free, complete injection-molded parts made of magnesium alloys with electrically conductive and optimally adhesive surface areas and application of this method |
| DE19723975B4 (en) * | 1997-06-06 | 2005-04-21 | Fa. Alfred R. Franz | Continuous, computer-controlled process for the production of black-chromated surface-defect-free, complete injection-molded parts made of magnesium alloys with electrically conductive and optimally adhesive surface areas, and application of this method |
| DE19724013A1 (en) * | 1997-06-06 | 1998-12-10 | Alfred R Franz Fa | Black chromed die cast magnesium alloy components |
| JP4023872B2 (en) * | 1997-06-26 | 2007-12-19 | 大豊工業株式会社 | Swash plate compressor swash plate |
| DE19756845A1 (en) * | 1997-12-19 | 1999-06-24 | Alfred R Franz Fa | Pre-galvanization treatment of magnesium alloy parts |
| WO1999042641A1 (en) * | 1998-02-23 | 1999-08-26 | Mitsui Mining And Smelting Co., Ltd. | Corrosion-resistant, magnesium-based product exhibiting luster of base metal and method for producing the same |
| US6579439B1 (en) * | 2001-01-12 | 2003-06-17 | Southern Industrial Chemicals, Inc. | Electrolytic aluminum polishing processes |
-
2001
- 2001-10-11 AT AT01124435T patent/ATE277207T1/en active
- 2001-10-11 EP EP01124435A patent/EP1302565B1/en not_active Expired - Lifetime
- 2001-10-11 DE DE50103781T patent/DE50103781D1/en not_active Expired - Lifetime
-
2002
- 2002-10-09 WO PCT/EP2002/011291 patent/WO2003033777A1/en not_active Application Discontinuation
- 2002-10-10 KR KR1020020061816A patent/KR100553233B1/en not_active IP Right Cessation
- 2002-10-10 JP JP2002297389A patent/JP2003221683A/en active Pending
- 2002-10-11 US US10/269,265 patent/US20030079997A1/en not_active Abandoned
- 2002-10-11 CN CNB021457549A patent/CN1213169C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101205609B (en) * | 2006-12-18 | 2010-08-11 | 比亚迪股份有限公司 | Composition for magnesium alloy surface activation |
| CN103305894A (en) * | 2012-03-09 | 2013-09-18 | 苏州汉扬精密电子有限公司 | Magnesium alloy surface treatment method |
| CN103305894B (en) * | 2012-03-09 | 2016-01-27 | 苏州汉扬精密电子有限公司 | Surface treatment method of Mg alloy |
| CN103498156A (en) * | 2013-09-27 | 2014-01-08 | 成都四威高科技产业园有限公司 | Surface coating technology of silicon carbide particle reinforced aluminium-based composite |
| CN104562004A (en) * | 2015-01-28 | 2015-04-29 | 江西富意美实业有限公司 | Aluminum-alloy temperature sensing pipe for various types of temperature controllers and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2003033777A1 (en) | 2003-04-24 |
| US20030079997A1 (en) | 2003-05-01 |
| KR100553233B1 (en) | 2006-02-22 |
| CN1213169C (en) | 2005-08-03 |
| EP1302565B1 (en) | 2004-09-22 |
| KR20030030953A (en) | 2003-04-18 |
| ATE277207T1 (en) | 2004-10-15 |
| EP1302565A1 (en) | 2003-04-16 |
| DE50103781D1 (en) | 2004-10-28 |
| JP2003221683A (en) | 2003-08-08 |
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