CN1139675C - Anticorrosion modifier for the surface of copper and copper alloy - Google Patents
Anticorrosion modifier for the surface of copper and copper alloy Download PDFInfo
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- CN1139675C CN1139675C CNB991132351A CN99113235A CN1139675C CN 1139675 C CN1139675 C CN 1139675C CN B991132351 A CNB991132351 A CN B991132351A CN 99113235 A CN99113235 A CN 99113235A CN 1139675 C CN1139675 C CN 1139675C
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- copper
- water
- solvent
- inhibiter
- organic solvent
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Abstract
The present invention relates to an anticorrosion modifier for the surface of copper and copper alloy, which is characterized in that the modifier is a solution system prepared from a corrosion inhibitor, an electrolyte and solvent, wherein the corrosion inhibitor is selected from one of benzotriazole (BTA), a derivative thereof, 2-mercapto benzoxazole (MBO) and a derivative thereof; the electrolyte is a compound which has no oxidizability or passivation performance and generates cations of first and second main group element cations or ammonium ions; the solvent is water, or polar organic solvent, or mixed solvent prepared from water and organic solvent mutually soluble with water or mixed solvent prepared from different kinds of mutually soluble polar organic solvent. The method has the advantages of short treatment time, simple and convenient operation, low preparation cost and few changes of original metal color.
Description
The present invention relates to the Corrosion of Metallic Materials protection, a kind of treatment agent to copper and alloy corrosion protection thereof is provided especially.
Inhibiter is meant and makes an addition to the significantly reduced material of the corrosion speed that can make material in the corrosive medium on a small quantity.Thereby inhibiter common feature in use is to keep its certain concentration in corrosive medium or the environment.Copper and alloy thereof are to carry out corrosion prevention the earliest and one of the most successful material with inhibiter.Some nitrogen heterocyclic organic compound have good protective effect as this and triazole (BTA) etc. to the corrosion of copper, by industrial scale applications for many years.But, the inhibiter of copper also uses as protection against corrosion surface modification (presetting anticorrosive film) material, mainly be: 1) by copper sample being carried out immersion treatment (Walker R under the condition that heats or do not heat with the aqueous solution of inhibiter or the solution of other solvent, " Benzotriazole asa Corrosion Inhibitor for Immersed Copper ", Corrosion, 1973,29 (7): 290-296; Brunoro G, Parmigiani F, Perboni G, RocchiniG, Trabanelli G, " Corrosion Inhibition of OFHC Copper byPrefilming with Organic Compounds ", British Corrosion Journal, 1992,27 (1): 75-79; Zhu Hongfan, " application of BTA inhibiter in historical relic's protection ", corrosion science and guard technology, 1999,11 (4): 255-256); 2) by solution copper or copper alloy are carried out immersion treatment (Zhu Hongfan under the condition of normal temperature or heating with inhibiter+oxidation or deactivation matter, " application of BTA inhibiter in historical relic's protection ", corrosion science and guard technology, 1999,11 (4): 255-256; Imperial court's inscription, " the BTAH passivation of copper and copper alloy part ", material protection, 1993,26 (1): 40-41).Experiment and result of study all show; if will reach preferably only dealing with the treatment time that agent need be grown of protection effect with the inhibiter aqueous solution; and deal with agent with the corrosion inhibitor solution that adds oxidizing substance; then owing to changed the formation mechanism of corrosion inhibiting film, the protective value of the corrosion inhibiting film that is obtained is unsatisfactory.
The object of the present invention is to provide a kind of copper and copper alloy surface protection against corrosion modification treatment agent, its treatment time is short, easy and simple to handle, cheap, do not change the virgin metal color and luster substantially.
The invention provides a kind of copper and copper alloy surface anticorrosion modifier, it is characterized in that: this treatment agent is the solution system that inhibiter, ionogen, solvent constituted; Inhibiter is selected from that benzotriazole, triazole derivative, 2-are dredged basic benzoxazoles, 2-dredges a kind of of basic benzoxazoles derivative; Ionogen is the compound of first main group, the second main group element positively charged ion or ammonium ion for the positively charged ion that does not possess oxidation or passivation and produced when ionization; Solvent can be water, polar organic solvent, also can be water with can and the mixed solvent of the mixed solvent formed of the organic solvent that dissolves each other of water or the opposed polarity organic solvent composition that dissolves each other to each other; The concentration range of inhibiter is 10
-2Mmol/L-10
3Between the mmol/L; Electrolytical mass percent concentration scope is between 0.001%-50%.
In general, the inhibition mechanism and the essence of the nitrogen heterocyclic inhibiter of copper are: inhibiter generates cupprous insoluble mixture (complex) at sample/solution corrosion medium interface place with the univalent copper ion generation chemical reaction that corrosion produces, constitute fine and close inhibition rete at sample surfaces, thereby mass transfer and charge transfer to corrosion process produce obstruction, play the control action kou to corrosion process.For example, the copper/solution interface place of copper in containing the chloride soln medium of nitrogen heterocyclic inhibiter has following variation to take place:
Cu+Cl
- CuCl+e
- (1)
Do not exist under the complexing ionic condition, as KNO
3Or Na
2SO
4Deng having in the solution:
The ionogen role only is by the high effect of electricity the electroconductibility of medium to be increased among the present invention, the electrochemical corrosion course that has promptly guaranteed copper or copper alloy is smooth, also promptly guarantees the carrying out of reaction (1), (2), (3) or reaction (4), (5).After with treatment agent of the present invention copper or copper alloy sample being handled, make sample in the liquid phase corrosive medium or the corrosion resistance in the atmospheric environment obtain to improve.
The present invention has following advantage:
1. need in sample usage or storage environment or medium, not keep inhibiter;
2. the treatment time is short;
3. with low cost;
4. easy and simple to handle;
5. do not change the virgin metal color and luster substantially.
Embodiment 1
With the 1mmol/L BTA+40%NaCl aqueous solution is treatment agent, under room temperature, the copper sample of degreasing and rust removal is made immersion treatment 1 hour, and the back is cleaned with water.Treated sample soaks a week in 3.5% sodium chloride medium after, the inhibition efficiency that records is 90%.
Embodiment 2
Chloroform soln with 1mmol/L BTA+20% perchloric acid tetraethyl-ammonium salt is a treatment agent, under room temperature, the copper sample of degreasing and rust removal is made immersion treatment 1 hour.Treated sample soaks a week in 3.5% sodium chloride medium after, the inhibition efficiency that records is 83%.
Embodiment 3
With 0.5mol/L BTA+5%K
3[Fe (SCN)
6] the aqueous solution be treatment agent, under room temperature, the copper sample of degreasing and rust removal was made immersion treatment 1 hour, the back clean with water.Treated sample soaks a week in 3.5% sodium chloride medium after, the inhibition efficiency that records is 88%.
Embodiment 4
With 5mmol/L BTA+1%Na
2SO
4Solution (solvent is the mixing of 10: 90 ethanol/water) is treatment agent, under 50 ℃, the copper sample of degreasing and rust removal is made immersion treatment 1 hour, and the back is cleaned with water.Treated sample soaks a week in 3.5% sodium chloride medium after, the inhibition efficiency that records is 92%.
Embodiment 5
With 50mmol/L BTA+1%LiBr+3%Na
2SO
4Solution be treatment agent, under 60 ℃, the copper sample of degreasing and rust removal was made immersion treatment 0.5 hour, sample is cleaned with water in the back.Treated sample soaks a week in 3.5% sodium chloride medium after, the inhibition efficiency that records is 96%.
Embodiment 6
Solution with 50mmol/L 5-methyl benzotriazazole+5%KSCN is treatment agent, under 50 ℃, the copper sample of degreasing and rust removal is made immersion treatment 0.5 hour, and sample is cleaned with water in the back.Treated sample soaks a week in 3.5% sodium chloride medium after, the inhibition efficiency that records is 84%.
Embodiment 7
So that 1mmol/L 4-butyl benzotriazole+the 3%NaCl aqueous solution is treatment agent, under room temperature, the copper sample of degreasing and rust removal was made immersion treatment 1 hour, the back is cleaned with water.Treated sample soaks a week in 3.5% sodium chloride medium after, the inhibition efficiency that records is 70%.
Embodiment 8
With 1mmol/L MBO (2-mercaptobenzoxazole, English name: 2-mercaptobenzoxazole)+10% CaCl
2Solution be treatment agent, under room temperature, with degreasing and rust removal polish copper sample immersion treatment 0.5 hour therein, the back is cleaned with water.Treated sample soaks a week in 3.5% sodium chloride medium after, the inhibition efficiency that records is 92%.
Embodiment 9
With 5mmol/L 4-methyl-5-ethyl-2-mercaptobenzoxazole+15%NH
4The solution of Ac (solvent is the mixing of 10: 90 ethanol/water) is treatment agent, and under room temperature, with copper sample immersion treatment 0.5 hour therein, the back is cleaned with water.Treated sample soaks a week in 3.5% sodium chloride medium after, the inhibition efficiency that records is 93%.
Embodiment 10
Solution (solvent is the mixing of 10: 90 ethanol/water) with 5mmol/L 4-methyl-5-ethyl-2-mercaptobenzoxazole+15%HAc is treatment agent, and under room temperature, with copper sample immersion treatment 0.5 hour therein, the back is cleaned with water.Treated sample soaks a week in 3.5% sodium chloride medium after, the inhibition efficiency that records is 90%.
Embodiment
With 0.5mmol/L MBO+0.01%MgSO
4Solution be treatment agent, under 50 ℃, degreasing and rust removal is polished brass sample immersion treatment 0.5 hour therein, the back is cleaned with water.Treated sample soaks a week in 3.5% sodium chloride medium after, the inhibition efficiency that records is 82%.
Embodiment 12
With 1mmol/L MBO+3%Na
2SO
4Solution be treatment agent, under 35 ℃, with degreasing and rust removal bronze sample immersion treatment 1 hour therein, the back is cleaned with water.Treated sample soaks a week in 3.5% sodium chloride medium after, the inhibition efficiency that records is 91%.
Embodiment 13
Solution with 1mmol/L MBO+5%NaOH is treatment agent, and under 35 ℃, with degreasing and rust removal bronze sample immersion treatment 1 hour therein, the back is cleaned with water.Treated sample soaks a week in 3.5% sodium chloride medium after, the inhibition efficiency that records is 87%.
Embodiment 14
Ethanolic soln with 0.3mmol/L MBO+3% tetramethyl ammonium hydroxide is a treatment agent, and under 35 ℃, with degreasing and rust removal bronze sample immersion treatment 1 hour therein, the back is cleaned with water.Treated sample soaks a week in 3.5% sodium chloride medium after, the inhibition efficiency that records is 71%.
Embodiment 15
With 0.1mmol/L MBO+45%Na
2SO
4Solution be treatment agent, under 35 ℃, with degreasing and rust removal bronze sample immersion treatment 1 hour therein, the back is cleaned with water.Treated sample soaks a week in 3.5% sodium chloride medium after, the inhibition efficiency that records is 68%.
Embodiment 16
With 1mmol/L MBO+5%H
2SO
4Solution be treatment agent, under 40 ℃, with degreasing and rust removal bronze sample immersion treatment 1 hour therein, the back is cleaned with water.Treated sample soaks a week in 3.5% sodium chloride medium after, the inhibition efficiency that records is 71%.
Embodiment 17
With 1mmol/L MBO+0.1%Cs
2SO
4Ethanol/methanol solution be treatment agent, under room temperature, with degreasing and rust removal copper sample immersion treatment 0.5 hour therein, the back is cleaned with water.Treated sample soaks a week in 3.5% sodium chloride medium after, the inhibition efficiency that records is 93%.
Embodiment 18
With 0.5mmol/L MBO+3%NaNO
3Ethanolic soln be treatment agent, under room temperature, with degreasing and rust removal polish copper sample immersion treatment 0.5 hour therein, the back is cleaned with water.Treated sample soaks a week in 3.5% sodium chloride medium after, the inhibition efficiency that records is 72%.
Embodiment 19
Solution (solvent is the mixing of 15: 85 methanol) with 0.5mol/L MBO+0.1mol/L HCl is treatment agent, and under room temperature, with degreasing and rust removal copper sample immersion treatment 0.5 hour therein, the back is cleaned with water.Treated sample soaks a week in 3.5% sodium chloride medium after, the inhibition efficiency that records is 86%.
Embodiment 20
Solution (solvent is the mixing of 15: 85 acetone) with 10mmol/L MBO+0.5mol/L HCl is treatment agent, and under room temperature, with degreasing and rust removal polish copper sample immersion treatment 0.5 hour therein, the back is cleaned with water.Treated sample soaks a week in 3.5% sodium chloride medium after, the inhibition efficiency that records is 83%.
Embodiment 21
Ethanolic soln with 10mmol/L MBO+0.5 mol/L HCl is a treatment agent, and under room temperature, with degreasing and rust removal polish copper sample immersion treatment 0.5 hour therein, the back is cleaned with water.Treated sample soaks a week in 3.5% sodium chloride medium after, the inhibition efficiency that records is 87%.
Claims (1)
1. copper and copper alloy surface anticorrosion modifier, it is characterized in that: this treatment agent is the solution system that inhibiter, ionogen, solvent constituted; Inhibiter is selected from that benzotriazole, triazole derivative, 2-are dredged basic benzoxazoles, 2-dredges a kind of of basic benzoxazoles derivative; Ionogen is the compound of first main group, the second main group element positively charged ion or ammonium ion for the positively charged ion that does not possess oxidation or passivation and produced when ionization; Solvent be water, polar organic solvent, water and can and the mixed solvent formed of the mixed solvent formed of the organic solvent that dissolves each other of water or the opposed polarity organic solvent that dissolves each other to each other; The concentration range of inhibiter is 10
-2Mmol/L-10
3Between the mmol/L; Electrolytical mass percent concentration scope is between 0.001%-50%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB991132351A CN1139675C (en) | 1999-09-03 | 1999-09-03 | Anticorrosion modifier for the surface of copper and copper alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB991132351A CN1139675C (en) | 1999-09-03 | 1999-09-03 | Anticorrosion modifier for the surface of copper and copper alloy |
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| Publication Number | Publication Date |
|---|---|
| CN1287187A CN1287187A (en) | 2001-03-14 |
| CN1139675C true CN1139675C (en) | 2004-02-25 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB991132351A Expired - Fee Related CN1139675C (en) | 1999-09-03 | 1999-09-03 | Anticorrosion modifier for the surface of copper and copper alloy |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101812690A (en) * | 2010-04-13 | 2010-08-25 | 范伟京 | Hard film anti-rusting agent and preparation method thereof |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100400709C (en) * | 2004-03-25 | 2008-07-09 | 中国印钞造币总公司 | Anti-discolouring technology for copper alloy coin blank and special preparation for anti-discolouring thereof |
| CN101445923B (en) * | 2008-12-30 | 2012-07-04 | 森鹤乐器股份有限公司 | Passivation method for brass antitarnish |
| CN101935839A (en) * | 2010-09-01 | 2011-01-05 | 六安市晖润粉末新材料有限公司 | Protective liquid for preventing oxidation of copper powder, and preparation method and using method thereof |
| CN104310603A (en) * | 2014-11-10 | 2015-01-28 | 乌鲁木齐市科发展精细化工有限公司 | Highly concentrated copper corrosion inhibitor and preparation method thereof |
| CN113976529A (en) * | 2021-10-25 | 2022-01-28 | 宁波江丰电子材料股份有限公司 | Cleaning method of copper target material |
-
1999
- 1999-09-03 CN CNB991132351A patent/CN1139675C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101812690A (en) * | 2010-04-13 | 2010-08-25 | 范伟京 | Hard film anti-rusting agent and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1287187A (en) | 2001-03-14 |
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