CN105803429A - Magnesium alloy surface activating liquid, preparation method and activating method - Google Patents
Magnesium alloy surface activating liquid, preparation method and activating method Download PDFInfo
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- CN105803429A CN105803429A CN201410854920.XA CN201410854920A CN105803429A CN 105803429 A CN105803429 A CN 105803429A CN 201410854920 A CN201410854920 A CN 201410854920A CN 105803429 A CN105803429 A CN 105803429A
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- magnesium alloy
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Abstract
The invention relates to magnesium alloy activating liquid. The activating liquid contains phosphoric acid, fluorides and polyethylene polyamine. The invention further provides a preparation method of the activating liquid and a magnesium alloy surface activating method. The activating liquid can be used for quickly forming a dense film oxide layer on the surface of a magnesium alloy, so that the realization of a later zinc sinking procedure and the protection of a magnesium alloy substrate are facilitated.
Description
Technical field
The present invention relates to electroplating technology field, particularly relate to a kind of magnesium alloy surface activation liquid, preparation method and activation method.
Background technology
Magnesium alloy is constantly subjected to extensive concern because of performance and the rich in natural resources of its uniqueness, is taken as ep-type material again in this century and extremely praises highly.But owing to magnesium alloy plating technique is still immature, the problem of corrosion resistance difference becomes the major obstacle playing its superiority, thus greatly limit its wider popularization and application.
Therefore, Mg alloy surface carrying out effectively decoration anticorrosion is particularly important, existing conventional treatment technology has a plating, and magnesium alloy is in conventional bath solution and unstable, it is necessary to its surface carries out pretreatment so that it is adapt to routine plating environment.It is applicable to industrial pre-treating technology at present and has two big classes: heavy zinc method and direct electroless nickel method.Both approaches is all released by DowChemical company of the U.S. the earliest, and each used producer in practical probation process later, has carried out improvement in various degree all based on this, has developed into similar multiple way.What be seen in report has NorskHydro technique and WCM technique etc..
Heavy zinc method in order that dissolve the oxide of magnesium;Form hydroxide one layer thin at Mg alloy surface simultaneously, prevent the further oxidation of magnesium.Present specification is exactly based on heavy zinc method, technical process therein is improved.The common technological process of heavy zinc method is: oil removing scale removal → pickling → activation → sink zinc → copper facing → chemical nickel plating → electro-coppering/ni cr etc..
Can there is vigorous reaction with the acid/base solution in process in magnesium alloy in heavy zinc technology, and normally used zincate solution is alkalescence, so for the speed controlling heavy zinc, magnesium alloy can be activated before heavy zinc.But the activation of existing activating solution is relatively slow, and soluble salt easily deposits and affects activating solution life cycle.
Summary of the invention
The present invention provides a kind of magnesium alloy activating solution, can accelerate the activation of magnesium alloy, improve the sealing effect of Mg alloy surface, can extend the life cycle of activating solution further simultaneously.
A kind of magnesium alloy activating solution of the present invention includes following component: phosphoric acid, fluoride and polyethylene polyamine.
The preparation method that present invention also offers a kind of magnesium alloy activating solution, described method is: add phosphoric acid in the aqueous solution of polyethylene polyamine, fluoride stirs to obtain described activating solution.
A kind of method that present invention also offers magnesium alloy surface activation, contacts with activating solution including by the magnesium alloy through pre-treatment, must arrive surface and have the magnesium alloy substrates of active layer；Wherein, described activating solution is magnesium alloy activating solution of the present invention.
Containing polyethylene polyamine in the magnesium alloy activating solution of the present invention, affiliated polyethylene polyamine can improve the life-span of activating solution, accelerates magnesium alloy activation, and improves sealing effect, reduces pin hole corner etc. and is not easy to activate situation about putting in place.
Detailed description of the invention
Technical scheme relates to a kind of magnesium alloy activating solution, and described activating solution comprises following component: phosphoric acid, fluoride and polyethylene polyamine.
Under preferable case, the content of described phosphoric acid is 150-200g/L, and the content of described fluoride is 30-100g/L, and the content of described polyethylene polyamine is 10-20g/L.
Under preferable case, described fluoride is at least one in ammonium acid fluoride, Fluohydric acid., fluoboric acid.
Under preferable case, described fluoride is Fluohydric acid..
Under preferable case, described polyethylene polyamine is at least one in ethylenediamine, divinyl triethylamine, triethylene triethylammonium tetrakis, four ethylene five ethamine, five hexamine, six ethylene seven amine.
The preparation method that present invention also offers a kind of magnesium alloy activating solution, described method is: adds fluoride in the aqueous solution of polyethylene polyamine and stirs to obtain described activating solution.
Under preferable case, the content of described phosphoric acid is 150-200g/L, and the content of described fluoride is 30-100g/L, and the content of described polyethylene polyamine is 10-20g/L.
Under preferable case, described fluoride is at least one in ammonium acid fluoride, Fluohydric acid., fluoboric acid.
Under preferable case, described polyethylene polyamine is at least one in ethylenediamine, divinyl triethylamine, triethylene triethylammonium tetrakis, four ethylene five ethamine, five hexamine, six ethylene seven amine.
A kind of method that present invention also offers magnesium alloy surface activation, contacts with activating solution including by the magnesium alloy through pre-treatment, must arrive surface and have the magnesium alloy substrates of oxide-film；Described activating solution is magnesium alloy activating solution of the present invention.
Below in conjunction with embodiment, the present invention is further described in detail, but is not limited to this.
All raw materials in heretofore described embodiment are such as non-to be refered in particular to, and is commercially available prod.
Embodiment 1
1, magnesium alloy activating solution is prepared
The phosphoric acid solution that will individually configure, ammonium hydrogen fluoride solution, polyethylene polyamine solution mix, after stirring activating solution A1.Wherein, phosphatase 11 70g/L, ammonium acid fluoride 90g/L, polyethylene polyamine are ethylenediamine 15g/L.
2, magnesium alloy surface activation
1) base material pretreatment: selecting the trade mark is that the magnesium alloy of AZ91D is as base material, base material is put into (formula: sodium carbonate 20g/L in degreasing fluid, sodium phosphate 20g/L, sodium citrate 10g/L, sodium lauryl sulphate 1g/L), embathe at 20-30 DEG C 10 minutes, clean with tap water after taking-up, then with the phosphoric acid pickling of 300g/L.
2) activation: by through 1), 2) magnesium alloy substrates crossed of step process puts in embodiment 1 in the activating solution of preparation, activating solution temperature is 15-30 DEG C, takes out, obtain plating piece Y1 after cleaning with tap water after soaking 30-90 time second.
Embodiment 2
The phosphoric acid solution that will individually configure, ammonium hydrogen fluoride solution, polyethylene polyamine solution mix, after stirring activating solution A2.Wherein, phosphatase 11 90g/L, ammonium acid fluoride 90g/L, polyethylene polyamine are ethylenediamine 10g/L, diethylenetriamine 8g/L.
According to the method for embodiment 1, use activating solution A2 that magnesium alloy is activated, obtain plating piece Y2.
Embodiment 3
The phosphoric acid solution that will individually configure, ammonium hydrogen fluoride solution, polyethylene polyamine solution mix, after stirring activating solution A3.Wherein, phosphatase 11 90g/L, ammonium acid fluoride 80g/L, polyethylene polyamine are diethylenetriamine 12g/L.
According to the method for embodiment 1, use activating solution A3 that magnesium alloy is activated, obtain plating piece Y3.
Embodiment 4
Substituting ammonium hydrogen fluoride solution with Fluohydric acid. 45g/L, all the other formula are identical with embodiment 1.
According to the method for embodiment 1, use activating solution A4 that magnesium alloy is activated, obtain plating piece Y4.
Embodiment 5
Substituting ammonium hydrogen fluoride solution with fluoboric acid 35g/L, all the other formula are identical with embodiment 1.
According to the method for embodiment 1, use activating solution A5 that magnesium alloy carries out leaching zinc, obtain plating piece Y5.
Comparative example 1
Except without polyethylene polyamine, all the other are identical with embodiment 1.
Performance test and result
1, active rate
Range estimation: when observing that magnesium alloy substrates thinks that activation completes when almost stopping producing bubble in activating solution.
2, the activating solution life-span
Whether range estimation: observe the activating solution in embodiment 1-5 and comparative example 1, often use and have precipitation to produce after once.
3, test result
| Test event | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative example 1 |
| Sealing effect | Complete in 60 seconds to close | Complete in 60 seconds to close | Complete in 60 seconds to close | Complete in 60 seconds to close | Complete in 60 seconds to close | Complete in 90 seconds to close |
| The activating solution life-span | Use and do not find precipitation for 10 times | Use and do not find precipitation for 10 times | Use and do not find precipitation for 10 times | Use and do not find precipitation for 10 times | Use and do not find precipitation for 10 times | 5 discoveries are used to have obvious white precipitate |
From above-mentioned test result: after adding polyethylene polyamine, the closing speed of activating solution promotes to some extent, activating solution also has obvious prolongation service life simultaneously.
Obviously, above-described embodiment is only for clearly demonstrating example, and is not the restriction to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here without also giving exhaustive to all of embodiment, and the apparent change thus extended out or variation are still among the invention scope of the claims.
Claims (10)
1. a magnesium alloy activating solution, it is characterised in that containing, for example lower component in described activating solution: phosphoric acid, fluoride and polyethylene polyamine.
2. magnesium alloy activating solution according to claim 1, it is characterised in that the content of described phosphoric acid is 150-200g/L, the content of described fluoride is 30-100g/L, and the content of described polyethylene polyamine is 10-20g/L.
3. magnesium alloy activating solution according to claim 1 and 2, it is characterised in that described fluoride is at least one in ammonium acid fluoride, Fluohydric acid., fluoboric acid.
4. magnesium alloy activating solution according to claim 1 and 2, it is characterised in that described fluoride is Fluohydric acid..
5. magnesium alloy activating solution according to claim 1, it is characterised in that described polyethylene polyamine is at least one in ethylenediamine, divinyl triethylamine, triethylene triethylammonium tetrakis, four ethylene five ethamine, five hexamine, six ethylene seven amine.
6. the preparation method of a magnesium alloy activating solution, it is characterised in that described method is: add phosphoric acid in the aqueous solution of polyethylene polyamine, fluoride stirs to obtain described activating solution.
7. the preparation side of magnesium alloy activating solution according to claim 6, it is characterised in that the content of described phosphoric acid is 150-200g/L, the content of described fluoride is 30-100g/L, and the content of described polyethylene polyamine is 10-20g/L.
8. the preparation side of magnesium alloy activating solution according to claim 6, it is characterised in that described fluoride is at least one in ammonium acid fluoride, Fluohydric acid., fluoboric acid.
9. the preparation side of magnesium alloy activating solution according to claim 6, it is characterised in that described polyethylene polyamine is at least one in ethylenediamine, divinyl triethylamine, triethylene triethylammonium tetrakis, four ethylene five ethamine, five hexamine, six ethylene seven amine.
10. a method for magnesium alloy surface activation, contacts with activating solution including by the magnesium alloy through pre-treatment, must arrive surface and have the magnesium alloy substrates of oxide-film；It is characterized in that, described activating solution is the magnesium alloy activating solution described in any one of claim 1-5.
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Citations (4)
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|---|---|---|---|---|
| CN1556247A (en) * | 2003-12-30 | 2004-12-22 | 上海交通大学 | Solution foumula of magnesium, aluminium alloy weak acid activation technology |
| JP2005200709A (en) * | 2004-01-16 | 2005-07-28 | Ky Japan:Kk | Method for forming copper-nickel plating layer on aluminum and magnesium alloy |
| CN101205609A (en) * | 2006-12-18 | 2008-06-25 | 比亚迪股份有限公司 | Composition for magnesium alloy surface activation |
| CN101435098A (en) * | 2007-11-13 | 2009-05-20 | 沈阳工业大学 | Cyanideless nickel layer electroplating method for magnesium alloy surface |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1556247A (en) * | 2003-12-30 | 2004-12-22 | 上海交通大学 | Solution foumula of magnesium, aluminium alloy weak acid activation technology |
| JP2005200709A (en) * | 2004-01-16 | 2005-07-28 | Ky Japan:Kk | Method for forming copper-nickel plating layer on aluminum and magnesium alloy |
| CN101205609A (en) * | 2006-12-18 | 2008-06-25 | 比亚迪股份有限公司 | Composition for magnesium alloy surface activation |
| CN101435098A (en) * | 2007-11-13 | 2009-05-20 | 沈阳工业大学 | Cyanideless nickel layer electroplating method for magnesium alloy surface |
Non-Patent Citations (2)
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| 方景礼: "《电镀配合物-理论与应用》", 30 September 2007 * |
| 贾瑛等: "《大学化学》", 31 January 2012, 西北工业大学出版社 * |
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