CN101824614A - Magnesium alloy surface conversion coating treating fluid and treating process thereof - Google Patents
Magnesium alloy surface conversion coating treating fluid and treating process thereof Download PDFInfo
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- CN101824614A CN101824614A CN 201010146804 CN201010146804A CN101824614A CN 101824614 A CN101824614 A CN 101824614A CN 201010146804 CN201010146804 CN 201010146804 CN 201010146804 A CN201010146804 A CN 201010146804A CN 101824614 A CN101824614 A CN 101824614A
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Abstract
The invention provides a magnesium alloy surface conversion coating treating fluid and a treating process thereof. The treating fluid takes water as a solvent, and per liter of the treating fluid has 0.8-1.2g of calcium oxide, 6-10ml of phosphoric acid, 0-11g of accelerator calcium nitride, 0-1.5g of accelerator sodium metanitrobenzene sulfonate and 0-0.8g of solution stabilizer calcium nitrite. The process flow is as follows: degreasing, rinsing, converting, rinsing and drying, wherein the conversion temperature is 30-60 DEG C, and the conversion time is 20-40 min. Due to the treatment process, a delicate and uniform phosphate conversion coating with good protection performance can be formed on the magnetism alloy surface. The treating fluid takes calcium salts as the main component, has the advantages of safety, environment protection and wide application, can be used in independent protection (immersion oil, grease, wax, and the like), and can be used as protection among working procedures and base for organic coatings such as paint, doup and the like. The conversion coating formed by the treating fluid has strong adhesive force and stable components, and can improve anti-corrosion performance of magnetism alloy parts and prolong the service life thereof.
Description
Technical field
The present invention relates to Mg alloy surface anti-corrosive treatment technology, be specifically related to a kind of magnesium alloy surface conversion coating treating fluid and treatment process thereof.
Background technology
Magnesium alloy is in metallic substance, and proportion is low, specific tenacity is high, electromagnetic shielding is good, damping performance is good and be suitable for recovery uses, at aircraft industry, and automotive industry, household electric appliances, the telecommunications field is by increasingly extensive application.But the electropotential of magnesium alloy extremely negative (2.34KV), poor chemical stability, corrosion resisting property is poor, in most of media, magnesium alloy is all unstable, easily is corroded.Solving magnesium alloy corrosion prevention problem, is to start with from the content of control impurity substantially, prepares highly purified alloy, and form etch-proof rete on Mg alloy surface, and a kind of mode in back is the method for most economical easy row.The Dow7 process using Sodium chromate and the magnesium fluoride of U.S. Dow Chemical company, generate chromic salts and metal jelly at Mg alloy surface, has certain resistance to corrosion, but sexavalent chrome is serious carcinogens, and environmental pollution is serious, do not meet environmental protection requirement, begun to forbid the use of chromic salt in the worldwide.The treatment technology that forms the Chrome-free chemical conversion film at Mg alloy surface is a problem demanding prompt solution, and the research and development of the treatment technology of magnesium alloy surface chromium-free chemical conversion film have become an important directions of magnesium alloy surface protective technical development.
Summary of the invention
Based on above reason, be necessary to develop a kind of magnesium alloy surface conversion coating treating fluid, this treatment solution chromate-free, compliance with environmental protection requirements, and rete is stable, strong adhesion.The objective of the invention is at the deficiencies in the prior art, a kind of safety and environmental protection is provided, the magnesium alloy surface conversion coating treating fluid of toxicological harmless effect and treatment process thereof.
Above-mentioned purpose of the present invention realizes by following technology side:
A kind of magnesium alloy surface conversion coating treating fluid is grouped into by following one-tenth, and every liter of treatment solution composition comprises: calcium oxide 0.8-1.2g, phosphoric acid 6-10ml, promotor nitrocalcite 0-11g, promotor m-nitrobenzene sodium sulfonate 0-1.5g, solution stabilizer calcium nitrite 0-0.8g.
A kind of processing method of carrying out the Mg alloy surface processing with the described magnesium alloy surface conversion coating treating fluid of claim 1, technical process is as follows:
Magnesium alloy work-piece surface degreasing → washing → conversion processing → washing → oven dry, conversion processing step wherein is specific as follows: the magnesium alloy workpiece after will washing pre-treatment through surperficial degreasing and after removing oxide film, dipping is statically placed in and transfers to pH value with phosphoric acid or sodium hydroxide is to carry out conversion processing in the 2.9-3.3 conversion treating solution, its working temperature is 30-60 ℃, and transformation time is 20-40 minute.
Technique effect of the present invention is: adopt conversion process of the present invention, can obtain protective value phosphate conversion film good, uniform and delicate at Mg alloy surface.This conversion film plays shielding effect to medium, and film adhesion is strong, stable components, can stop the erosion of corrosive medium to matrix effectively, makes magnesium alloy erosion resistance and surface that the improvement of essence take place, and makes it effectively to be utilized in actual environment.This conversion coating treating fluid major ingredient is a calcium salt, and safety and environmental protection is free from environmental pollution, of many uses, can be used for independent protection (immersion oil, grease, wax etc.), can also be used for the protection of inter process and the substrate of organic membrane such as paint and foundation cream.The technology of magnesium alloy surface conversion coating of the present invention is easy to control, process stabilizing, and additive is few, and safety and environmental protection has reduced cost in application process.
Description of drawings
Fig. 1 is through the SEM photo of the AM60 magnesium alloy surface conversion coating of treatment solution processing of the present invention.
Fig. 2 is through the SEM photo of the AZ60 magnesium alloy surface conversion coating of treatment solution processing of the present invention.
Fig. 3 is through the SEM photo of the AD91D magnesium alloy surface conversion coating of treatment solution processing of the present invention.
Embodiment
Embodiment 1:
AZ60 magnesium alloy extruded sample is handled.
Make the magnesium alloy treatment soln by following prescription:
Calcium oxide 1.2 gram/every premium on currency solution
8 milliliters/every premium on currency solution of phosphoric acid
Nitrocalcite 10 gram/every premium on currency solution
M-nitrobenzene sodium sulfonate 1.5 gram/every premium on currency solution
Calcium nitrite 0.8 gram/every premium on currency solution
Wash to the degreasing of AZ60 magnesium alloy sample surface and after removing oxide film, put into then and be immersed in that to transfer to pH value with phosphoric acid or sodium hydroxide be 3.2 the above-mentioned treatment solution for preparing, left standstill 40 minutes at 40 ℃, after water cleans then, oven dry again.Certainly corrode voltage and from original-1.5mV rise to-0.89mV through electrochemical tests test this moment, from corrosion current by original 3.2 * 10
-3A/cm
2Be reduced to 3.25 * 10
-4A/cm
2
Embodiment 2:
AZ60 magnesium alloy extrusion sample is handled.
Make the magnesium alloy treatment soln by following prescription:
Calcium oxide 0.8 gram/every premium on currency solution
6 milliliters/every premium on currency solution of phosphoric acid
Nitrocalcite 4 gram/every premium on currency solution
M-nitrobenzene sodium sulfonate 0.5 gram/every premium on currency solution
Wash with the surface degreasing of AZ60 magnesium alloy sample and after removing oxide film, put into then and be immersed in that to transfer to pH value with phosphoric acid or sodium hydroxide be 2.9 the above-mentioned treatment solution for preparing, left standstill 30 minutes at 50 ℃, wash then, dry, through the electrochemical tests test, rise to-0.67mV from original-1.49mV from corrosion voltage, from corrosion current from original 3.0 * 10
-3A/cm
2Rise to 2.90 * 10
-5A/cm
2
Can see that by examples of implementation 1,2 magnesium alloy of handling through this treatment solution corrodes voltage certainly, obviously raises, and also reduces the 1-2 order of magnitude from corrosion current simultaneously.
Embodiment 3:
AZ91D magnesium alloy extruded sample is handled.
Make the magnesium alloy treatment soln by following prescription:
Calcium oxide 0.8 gram/every premium on currency solution
8 milliliters/every premium on currency solution of phosphoric acid
Nitrocalcite 8 gram/every premium on currency solution
M-nitrobenzene sodium sulfonate 1.5 gram/every premium on currency solution
Calcium nitrite 0.5 gram/every premium on currency solution
With after the degreasing of AZ91D Mg alloy surface and remove oxide film and wash, immerse then that to transfer to pH value with phosphoric acid or sodium hydroxide be in 3.1 the above-mentioned treatment solution for preparing in the conversion fluid, left standstill 30 minutes at 40 ℃, after water cleans then, oven dry again.Through electrochemical tests test, corrode voltage-1.47mV certainly and rise to-1.22mV, from corrosion current by-0.25A/cm
2Rise to 6.3 * 10
-4A/cm
2
Embodiment 4:
AM60 magnesium alloy die casting sample is handled.
Make the magnesium alloy treatment soln by following prescription:
Calcium oxide 1.0 gram/every premium on currency solution
0 milliliter/every premium on currency solution of phosphatase 11
Nitrocalcite 11 gram/every premium on currency solution
M-nitrobenzene sodium sulfonate 1.5 gram/every premium on currency solution
Calcium nitrite 0.8 gram/every premium on currency solution
Wash to the degreasing of AM60 magnesium alloy sample surface and after removing oxide film, put into then and be immersed in that to transfer to pH value with phosphoric acid or sodium hydroxide be 3.2 the above-mentioned treatment solution for preparing, left standstill 40 minutes at 30 ℃, after water cleans then, oven dry again.Through electrochemical tests test, corrode voltage certainly and rise to-0.89mV by-1.46mV, from corrosion current by-0.27A/cm
2Rise to 1.56 * 10
-4A/cm
2
Embodiment 5:
AM60 magnesium alloy extruded sample is handled.
Make the magnesium alloy treatment soln by following prescription:
Calcium oxide 1.2 gram/every premium on currency solution
0 milliliter/every premium on currency solution of phosphatase 11
Nitrocalcite 8 gram/every premium on currency solution
M-nitrobenzene sodium sulfonate 2.5 gram/every premium on currency solution
Calcium nitrite 0.5 gram/every premium on currency solution
Wash to the degreasing of AM60 magnesium alloy sample surface and after removing oxide film, put into then and be immersed in that to transfer to pH value with phosphoric acid or sodium hydroxide be 3.0 the above-mentioned treatment solution for preparing, left standstill 20 minutes at 60 ℃, after water cleans then, oven dry again.Through electrochemical tests test, corrode voltage certainly and rise to-0.95mV by-1.47mV, from corrosion current by-0.30A/cm
2Rise to-0.086A/cm
2
Can sum up corroding voltage certainly and all having improved many of the AZ91D that crosses through this solution-treated and AM60 magnesium alloy by 3,4,5 examples than magnesium alloy not through solution-treated from corrosion current.
By above-mentioned example as can be seen, the corrosion stability of magnesium alloy of crossing through this kind solution-treated has strengthened greatly.
Promotor among the present invention is nitrocalcite and m-nitrobenzene sodium sulfonate, and wherein nitrate radical, m-nitrobenzene sulfonic acid root and sodium ion can quicken conversion reaction, simultaneously can crystallization of refinement, guarantee film quality.Can stop thick crystallization to form, make crystallization careful, evenly.And calcium ion wherein can supplemental calcium the deficiency of calcium ion.
Calcium nitrite is a solution stabilizer in the present invention, and nitrite anions is to play stabilization, though nitrite anions has carcinogenic effect, contaminate environment, but along with the carrying out of reaction, nitrite ion is oxidized to nitrate ion, thereby can pollution not arranged to environment.
Compared to prior art, magnesium alloy surface conversion coating treating fluid main component of the present invention is nontoxic calcium oxide and phosphoric acid, environmentally friendly, material in this prescription is all nontoxic or low toxicity material, the calcium salt that forms can form even, careful rete on Mg alloy surface, this rete is very strong to the sticking power of lacquer, and to water, the avidity of oil is all very strong.The rete that the present invention obtains can effectively stop the erosion of corrosive medium to matrix, makes the magnesium alloy component corrosion resistance that the change of essence take place, thereby has guaranteed the life-span of magnesium alloy component.Magnesium alloy conversion film treatment process of the present invention is easy to control, and is stable, and with low cost.
Claims (2)
1. a magnesium alloy surface conversion coating treating fluid is characterized in that, is grouped into by following one-tenth, every liter of treatment solution composition comprises: calcium oxide 0.8-1.2g, phosphoric acid 6-10ml, promotor nitrocalcite 0-11g, promotor m-nitrobenzene sodium sulfonate 0-1.5g, solution stabilizer calcium nitrite 0-0.8g.
2. one kind is carried out the processing method that Mg alloy surface is handled with the described magnesium alloy surface conversion coating treating fluid of claim 1, it is characterized in that technical process is as follows:
Magnesium alloy work-piece surface degreasing → washing → conversion processing → washing → oven dry, conversion processing step wherein is specific as follows: the magnesium alloy workpiece after will washing pre-treatment through surperficial degreasing and after removing oxide film, dipping is statically placed in and transfers to pH value with phosphoric acid or sodium hydroxide is to carry out conversion processing in the 2.9-3.3 conversion treating solution, its working temperature is 30-60 ℃, and transformation time is 20-40 minute.
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| CN2010101468044A CN101824614B (en) | 2010-04-15 | 2010-04-15 | Magnesium alloy surface conversion coating treating fluid and treating process thereof |
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| CN2010101468044A CN101824614B (en) | 2010-04-15 | 2010-04-15 | Magnesium alloy surface conversion coating treating fluid and treating process thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104894621A (en) * | 2015-05-11 | 2015-09-09 | 上海电力学院 | Preparation method for Ca-P-phase bioactive anticorrosive coating on medical magnesium alloy matrix surface |
| CN108624877A (en) * | 2018-06-15 | 2018-10-09 | 莱诺斯科技（北京）股份有限公司 | A kind of magnesium lithium alloy material surface anti-corrosive treatment method |
| CN110592570A (en) * | 2019-09-27 | 2019-12-20 | 山东华盛荣镁业科技有限公司 | Magnesium alloy surface black chemical conversion process |
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2010
- 2010-04-15 CN CN2010101468044A patent/CN101824614B/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104894621A (en) * | 2015-05-11 | 2015-09-09 | 上海电力学院 | Preparation method for Ca-P-phase bioactive anticorrosive coating on medical magnesium alloy matrix surface |
| CN108624877A (en) * | 2018-06-15 | 2018-10-09 | 莱诺斯科技（北京）股份有限公司 | A kind of magnesium lithium alloy material surface anti-corrosive treatment method |
| CN110592570A (en) * | 2019-09-27 | 2019-12-20 | 山东华盛荣镁业科技有限公司 | Magnesium alloy surface black chemical conversion process |
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| CN101824614B (en) | 2012-08-08 |
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Granted publication date: 20120808 Termination date: 20130415 |