CN106756931A - A kind of modified copper nano-wire rare-earth salts conversion fluid and its application method for Mg alloy surface treatment - Google Patents
A kind of modified copper nano-wire rare-earth salts conversion fluid and its application method for Mg alloy surface treatment Download PDFInfo
- Publication number
- CN106756931A CN106756931A CN201611215847.7A CN201611215847A CN106756931A CN 106756931 A CN106756931 A CN 106756931A CN 201611215847 A CN201611215847 A CN 201611215847A CN 106756931 A CN106756931 A CN 106756931A
- Authority
- CN
- China
- Prior art keywords
- wire
- rare
- copper nano
- earth salts
- conversion fluid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
The invention discloses a kind of modified copper nano-wire rare-earth salts conversion fluid for Mg alloy surface treatment,The conversion fluid is from rare-earth salts as main film-former,Assistant is with potassium permanganate,Sodium fluoride,Phytic acid,The auxiliary agents such as polyvinylpyrrolidone,So that the conversion fluid has film forming speed fast,Adhesion is strong,Corrosion protection high,The features such as high-efficiency environment friendly,In addition it is also added into through the copper nano-wire after stearic acid surface coating modification,Modified copper nano-wire good stability in the solution,It is difficult to reunite and aoxidizes,And with certain hydrophobicity,The nano material of this one-dimensional wire can form finer and close than nano-particle in alloy surface,Thicker film layer,So as to reach more long-acting protection effect,It also has good power simultaneously,Light,Electricity,Heat,The macro properties such as magnetic,Improve the performance of alloy surface,Further improve the feature of material,Lifting material value.
Description
Technical field
The present invention relates to technical field of magnesium alloy surface treatment, more particularly to a kind of being modified for Mg alloy surface treatment
Copper nano-wire-rare-earth salts conversion fluid and its application method.
Background technology
Magnesium alloy is the metal material of a kind of lightweight, high intensity, and the product weight of equality strength even can compare plastic cement
Also light, the ability of its load that withstands shocks is bigger than aluminium alloy, at the same magnesium alloy also have good processability, rapid heat dissipation, antidetonation,
The advantages of anti electromagnetic wave, recoverable, is widely used in fields such as Aero-Space, 3C Product, sports equipments, especially closely
3C Product gradually develops to compact direction over year so that high performance magnesium alloy is more favored by manufacturer.
Although magnesium alloy possesses above-mentioned advantage, because magnesium and its alloy activity are high, its oxide-film is loose porous,
Cause that material surface corrosion resistance is poor, environmental suitability is poor, limits the use of magnesium alloy.In order to improve these shortcomings, work
Magnesium alloy is surface-treated frequently with surface protection technique in industry application, wherein chemical conversion treatment be it is most quick, effectively,
A kind of economic processing mode, can not only improve alloy corrosion ability, go back the further protective treatment of alloy surface and lay
Good basis.The conventional chemical pretreatment solution of current magnesium alloy mainly have chromate, permanganate, phosphate, permanganate-
The technique of the solution systems such as phosphate, wherein chromate conversion coating is the most ripe, but Cr VI is carcinogen high, at present
Prohibit the use of, although the treatment fluid of other classes is more environmentally friendly to a certain extent, the conversion film for being formed exists corrosion-resistant
The problems such as poor, film layer of property is also easy to produce crackle, it is difficult to meet engineering demand.In order to improve chemical composition coating presence these lack
Fall into, researchers can significantly improve the microstructure of conversion film by adding nano-particle in conversion fluid, such as《Nanometer is hard
The influence of matter relative chemical conversion film microstructure》The result of study of one text shows a nanometer Al2O3, Nano-meter SiO_22Addition can have
The raising conversion film crystal grain quantity of effect, improves the consistency of conversion film, obtains corrosion resistance higher, but improve nano-powder and exist
Dispersiveness in conversion fluid is still more formidable problem, very high to technological operation requirement, using limited.
The content of the invention
A kind of defect in order to make up prior art of the invention, there is provided Modified Cu nanometer for Mg alloy surface treatment
Line-rare-earth salts conversion fluid and its application method, the property of traditional rare earth salt conversion film is improved using the unique performance of copper nano-wire
Can, further improve the surface property of magnesium alloy.
The present invention is achieved by the following technical solutions：
A kind of modified copper nano-wire-rare-earth salts conversion fluid for Mg alloy surface treatment, the conversion fluid is by following weight portion
Raw material is formulated：Rare-earth salts 35-48, potassium permanganate 3-5, phytic acid 1-2, copper nano-wire 4-5, stearic acid 0.5-1, sodium fluoride 1-
2nd, hydrogen peroxide 1-2, neopelex 1-2, polyvinylpyrrolidone 1-2, appropriate deionized water, appropriate glacial acetic acid, nothing
Appropriate water-ethanol.
Described rare-earth salts is one or more compound in lanthanum, cerium, praseodymium, the villaumite of rubidium, nitrate and sulfate.
The a diameter of 20-50nm of described copper nano-wire, length is 40-50 μm.
A kind of described modified copper nano-wire-rare-earth salts conversion fluid for Mg alloy surface treatment is prepared by following steps
Obtain：
（1）Rare-earth salts is mixed with a small amount of deionized water, stirring is completely dissolved it, and resulting solution is standby；
（2）Potassium permanganate is mixed with a small amount of deionized water, stirring is completely dissolved it, and resulting solution is standby；
（3）Sodium fluoride is mixed with a small amount of deionized water, stirring is completely dissolved it, and resulting solution is standby；
（4）The absolute ethyl alcohol of stearic acid and 20-30 weight portions is mixed and heated to 40-50 DEG C, is stirred completely molten to stearic acid
Add copper nano-wire after solution, suction filtration after sonic oscillation dispersion 2-3h, product through after absolute ethanol washing 2-3 times in 30-40 DEG C of bar
1-2h is vacuum dried under part, modified copper nano-wire is obtained standby；
（5）Take 30-50 parts by weight of deionized water to mix with neopelex, be stirring evenly and then adding into Modified Cu nanometer
Line, it is standby after ultrasonic disperse is uniform；
（6）Polyvinylpyrrolidone is mixed with appropriate deionized water, stirring is completely dissolved it, and resulting solution is standby；
（7）By step（1）To step（6）The solution of preparation and other leftover materials are mixed together uniform rear addition deionized water and adjust
Section to system middle rare earth salinity is 20-30g/L, then is 3.5-4 with glacial acetic acid regulation system pH value, obtains final product described conversion
Liquid.
A kind of application method of described modified copper nano-wire-rare-earth salts conversion fluid for Mg alloy surface treatment, bag
Include following steps：
（1）Mg alloy surface is dried naturally after the steps such as oil removing, water rinsing, acid attack, water rinsing, alkali activation, water rinsing
It is standby；
（2）Pretreated magnesium alloy is soaked in modified copper nano-wire-rare-earth salts conversion fluid that temperature is 70-80 DEG C and is reacted
Taken out after 20-30min, then workpiece is rinsed with water, dried naturally.
The present invention, as main film-former, is helped with potassium permanganate, sodium fluoride, phytic acid, polyvinylpyrrolidine from rare-earth salts
The auxiliary agents such as ketone so that the conversion fluid has that film forming speed is fast, adhesion is strong, corrosion protection high, high-efficiency environment friendly the features such as, be additionally added in addition
Through copper nano-wire after stearic acid surface coating modification, modified copper nano-wire good stability in the solution, the group of being difficult
Poly- and oxidation, and with certain hydrophobicity, the nano material of this one-dimensional wire can be in alloy surface shape than nano-particle
Into finer and close, thicker film layer, so as to reach more long-acting protection effect, while its also have good power, light, electricity, heat,
The macro properties such as magnetic, improve the performance of alloy surface, further improve the feature of material, lift material value.
Specific embodiment
A kind of modified copper nano-wire rare-earth salts conversion fluid for Mg alloy surface treatment, the conversion fluid is by following weight portion
Raw material be formulated：Lanthanum chloride 35, potassium permanganate 3, phytic acid 1, copper nano-wire 4, stearic acid 0.5, sodium fluoride 1, hydrogen peroxide 1,
Neopelex 1, polyvinylpyrrolidone 1, appropriate deionized water, appropriate glacial acetic acid, appropriate absolute ethyl alcohol.
The wherein a diameter of 20nm of copper nano-wire, length is 40 μm.
The conversion fluid is prepared by following steps：
（1）Lanthanum chloride is mixed with a small amount of deionized water, stirring is completely dissolved it, and resulting solution is standby；
（2）Potassium permanganate is mixed with a small amount of deionized water, stirring is completely dissolved it, and resulting solution is standby；
（3）Sodium fluoride is mixed with a small amount of deionized water, stirring is completely dissolved it, and resulting solution is standby；
（4）The absolute ethyl alcohol of stearic acid and 20 weight portions is mixed and heated to 40 DEG C, stirring adds after being completely dissolved to stearic acid
Enter copper nano-wire, suction filtration after sonic oscillation dispersion 2h, product under the conditions of 30 DEG C after absolute ethanol washing 2 times through being vacuum dried
1h, obtains modified copper nano-wire standby；
（5）Take 30 parts by weight of deionized water to mix with neopelex, be stirring evenly and then adding into modified copper nano-wire, surpass
Sound is standby after being uniformly dispersed；
（6）Polyvinylpyrrolidone is mixed with appropriate deionized water, stirring is completely dissolved it, and resulting solution is standby；
（7）By step（1）To step（6）The solution of preparation and other leftover materials are mixed together uniform rear addition deionized water and adjust
Section to system middle rare earth salinity is 20g/L, then is 3.5 with glacial acetic acid regulation system pH value, obtains final product described conversion fluid.
The application method of the conversion fluid is comprised the following steps：
（1）Mg alloy surface is dried naturally after the steps such as oil removing, water rinsing, acid attack, water rinsing, alkali activation, water rinsing
It is standby；
（2）Pretreated magnesium alloy sample is soaked in the modified copper nano-wire rare-earth salts conversion fluid that temperature is 70 DEG C and is reacted
Taken out after 30min, then workpiece is rinsed with water, dried naturally.
Conversion film to magnesium alloy sample surface carries out performance test, and test result is：
Pattern:Macroscopic view is brownish black, and film forming uniform ground, microcosmic result is solid netted result, there is slight crackle, the μ of thickness 7.2
m。
Corrosion resistance：Undressed magnesium alloy substrate and sample are distinguished into salt spray test and damp heat test, it is as a result as follows：
| Project | Salt spray test | Damp heat test |
| Matrix | General corrosion after 8h, produces a large amount of erosions | Surface discolouration, a large amount of bubbles of appearance after 24h |
| Sample | There is corrosion pit in surface after 52h | Surface light discolouration after 175h, a small amount of bubble |
Claims (5)
1. it is a kind of for Mg alloy surface treatment modified copper nano-wire-rare-earth salts conversion fluid, it is characterised in that the conversion fluid by
The raw material of following weight portion is formulated：Rare-earth salts 35-48, potassium permanganate 3-5, phytic acid 1-2, copper nano-wire 4-5, stearic acid
0.5-1, sodium fluoride 1-2, hydrogen peroxide 1-2, neopelex 1-2, polyvinylpyrrolidone 1-2, appropriate deionized water,
Appropriate glacial acetic acid, appropriate absolute ethyl alcohol.
2. a kind of modified copper nano-wire-rare-earth salts conversion fluid for Mg alloy surface treatment as claimed in claim 1, it is special
Levy and be, described rare-earth salts is one or more compound in lanthanum, cerium, praseodymium, the villaumite of rubidium, nitrate and sulfate.
3. a kind of modified copper nano-wire-rare-earth salts conversion fluid for Mg alloy surface treatment as claimed in claim 1, it is special
Levy and be, a diameter of 20-50nm of described copper nano-wire, length is 40-50 μm.
4. a kind of modified copper nano-wire-rare-earth salts conversion for Mg alloy surface treatment as described in claim 1 or 2 or 3
Liquid, it is characterised in that described conversion fluid is prepared by following steps：
（1）Rare-earth salts is mixed with a small amount of deionized water, stirring is completely dissolved it, and resulting solution is standby；
（2）Potassium permanganate is mixed with a small amount of deionized water, stirring is completely dissolved it, and resulting solution is standby；
（3）Sodium fluoride is mixed with a small amount of deionized water, stirring is completely dissolved it, and resulting solution is standby；
（4）The absolute ethyl alcohol of stearic acid and 20-30 weight portions is mixed and heated to 40-50 DEG C, is stirred completely molten to stearic acid
Add copper nano-wire after solution, suction filtration after sonic oscillation dispersion 2-3h, product through after absolute ethanol washing 2-3 times in 30-40 DEG C of bar
1-2h is vacuum dried under part, modified copper nano-wire is obtained standby；
（5）Take 30-50 parts by weight of deionized water to mix with neopelex, be stirring evenly and then adding into Modified Cu nanometer
Line, it is standby after ultrasonic disperse is uniform；
（6）Polyvinylpyrrolidone is mixed with appropriate deionized water, stirring is completely dissolved it, and resulting solution is standby；
（7）By step（1）To step（6）The solution of preparation and other leftover materials are mixed together uniform rear addition deionized water and adjust
Section to system middle rare earth salinity is 20-30g/L, then is 3.5-4 with glacial acetic acid regulation system pH value, obtains final product described conversion
Liquid.
5. a kind of modified copper nano-wire-rare-earth salts conversion fluid for Mg alloy surface treatment as described in Claims 1-4
Application method, it is characterised in that comprise the following steps：
（1）Mg alloy surface is dried naturally after the steps such as oil removing, water rinsing, acid attack, water rinsing, alkali activation, water rinsing
It is standby；
（2）Pretreated magnesium alloy is soaked in modified copper nano-wire-rare-earth salts conversion fluid that temperature is 70-80 DEG C and is reacted
Taken out after 20-30min, then workpiece is rinsed with water, dried naturally.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611215847.7A CN106756931A (en) | 2016-12-26 | 2016-12-26 | A kind of modified copper nano-wire rare-earth salts conversion fluid and its application method for Mg alloy surface treatment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611215847.7A CN106756931A (en) | 2016-12-26 | 2016-12-26 | A kind of modified copper nano-wire rare-earth salts conversion fluid and its application method for Mg alloy surface treatment |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106756931A true CN106756931A (en) | 2017-05-31 |
Family
ID=58927304
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611215847.7A Pending CN106756931A (en) | 2016-12-26 | 2016-12-26 | A kind of modified copper nano-wire rare-earth salts conversion fluid and its application method for Mg alloy surface treatment |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106756931A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107699888A (en) * | 2017-10-18 | 2018-02-16 | 江西华立金属制品有限公司 | A kind of processing method of environment-friendly type spring steel wire |
| CN108728839A (en) * | 2018-05-15 | 2018-11-02 | 沈阳明腾科技有限公司 | A kind of Chrome-free chemical conversion liquid for magnesium alloy |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1715458A (en) * | 2004-06-30 | 2006-01-04 | 中南大学 | Aliminium base wave absorbing material and preparing method |
| CN103614716A (en) * | 2013-12-10 | 2014-03-05 | 广西大学 | Preparation method of environment-friendly aluminum alloy surface rare-earth inorganic composite conversion coating |
| CN106205774A (en) * | 2016-07-19 | 2016-12-07 | 哈尔滨工业大学深圳研究生院 | A kind of electrocondution slurry and transparent conducting coating |
-
2016
- 2016-12-26 CN CN201611215847.7A patent/CN106756931A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1715458A (en) * | 2004-06-30 | 2006-01-04 | 中南大学 | Aliminium base wave absorbing material and preparing method |
| CN103614716A (en) * | 2013-12-10 | 2014-03-05 | 广西大学 | Preparation method of environment-friendly aluminum alloy surface rare-earth inorganic composite conversion coating |
| CN106205774A (en) * | 2016-07-19 | 2016-12-07 | 哈尔滨工业大学深圳研究生院 | A kind of electrocondution slurry and transparent conducting coating |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107699888A (en) * | 2017-10-18 | 2018-02-16 | 江西华立金属制品有限公司 | A kind of processing method of environment-friendly type spring steel wire |
| CN108728839A (en) * | 2018-05-15 | 2018-11-02 | 沈阳明腾科技有限公司 | A kind of Chrome-free chemical conversion liquid for magnesium alloy |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106544710B (en) | A kind of anti-corrosion anti-bacteria stainless steel plate of anti-soil and preparation method thereof | |
| CN102993846B (en) | Aqueous anticorrosive paint of steel structure and preparation method thereof | |
| CN104593793B (en) | A kind of aluminium and aluminum alloy surface pre-process neutralizer | |
| CN105839093B (en) | A kind of electro-coppering room temperature chromium-free passivation liquid and its passivation technology | |
| CN104831332B (en) | A kind of method that steel surface directly generates the anti-corrosion differential arc oxidation film layer of black | |
| CN111058068A (en) | Processing technology of zinc-plated nickel alloy | |
| CN106756931A (en) | A kind of modified copper nano-wire rare-earth salts conversion fluid and its application method for Mg alloy surface treatment | |
| CN105153782B (en) | Aluminium paste anode electrophoresis tank liquid and aluminium paste anode electrophoresis technology | |
| CN107475704B (en) | Metal surface silane treatment agent and preparation method thereof | |
| CN113106434A (en) | Environment-friendly aluminum alloy chemical oxidation liquid and chemical oxidation method | |
| CN106399994A (en) | Schiff base complex-phosphate conversion liquid for magnesium alloy surface treatment and utilization method of Schiff base complex-phosphate conversion liquid | |
| CN105063596A (en) | Treating fluid for chromate-free passivation of aluminum profiles before coating and preparation method thereof | |
| CN101314808A (en) | High-efficiency low-cost high-temperature inoxidzable coating material | |
| CN108411138A (en) | A kind of enhancing aluminum alloy materials | |
| CN106756951A (en) | A kind of modified silicon carbide nanometer line rare-earth salts conversion fluid and its application method for Mg alloy surface treatment | |
| CN106752830A (en) | One kind is for electric armour clamp corrosion-resistant high-strength composite organic silicon modified polyurethane water paint and preparation method thereof | |
| CN106756944A (en) | A kind of hydridization polypyrrole nano line molybdate conversion liquid and its application method for Mg alloy surface treatment | |
| CN106756952A (en) | The tin molybdate conversion liquid and its application method of a kind of compound nano-zinc sulfide for Mg alloy surface treatment | |
| CN105088212A (en) | Crack-prevention aluminium profile chromate-free passivation treating liquid and preparation method thereof | |
| CN106756954A (en) | A kind of polyaniline nano fiber zirconium titanium salt conversion fluid and its application method for Mg alloy surface treatment | |
| CN104611689A (en) | Chemical oxidation liquid for magnesium alloy | |
| CN102560465B (en) | A kind of metal surface protection pre-processing process | |
| CN107326349A (en) | High-performance multi-component alloy catalytic liquid and preparation method thereof | |
| CN106399992A (en) | Compound-mixed tea polyphenol-rare-earth salt conversion liquid for magnesium alloy surface treatment and use method thereof | |
| CN105088215A (en) | High-abrasion-resistance aluminum profile chromate-free passivation treating fluid and preparing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170531 |
|
| RJ01 | Rejection of invention patent application after publication |