CN103695888B - Bundy tube galvanized chromium-free olive passivation agent I - Google Patents
Bundy tube galvanized chromium-free olive passivation agent I Download PDFInfo
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- CN103695888B CN103695888B CN201310722065.2A CN201310722065A CN103695888B CN 103695888 B CN103695888 B CN 103695888B CN 201310722065 A CN201310722065 A CN 201310722065A CN 103695888 B CN103695888 B CN 103695888B
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- Prior art keywords
- bundy tube
- chromium
- passivation
- passivation agent
- free
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- 238000002161 passivation Methods 0.000 title claims abstract description 31
- 240000007817 Olea europaea Species 0.000 title claims abstract description 17
- 244000239634 longleaf box Species 0.000 title claims abstract description 17
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 12
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 6
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001509 sodium citrate Substances 0.000 claims abstract description 6
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims abstract description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims abstract description 6
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims abstract description 6
- 229940038773 trisodium citrate Drugs 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 7
- 238000000576 coating method Methods 0.000 abstract description 7
- 230000007797 corrosion Effects 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- 229910052802 copper Inorganic materials 0.000 description 10
- 239000010949 copper Substances 0.000 description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 8
- 239000011651 chromium Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 229910052804 chromium Inorganic materials 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000012876 topography Methods 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 238000004500 asepsis Methods 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- JTYRXXKXOULVAP-UHFFFAOYSA-N 1,2-dibromo-3-phenoxybenzene Chemical compound BrC1=CC=CC(OC=2C=CC=CC=2)=C1Br JTYRXXKXOULVAP-UHFFFAOYSA-N 0.000 description 1
- KTADSLDAUJLZGL-UHFFFAOYSA-N 1-bromo-2-phenylbenzene Chemical group BrC1=CC=CC=C1C1=CC=CC=C1 KTADSLDAUJLZGL-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- GOLXNESZZPUPJE-UHFFFAOYSA-N spiromesifen Chemical compound CC1=CC(C)=CC(C)=C1C(C(O1)=O)=C(OC(=O)CC(C)(C)C)C11CCCC1 GOLXNESZZPUPJE-UHFFFAOYSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The present invention relates to Bundy tube galvanized chromium-free olive passivation agent I, adopt the article such as Sodium orthomolybdate, Trisodium Citrate, S-WAT, propanedioic acid, nickelous nitrate to be mixed by the dissolving of certain ratio to form, the passive film of synthesis improves the corrosion resisting property of coating, gives coating deeply bright olive passivation film simultaneously.
Description
Technical field
The present invention relates to Bundy tube galvanized chromium-free olive passivation agent I, particularly relate to the composition of Bundy tube galvanized chromium-free olive passivation agent, the effect of each composition and compound method.
Background technology
Bundy tube just refers to the fine steel tube of diameter at 4.6-10.6mm.Be mainly used in the oil-pressure gauge(feed)pipe in automotive industry, refrigeration industry, well heater process industry, oil fuel pipe, brake line and similar device, alternative copper pipe can also be widely used in, reduce use cost, Bundy tube is with cold rolled strip thin plate pipe crimping, welding, with cyanide electroplating bottoming, layers of copper is zinc-plated to be completed.Copper coating in use plays protection Bundy tube, the effect of slowing down corrosion matrix, and can help through welding, so Bundy tube must cover copper or Copper substrate in surface.Because Bundy tube requires higher, so generally all adopt olive passivation to meet its requirement to wear and corrosion behavior.Traditional olive passivation technique is all adopt sexavalent chrome passivation, but sexavalent chrome has severe toxicity, has the harm of carcinogenic teratogenesis.According to GB-2008 " plating pollutant emission standard ", to Pd, Hg, Cd, Cr
6+, poly-6 kinds of first kind pollutents such as dibromodiphenyl ether and poly-bromo biphenyl emission standard had lower restriction, European Union " about prohibitting the use some Hazardous Substances Directive in electronic electric equipment " (ROHS) of enforcement in 1 day July in 2006, forbid containing 6 kinds of objectionable impuritiess such as sexavalent chromes in electronics that EU market is thrown in and electrical equipment, so the products substitution sexavalent chrome passivation of environment-friendly type becomes an urgent demand.
The passivation of environment-friendly type mainly adopts trivalent chromium and chromium-free deactivation both direction.Trivalent chromium passivator as: Olive passivator with trivalent chromium of Bundy tube ZL201210147166.7, it is applicable to iron-based body or Copper substrate, but trivalent chromium has certain toxicity, does not therefore meet the requirement of asepsis environment-protecting.Chromium-free deactivation system has titanate, molybdate, tungstate, rare earth, silicate, the passive film asepsis environment-protecting of chromium-free deactivation in recent years, solidity to corrosion and outward appearance all improve a lot, and meet common handware plating requirement, so non-chromium inactivating technique industrially has wide practical use.
Passive film burnt hair, the blackout of current molybdate Chrome-free olive passivation system on iron-based body, green black colour display is shallow, few, and Copper substrate or copper coating zinc-plated after carry out passivation, passive film has obvious green black colour, therefore this Bundy tube galvanized chromium-free olive passivation agent I be applicable to Copper substrate or copper coating zinc-plated after carry out passivation, passive film particle is evenly thick.
Summary of the invention
The present invention, in order to improve zinc coating passivation film asepsis environment-protecting, makes in passivating solution not containing Cr simultaneously
6+, Cr
3+and invented Bundy tube galvanized chromium-free olive passivation agent I.
The present invention adopts Sodium orthomolybdate 10 ~ 20g/L, Trisodium Citrate 5 ~ 15g/L, S-WAT 10 ~ 20g/L, propanedioic acid 5 ~ 15g/L, nickelous nitrate 10 ~ 20g/L, waits article to form Bundy tube galvanized chromium-free olive passivation agent I.
Concrete preparation method of the present invention comprises the step of following order:
A. the Sodium orthomolybdate of calculated amount is poured in a small amount of water, stir and make it fully dissolve;
B. the Trisodium Citrate of calculated amount and S-WAT are slowly added, stir and make it fully dissolve;
C. the propanedioic acid of calculated amount is poured into, stir;
D. the nickelous nitrate of calculated amount is slowly added, stir rapidly, make it fully dissolve;
E. by after water (the specific conductivity < 5us/cm) constant volume of calculated amount, leave standstill 10 minutes, adjust pH in 2 ~ 2.5 scopes with nitric acid.
Gained Bundy tube galvanized chromium-free olive passivation agent I of the present invention is the liquid of clarification in nattierblue.
Description of test
The present invention, by after the cyanide electroplating bottoming on matrix, zinc-plated experiment, implements Passivation Treatment in Chrome-free olive passivation liquid, after the process of different time, observes the color and luster of coating, and carries out neutral salt spray test and measure its corrosion resisting property.
Accompanying drawing explanation
Fig. 1 is the polarization curve of the passivating solution that embodiment 1 is prepared;
Fig. 2 be print after passivation under scanning electron microscope × surface topography of 500 times;
Fig. 3 be print after passivation under scanning electron microscope × surface topography of 1000 times;
Fig. 4 be print after passivation under scanning electron microscope × surface topography of 2000 times;
Fig. 5 be print after passivation under scanning electron microscope × surface topography of 5000 times;
The image analysis of Fig. 6 passive film that to be print after passivation observe at XRD;
Fig. 7 be print after passivation under scanning electron microscope × Cross Section Morphology of 2000 times.
Embodiment
Embodiment 1
The concrete preparation process of the present embodiment is as follows:
Sodium orthomolybdate 15g/L, nickelous nitrate 25g/L, Trisodium Citrate 10g/L, S-WAT 10g/L, propanedioic acid 10g/L.
A. the Sodium orthomolybdate of 15g/L is poured in a small amount of water, stir and make it fully dissolve;
B. the Trisodium Citrate of 10g/L and the S-WAT of 10g/L are slowly added, stir and make it fully dissolve;
C. the propanedioic acid of 10g/L is poured into, stir;
D. the nickelous nitrate of 25g/L is slowly added, stir rapidly, make it fully dissolve;
E. by after water (the specific conductivity < 5us/cm) constant volume of calculated amount, leave standstill 10 minutes, adjust pH in 2.5 scopes with nitric acid.
F. general Low-Cyanide Zinc Plating is prepared, and adjusted to ph, electroplate.
G. take out sample after certain hour, in the nitric acid of 3%, carry out Passivation Treatment after bright dipping, passivation time is 10s.
Claims (1)
1. be applied to Bundy tube galvanized chromium-free olive passivation agent I, it is characterized in that the raw material of passivator is composed as follows: containing Sodium orthomolybdate 10 ~ 20g/L, Trisodium Citrate 5 ~ 15g/L, S-WAT 10 ~ 20g/L, propanedioic acid 5 ~ 15g/L, nickelous nitrate 10 ~ 20g/L, all the other are water, specific conductivity < 5 μ s/cm; When Bundy tube galvanized chromium-free olive passivation agent I uses, pH value maintains in 2 ~ 2.5 scopes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310722065.2A CN103695888B (en) | 2013-12-24 | 2013-12-24 | Bundy tube galvanized chromium-free olive passivation agent I |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310722065.2A CN103695888B (en) | 2013-12-24 | 2013-12-24 | Bundy tube galvanized chromium-free olive passivation agent I |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103695888A CN103695888A (en) | 2014-04-02 |
| CN103695888B true CN103695888B (en) | 2015-12-02 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310722065.2A Expired - Fee Related CN103695888B (en) | 2013-12-24 | 2013-12-24 | Bundy tube galvanized chromium-free olive passivation agent I |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105483676A (en) * | 2015-12-17 | 2016-04-13 | 山东建筑大学 | Environment-friendly archaizing method for household galvanized decorative sheet |
| CN105506607B (en) * | 2015-12-17 | 2018-05-18 | 山东建筑大学 | The method that galvanized sheet imitates gold |
| CN109280914A (en) * | 2018-11-26 | 2019-01-29 | 山东建筑大学 | A kind of preparation method of green galvanized chromium-free sky blue passivator |
| CN109280913A (en) * | 2018-11-26 | 2019-01-29 | 山东建筑大学 | Green galvanized chromium-free sky blue passivator |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102644073A (en) * | 2012-05-14 | 2012-08-22 | 山东建筑大学 | Olive passivator with trivalent chromium of Bundy tube |
| CN103255403A (en) * | 2013-05-16 | 2013-08-21 | 山东建筑大学 | Non-chrome black passivator |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060042726A1 (en) * | 2004-09-02 | 2006-03-02 | General Electric Company | Non-chrome passivation of steel |
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- 2013-12-24 CN CN201310722065.2A patent/CN103695888B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102644073A (en) * | 2012-05-14 | 2012-08-22 | 山东建筑大学 | Olive passivator with trivalent chromium of Bundy tube |
| CN103255403A (en) * | 2013-05-16 | 2013-08-21 | 山东建筑大学 | Non-chrome black passivator |
Non-Patent Citations (1)
| Title |
|---|
| 镀锌层军绿色钝化工艺研究;肖鑫等;《湖南工程学院学报》;20070630;第17卷(第2期);第78－80页 * |
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| CN103695888A (en) | 2014-04-02 |
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Inventor after: Shi Lei Inventor after: Shi Jiazheng Inventor after: Song Wenting Inventor after: Liu Kegao Inventor after: Lin Xiaojuan Inventor after: Du Jie Inventor before: Shi Lei |
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Free format text: CORRECT: INVENTOR; FROM: SHI LEI TO: SHI LEI SHI JIAZHENG SONG WENTING LIU KEGAO LIN XIAOJUAN DU JIE |
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Effective date of registration: 20150818 Address after: Fengming road Licheng District 250101 Shandong city in Ji'nan Province, Shandong Jianzhu University Applicant after: Shandong Construction University Address before: Fengming Road District of Ji'nan City, Shandong province 250101 port development Shandong Jianzhu University Applicant before: Shi Lei |
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