CN1080671A - The two-step chemical/electrochemical coating process of magnesium - Google Patents
The two-step chemical/electrochemical coating process of magnesium Download PDFInfo
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- CN1080671A CN1080671A CN92105170.0A CN92105170A CN1080671A CN 1080671 A CN1080671 A CN 1080671A CN 92105170 A CN92105170 A CN 92105170A CN 1080671 A CN1080671 A CN 1080671A
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/30—Anodisation of magnesium or alloys based thereon
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Abstract
A kind of two step coating process that are used for magnesium and its alloy have been disclosed.The first step comprise the magnesium workpiece is immersed in contain that about 0.2 to 5 mole Neutral ammonium fluoride, pH are about 5 to 8, temperature is about in 40 to 100 ℃ the no aqueous silicate solution.Second step be through pretreated workpiece in pH is at least about 12.5 electrolytic aqueous solution, carry out electrochemical treatment, this electrolytic aqueous solution is by about water soluble hydroxide of 2 to 12g/l, about 2 to 15g/l fluorochemical, this fluorochemical component is to choose from the cohort of fluorochemical and silicofluoride formation, and about silicate of 5 to 30g/l is formed.The good coating that this method formation wear resistance and solidity to corrosion are improved.
Description
The present invention relates to a kind of method of inorganic coating and goods that adopt this method to obtain of on magnesium alloy, forming.The present invention be more particularly directed to a kind of method, be included in the chemical plating fluid, when neutral pH, the workpiece of being made up of magnesium alloy is carried out pre-treatment, then in the aqueous solution to carrying out electro deposition through pretreated workpiece.
Magnesium increases rapidly as the application of structured material.Magnesium usually can with aluminium, manganese, thorium, lithium, tin, zirconium, zinc, rare earth metal or other alloy alloying, thereby increase its structural stability.This magnesium alloy is commonly used in the desired strength place high to weight ratio.Suitable magnesium alloy also can demonstrate it and have the highest intensity to weight ratio in the ultralight metal when high temperature.In addition, the alloy of magnesium and rare earth or thorium is still keeping significant intensity up to 315 ℃ or during higher temperature.The available multiple usual manner of the assembling of structure magnesium alloy carries out, and comprising: riveted joint and bolt, electric-arc welding and resistance welding, soldering, low temperature welding and bonding.Contain in the vehicle body and component, manipulative device and materials processing that the magnesium workpiece is used in aircraft and aerospace industry, military equipment, electronic machine, automobile.Although magnesium and alloy thereof demonstrate satisfactory stability in many chemical substances exist, still have the needs of further this metal of protection, particularly in sour environment and under the salt water condition.Therefore, in marine use, must provide one deck coating not weather especially with the protection metal.
The developed and use of the coating of many dissimilar magnesium.Prevailing coating is chemical treatment or the inversion cladding material that is used as priming paint and produces certain corrosion-resisting function.Chemistry and two kinds of methods of electrochemistry are used for the conversion of magnesium surface.The most common to the surface treatment of magnesium alloy is to use chromate film.These provide a kind of surface of good priming paint but its non-corrosibility is limited through poly-chromate film hydration, the similar gels structure.
It is a kind of electrochemical process of Gong selecting for use for the coating that is protected that the anodizing of magnesium alloy is electroplated.Have two kinds of low voltage negative electrode methods at least, DOW17 and HAE are applied industrial.Yet, by the solidity to corrosion that these treatment processs provided be have circumscribed.The DOW17 method is used potassium bichromate, and this is a kind of chromium (VI) compound severe toxicity and that be strictly controlled that has.Though the major constituent of anodic coating is a potassium permanganate in the HAE method,, must use the chromic salt seal gum with this coating in order to obtain good solidity to corrosion.Therefore no matter any in above-mentioned two kinds of methods, in order to obtain desired solidity to corrosion coating, the essential chromium (VI) that uses in whole process.The use of chromium (VI) means that the wastewater treatment that produces is a major issue from these processes.
Recently, developed the coating of metal and similar pottery.These coating can generate by no method for electrically or electrochemical process.Well-known is to make the nickel electroless plating on magnesium and magnesium alloy with chemical reducing agent in coating forms.But this method also causes producing the waste water that is subjected to heavy metal contamination that hazardness is arranged in a large number, must handle before this waste water is discharged.The electrochemical plating method can be used to make metal and nonmetal coating.Metal coating still is faced with and produces the wastewater problem that is subjected to heavy metal contamination.
The nonmetal coating process that has developed partly overcomes and has comprised the problems such as waste water that are subjected to heavy metal contamination.Kozak is in U.S. Patent No. 4,184, disclosed a kind of two-step approach that forms coating against corrosion on magnesium and alloy thereof in 926.The first step is to carry out with hydrofluoric acid workpiece sheet to magnesium under about room temperature, and acidic chemical embathes or handles, to form one deck fluoro-magnesium layer in the metallic surface.Second step was included in the solution that contains alkalimetal silicate and alkali metal hydroxide carries out electrochemical plating to the workpiece sheet.Put on the about 150-300 volt of voltage of electrode, and the current density in plating tank is maintained at about 50-200mA/cm
2Though second step of present method is when carrying out in the electrochemical plating cell that does not contain fluorochemical, the first step of present method is that step is washed in a direct acidleach.The test of present method shows that needs strengthen the integrity of solidity to corrosion and coating.
Kozak is in U.S. Patent No. 4,620, disclosed the single stage method that a kind of electroplate liquid with alkali metal containing silicate, alkalimetal oxide and fluorochemical is electroplated the magnesium workpiece in 904.This electroplate liquid keeps temperature to be about 5-70 ℃, and pH is about 12-14.This electrochemical plating is to carry out under the voltage of about 150-400 volt.The test of present method also shows still needs to strengthen solidity to corrosion.
Based on the experience of prior art, need be a kind of to containing the method that the magnesium workpiece carries out coating, this method produces the homogeneous coating that a kind of solidity to corrosion is improved.In addition, needs are a kind of low to matching requirements, and do not produce the more economical method of coating of the waste water that is subjected to heavy metal contamination.
The present invention discloses the method that a kind of plating contains the magnesium workpiece.This workpiece contain that have an appointment 0.2 to 5 mole of Neutral ammonium fluoride, pH are about 5 to 8, temperature is pretreated from 40 to 100 ℃ the aqueous solution that does not contain silicate approximately.This pre-treatment step has been cleaned workpiece, and produces one deck successive fluorinated ammonium thin layer basically at workpiece surface, thereby forms through pretreated workpiece.Then, have in pH is at least about 12.5 aqueous electrolyte through pretreated workpiece dipping, this solution is by about water soluble hydroxide of 2 to 12g/L, about 2 to 15g/L fluorochemical, the component of this fluorochemical is to choose from the cohort of fluorochemical and silicofluoride formation, and about silicate of 5 to 30g/L is formed.By through anode that pretreated workpiece constituted and also with negative electrode that electrolytic solution contact between the potential difference that produced be at least about 100 volts, arrive 90mA/cm thereby produce about 2
2Current density.Use present method, on magniferous workpiece, form the coating of silicon oxide-containing.
The term " magniferous workpiece " that uses in this specification sheets and these claims, its connotation are meant all or part of metal works of being made up of MAGNESIUM METAL or magnesium alloy in surface.Be that workpiece is made of MAGNESIUM METAL or magnesium alloy and the magnesium that contains capacity preferably.Better, workpiece is made of the rich magnesium alloy that contains about 50wt-% magnesium at least, and best situation is that workpiece is made of the magnesium that is about 80wt-% at least.
Fig. 1 illustrates and of the present inventionly contains the magnesium workpiece through coating.
Fig. 2 skeleton diagram of the present invention.
Fig. 3 is the synoptic diagram of electrochemical method of the present invention.
Fig. 4 contains the magnesium substrate and according to the scanning electron microscope Photomicrograph of the cross section of coating of the present invention.
Fig. 1 illustrates the cross section that contains the magnesium workpiece with method coating of the present invention. At Fig. 1 In shown and contained magnesium workpiece 10 with the second layer 14 of fluorinated ammonium ground floor 12 and similar pottery. Thereby the combination of layer 12 and 14 is containing magnesium surface of the work formation corrosion resistance coating.
Coating comprise similar pottery, contain silica and magnesian coating. Fig. 2 illustrates for the manufacture of these steps through the workpiece of coating. At first, untreated workpiece 20 is placed in the chemical plating fluid 22 and cleans, and forms the coating of one deck fluorinated ammonium at workpiece. Then, this workpiece is interior processed at electrochemical plating bath 24, thereby produces the workpiece 26 through coating.
Chemical plating fluid 22 be no silicate and form by ammonium fluoride aqueous solution.Situation is preferably, and this plating bath contains 0.2 to 5 mole Neutral ammonium fluoride in water, better, contains 0.3 to 2.0 mole Neutral ammonium fluoride, and best situation is to contain about 0.5 to 1.2 mole Neutral ammonium fluoride.Reaction conditions is shown in down in the tabulation I.
The table I
State is better best preferably
pH 4-8 5-7 6-7
Temperature (℃) 40-100 55-90 70-85
Time (branch) 15-60 30-45 30-40
If plating bath acidity is too high or too hot, then oxidizing reaction (etch) takes place too violently, and if electroplate liquid alkalescence is too high or too cold, then the actual reaction process that forms coating is carried out too slowly on workpiece.
Contain the magnesium workpiece and in chemical plating fluid, keep the enough time, remove impurity on the workpiece surface, and form one deck successive fluorinated ammonium layer basically on the magnesium workpiece containing with cleaning.This has caused forming, and no silicate layer with metal ammonium fluorochemical and/or metal ammonium oxidation fluorochemical carries out coating contains the magnesium workpiece, and according to the character of alloy, most of metal is a magnesium.In chemical plating fluid as the residence time the too short basic unit that will cause fluoride not exclusively and/or to contain the cleaning of magnesium workpiece incomplete, finally cause reducing the solidity to corrosion of electroplating the back workpiece.Long as the residence time, along with the increase in reaction times, basic unit does not almost have much improvement, so be uneconomic.Topped basic unit at workpiece surface is uniformly substantially on component and thickness, and provides a fabulous basal plane that can deposit on it for the second layer of similar pottery.The better thickness of fluoride layer is about 1 to 2 micron.
We do not wish to be limited to this in theory; because first chemical plating fluid provides one deck and substrate to combine closely and has protected the basic unit of substrate; thereby demonstrating first chemical plating fluid is of great use, this basic unit and the component compatibility that constitutes the second layer, and the second layer is adhered on the substrate.This also demonstrate the basic unit that forms by metal ammonium fluorochemical and oxidation fluorochemical be no silicate, and be adhered on the metal substrate forcefully.This also demonstrates these compounds has guaranteed in other compound with the consistency of the component that constitutes the second layer, metal substrate is not had the even mode cvd silicon oxide and the magnesium oxide of obvious etch.
This basic unit provides certain protection to metal substrate, but it does not provide wear resistance and hardness, and wear resistance and hardness be by completely, two-layer coating provided.On the other hand, if the silicon oxide-containing layer imposes on the metal substrate that does not at first deposit basic unit, then because silicon oxide-containing layer and substrate are bonding bad, the solidity to corrosion of coating and wear resistance reduce.
Between chemical plating fluid 22 and electrochemical plating bath 24, be that water thoroughly cleans preferably through pretreated workpiece, to remove any unreacted Neutral ammonium fluoride.This cleaning makes electrochemical plating bath 24 avoid contaminated.
Then, will carry out as the electrochemical plating process among Fig. 3 through cleaning and pretreated workpiece.Electrification plating bath 26 is by the electrolytic aqueous solution that contains about 2 to 12g/L solubility hydroxide compound, about 2 to 15g/L soluble fluoride, this soluble fluoride is to choose from the cohort of fluorochemical and silicofluoride formation, and about silicate of 5 to 30g/L is formed.Oxyhydroxide comprises alkali metal hydroxide preferably.Better basic metal is lithium, sodium or potassium, and best oxyhydroxide is potassium hydroxide.
Fluoride is that compound can be the fluorochemical such as alkaline metal fluoride cpd, for example lithium fluoride, Sodium Fluoride and Potassium monofluoride, or the acid fluorochemical such as hydrogen fluoride or fluoram.Also can use the silicofluoride such as potassium silicofluoride or Sodium Silicofluoride.The compound of fluoride is to comprise alkaline metal fluoride cpd, alkali metal fluorosilicates, hydrogen fluoride and their mixture thereof preferably.The compound of best fluoride comprises Potassium monofluoride.
The electrification plating bath also contains silicate.Useful silicate comprises alkalimetal silicate and/or alkali metal fluorosilicates.Better silicate comprises lithium silicate, water glass or potassium silicate, and best silicate is potassium silicate.A useful source is the potassium silicate concentrated solution (SiO that contains 20wt% in the water that can buy commodity KASIL30 ° of Baume (Baum'e) by name to the quartzy company in Philadelphia (Philadelphia Quartz CO.)
2).
The compositing range of electrolytic aqueous solution is shown in down in the tabulation II.
The table II
Component is better best preferably
Oxyhydroxide 2-12g/L 4-8g/L 5-7g/L
Fluorochemical 2-15g/L 3-10g/L 8-10g/L
Silicate 5-30g/L 10-25g/L 15-20g/L
Be submerged in the electrochemical plating bath 24 as anode through pretreated workpiece 30.The container 32 that contains electrochemical plating bath 24 can be used as negative electrode and uses.Container 32 can be directly connected on the rectifier 36, and anode can be connected on the rectifier 36 by switch 34.The voltage that these rectifier 36 rectifications are imported from voltage source 38, thus direct supply provided to electrochemical plating bath.Rectifier 36 can be connected placement with the controller 40 of microprocessor with switch 34, to be used to control the electrochemistry component.Under better situation, this rectifier provides pulsation DC signal, to impel deposition process.
The condition of electrochemical precipitation process process is shown in down in the tabulation III preferably.
The table III
Parameter is better best preferably
pH 12-14 12-13 12.5-13
Temperature (℃) 5-30 10-25 10-20
Time (branch) 5-80 15-60 20-30
Current density 2-90 5-70 10-50
（mA/cm
2）
It is that the coating of the similar pottery that forms is at about 80 minutes or still less reach about 40 micron thickness in the time that these reaction conditionss make.The time longer as potential difference brought will deposit thicker coating.Yet, to proceed from the reality, about 10 to the 30 microns coating of thickness is preferably, this can obtain by about 10 to 30 minutes coating time.
The coating that obtains according to the method described above is similar ceramic-like, and has fabulous solidity to corrosion, wear resistance and hardness property.Although do not wish to be confined to this theory, demonstrate structure and the cementability that these character are coating on the metal substrate and produce.Coating is by the fused silicon oxide preferably, and magnesium oxide, and the mixture of alkalimetal oxide is formed.
The cementability of coating of the present invention demonstrates much better than any known commercialization coating.This is owing to produced the internal surface of mutual driving fit between metal substrate and coating.By the internal surface of mutual driving fit, this means what internal surface was made up of the continuum of magnesium, magnesium oxide, oxo magnesium fluoride, magnesium fluoride and silicon oxide.
Shown in the scanning electron microscope Photomicrograph of Fig. 4 is continuous internal surface, and metal substrate 50 has an irregular surface, and border, a face border, and this border, face border has comprised the fluorinated ammonium layer 52 that forms on substrate 50 surfaces.The silicon oxide-containing and the magnesian thin layer 54 that form in basic unit 52 demonstrate fabulous integrity, so coating 52 and 54 provides outstanding anti-corrosion and wearing face.
Wear resistance can be according to federal standard testing method (Federal Test Method Std.) NO.141C, and method (Method) 6192.1 is measured.The coating of the thickness of producing according to the present invention 0.5 to 1.0mil, situation is preferably, when using the 1.0Kg load on the CS-17 grinding miller, withstands the metal substrate that just occurs gymnosis after about 1,000 abrasion cycles at least.Better, before the metal substrate of gymnosis occurs, coating will stand about 2,000 abrasion cycles at least, and best situation is, when using the 1.0Kg load on the CS-17 grinding miller, coating will stand about 4,000 abrasion cycles at least.
Solidity to corrosion can be according to the ASTM canonical measure.When measuring, in these tests, also comprise salt-fog test (ASTM B117) with the method A of ASTM D1654 and B.When testing with method B, then the coating that makes according to the present invention was at least 9 in the class rating that situation preferably is issued to after 24 hours in salt fog.Better, after 100 hours, the class rating that coating reaches is at least 9.And best situation is, is at least 9 in salt fog after 200 hours.
After containing the magnesium workpiece according to present method coating, they can be used as has fabulous protective layer and excellent abrasion resistance is used, and perhaps their available a kind of optional supercoat (for example coating or seal gum) come further coating.The structure of silicon oxide-containing coating and shape allow to use easily can further provide many kinds of additional protection coatings of solidity to corrosion or decorating feature to containing the magnesium workpiece.In fact, the coating of silicon oxide-containing is a kind of fabulous solidity to corrosion that has, and is doing the good priming paint that (for example water immersion test, ASTM D3359, test method B) under the wet condition all gives fabulous cementability.Optional protective coating also can comprise organic except that enamelled coating and inorganic compositions and other ornamental and organic coating of protectiveness.Can use any and vitreous state and metallic state surface that the enamelled coating of better cementability is arranged as optional protective coating.Representative is that as non-the placing restrictions on property inorganic compositions that a kind of serving uses, it comprises additional alkalimetal silicate, phosphoric acid salt, borate, molybdate and vanadate.The representative organic serving of non-placing restrictions on property comprises the polymkeric substance such as fluorinated ethylene propylene, polyurethane(s) and polyoxyethylene glycol.The protective coating material that is added will be known to those skilled persons of this area.Emphasize that again these optional protective coatings are need not obtain fabulous solidity to corrosion, their use can obtain ornamental or a protection quality of advancing to improve coating more.
After further using optional protective coating, fabulous solidity to corrosion will be produced.According to the prepared coating of the present invention, and have optional protective coating, when measuring with method B, preferably situation be in salt fog after 700 hours class rating reach 8 at least.Better, coating class rating after 700 hours reaches at least about 9, and best situation be in salt fog after 700 hours class rating be at least 10.
The specific embodiments that comprises best mode below can using is further showed the present invention.These embodiment only are in order to show the present invention rather than to be used for limiting scope of the present invention.
Embodiment 1
Magnesium test piece (AZ91D) is immersed in trisodium phosphate, Sodium Tetraborate and the sodium fluoride aqueous solution, is to clean about 5 minutes under 10.5 the condition at about 70 ℃, pH.Then test piece is placed 70 ℃ 0.5M Neutral ammonium fluoride electroplate liquid 30 minutes.Rinsing test piece then, and place the plating bath that contains silicate.This silicate plating bath prepares by at first dissolve 50 gram potassium hydroxide in 10L water.Again 200 milliliters of commodity are called the potassium silicate enriched material (20%w/wSiO of KASIL
2) join in the top solution.At last 50 gram Potassium monofluorides are joined in the top solution.The plating bath that makes like this has that pH is about 12.5, the concentration that contains potassium hydroxide is about 5g/L, potassium silicate is about 16g/L and Potassium monofluoride is about 5g/L.Next again test piece is inserted in the plating bath and join with the positive wire of rectifier.The stainless steel test piece is joined as negative electrode and with the rectifier cathode leg that can transmit pulsed D C signal.Voltage was raised to 150V in more than 30 seconds, and electric current was adjusted to maintain 30mA/cm
2Current density.After 30 minutes, the coating of silicon oxide-containing is about 20 micron thickness.
Embodiment II-VIII
Embodiment II-VIII is according to the method for embodiment I, is prepared by the component parameter shown in following table IV and the V.
The table IV
Chemical plating fluid
Embodiment NH
4The F concentration bath temperature residence time
(M) (℃) (branch)
II 1.0 70 30
III 1.5 60 30
IV 0.7 80 30
V 1.0 80 20
VI 1.0 70 30
VII 0.8 80 40
VIII 1.2 60 30
Table V electrification plating bath (10L)
The potassium silicate bath temperature current density residence time
The oxyhydroxide enriched material
*Fluorochemical (℃) pH mA/cm
2(branch)
60gKOH 300ml 150gKF 20 12.8 40 30
70gKOH 200ml 100gNaF 20 12.9 60 25
60gNaOH 250ml 100gNaF 20 12.9 80 15
40gLiOH 200ml 100gKF 20 12.8 20 40
50gNaOH 300ml 80gNaF 20 12.9 50 30
60gKOH 200ml 100gKF 20 12.9 30 40
30gKOH 250ml 120gKF 20 12.9 20 30
10gLiOH
*Commodity KASIL(by name contains 20%w/wSiO in water
2)
Cut resistance test (141C) is carried out in these test pieces, before gymnosis appears in metal substrate, stood about 2,000 abrasion cycles at least when consequently on the CS-17 grinding miller, loading with 1.0kg.
The embodiment IX
Press embodiment 1 coating magnesium test piece.After drying, bestow additional coating in the following manner.Be about in the solution (pH=7.2) of 12% potassium hydrogen phosphate that test piece is immersed in 60 ℃ 5 minutes.Rinsing and dry test piece, and stand salt fog ASTM B117 test.The specified grade that test piece reaches through 700 hours rear panels in salt fog very 10.
The embodiment X
According to embodiment I and IX through the test piece of coating with a kind of an acidic catalyst priming paint priming, and carry out coating with a kind of high-temperature enamel again.Then stain is immersed in test piece and in the water of 100F, reach 4 days, then carry out the test of method B among the ASTM D3359.The class rating that test piece reaches is 5/5, and the maximum amount that does not at this moment observe plating exfoliation is decided grade.
The present invention that the content of above-mentioned announcement, embodiment and data illustrate here to be disclosed, but it should be by inadequately as the scope that limits the present invention or claims.Therefore, when keeping the spirit and scope of the present invention, can do many concrete things and change, the present invention belongs in the appending claims of back generally.
Claims (21)
1, a kind ofly form the method for having improved corrosion proof coating containing on the magnesium workpiece, it is characterized in that comprising:
(a) with first kind of no silicate, pH is about 5 to 8, temperature is about 40 to 100 ℃ the aqueous solution and handles workpiece, this solution contains about 0.2 to 5 mole Neutral ammonium fluoride, thereby, so that workpiece surface produces the basic successive of one deck, contains the thin layer of metal ammonium fluorochemical, pass through pretreated workpiece thereby form;
(b) will insert second kind of pH to being about less in 12.5 the electrolytic aqueous solution through pretreated workpiece, this electrolytic aqueous solution by:
(i) about 2 to 12g/L water soluble hydroxide,
(ii) about 2 to 15g/L soluble fluoride, the component of this soluble fluoride are to choose from the cohort that fluorochemical, silicofluoride and composition thereof constitute, and
(iii) about alkalimetal silicate of 5 to 30g/L is formed;
(c) in electrolytic solution, form between process sun level that pretreated workpiece constituted and the negative electrode and be at least about 100 volts potential difference, thereby being about 2, generation arrives 90mA/cm
2Current density;
So, the coating of formation silicon oxide-containing on workpiece.
2, the method for claim 1 is characterized in that, (b) oxyhydroxide in is a kind of alkali metal hydroxide.
3, the method for claim 1 is characterized in that, (b) component of the fluoride in is to choose from the cohort that Sodium Fluoride, Potassium monofluoride, hydrofluoric acid, lithium fluoride, rubidium fluoride, cesium fluoride and composition thereof constitute.
4, the method for claim 1 is characterized in that, (b) silicofluoride in is to choose from the cohort that potassium silicofluoride, Sodium Silicofluoride, lithium fluosilicate and composition thereof constitute.
5, the method for claim 1 is characterized in that, (b) silicate in be from potassium silicate, water glass, lithium silicate, and composition thereof choose the cohort that constituted.
6, the method for claim 1 is characterized in that, the temperature of second kind of solution is about 5 to 30 ℃.
7, the method for claim 1 is characterized in that, (c) potential difference in is about 200 to 400 volts.
8, the method for claim 1 is characterized in that, comprises that further anode and negative electrode connect with the mains.
9, method as claimed in claim 8 is characterized in that, power supply is a kind of AC power through rectification.
10, method as claimed in claim 9 is characterized in that, is a kind of pulse full-wave rectifier power supply through the AC power of rectification.
11, the method for claim 1 is characterized in that, further comprises the coating of sealing-in silicon oxide-containing.
12, the method for claim 1 is characterized in that, this method is basically without chromium (VI).
13, the method for claim 1 is characterized in that, a kind of magniferous substrate of plating.
14, a kind ofly form the method for having improved corrosion proof coating containing on the magnesium workpiece, it is characterized in that comprising:
(a) with first kind of no silicate, pH is about 5 to 8, temperature is about 40 to 100 ℃ the aqueous solution and handles workpiece, this solution contains about 0.2 to 5 mole Neutral ammonium fluoride, so that workpiece surface produces the basic successive of one deck, contains the thin layer of metal ammonium fluorochemical, pass through pretreated workpiece thereby form;
(b) will insert second kind of pH through pretreated workpiece and be at least about in 12.5 the electrolytic aqueous solution, this electrolytic aqueous solution by:
(ⅰ) about 2 to 12g/L water soluble hydroxide,
(ⅱ) about 2 to 30g/L alkali metal fluorosilicates; And
(c) in electrolytic solution, form between process anode that pretreated workpiece constituted and the negative electrode and be at least about 100 volts potential difference, be about 2 to 90mA/cm thereby produce
2Current density;
So, the coating of formation silicon oxide-containing on workpiece.
15, a kind of have improved solidity to corrosion and wear resistance contain the magnesium workpiece, it is characterized in that this workpiece is by first basic unit that contains the no silicate that magnesium substrate, metal ammonium fluorochemical form and second skin of being made up of silicon oxide and magnesium oxide.
16, workpiece as claimed in claim 15 is characterized in that, the metal ammonium fluorochemical comprises Neutral ammonium fluoride magnesium.
17, workpiece as claimed in claim 15 is characterized in that, additional basic unit comprises metal ammonium oxo fluorochemical.
18, workpiece as claimed in claim 15 is characterized in that, further comprises the 3rd sealing layer that is deposited on second skin.
19, workpiece as claimed in claim 15 is characterized in that, further comprises the 4th trim layer that is deposited on second skin.
20, workpiece as claimed in claim 19 is characterized in that, further comprises the fourth face layer that is deposited on the 3rd sealing layer.
21, workpiece as claimed in claim 15 is characterized in that, this workpiece is substantially free of chromium (VI).
Priority Applications (15)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BR9205679A BR9205679A (en) | 1991-02-26 | 1992-02-25 | Two-step chemical / electrochemical process for coating magnesium |
| PCT/US1992/001495 WO1992014868A1 (en) | 1991-02-26 | 1992-02-25 | Two-step chemical/electrochemical process for coating magnesium |
| EP92907909A EP0573585B1 (en) | 1991-02-26 | 1992-02-25 | Two-step chemical/electrochemical process for coating magnesium |
| DK92907909.3T DK0573585T3 (en) | 1991-02-26 | 1992-02-25 | Two-step chemical / electrochemical process for coating magnesium |
| JP50738392A JP3183512B2 (en) | 1991-02-26 | 1992-02-25 | Two-step chemical / electrochemical method of magnesium coating |
| DE69200922T DE69200922T2 (en) | 1991-02-26 | 1992-02-25 | TWO-STAGE CHEMICAL OR ELECTROCHEMICAL METHOD FOR COATING MAGNESIUM. |
| CA002100168A CA2100168C (en) | 1991-02-26 | 1992-02-25 | Two-step chemical/electrochemical process for coating magnesium alloys |
| AT92907909T ATE115653T1 (en) | 1991-02-26 | 1992-02-25 | TWO-STAGE CHEMICAL OR ELECTROCHEMICAL PROCESS FOR COATING MAGNESIUM. |
| AU15353/92A AU1535392A (en) | 1991-02-26 | 1992-02-25 | Two-step chemical/electrochemical process for coating magnesium |
| ES92907909T ES2068710T3 (en) | 1991-02-26 | 1992-02-25 | CHEMICAL / ELECTROCHEMICAL PROCEDURE OF TWO STAGES FOR COATING MAGNESIUM. |
| CN92105170A CN1049701C (en) | 1991-02-26 | 1992-06-26 | Two-step chemical/electrochemical magnesium coating process |
| US07/918,946 US5240589A (en) | 1991-02-26 | 1992-07-22 | Two-step chemical/electrochemical process for coating magnesium alloys |
| NO933024A NO308907B1 (en) | 1991-02-26 | 1993-08-25 | Two-step chemical/electrochemical process for coating magnesium and a magnesium-containing object with improved corrosion and wear resistance |
| US08/271,052 US5470664A (en) | 1991-02-26 | 1994-07-06 | Hard anodic coating for magnesium alloys |
| GR940404119T GR3015377T3 (en) | 1991-02-26 | 1995-03-13 | Two-step chemical/electrochemical process for coating magnesium. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US66150391A | 1991-02-26 | 1991-02-26 | |
| CN92105170A CN1049701C (en) | 1991-02-26 | 1992-06-26 | Two-step chemical/electrochemical magnesium coating process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1080671A true CN1080671A (en) | 1994-01-12 |
| CN1049701C CN1049701C (en) | 2000-02-23 |
Family
ID=25742761
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN92105170A Expired - Fee Related CN1049701C (en) | 1991-02-26 | 1992-06-26 | Two-step chemical/electrochemical magnesium coating process |
Country Status (13)
| Country | Link |
|---|---|
| EP (1) | EP0573585B1 (en) |
| JP (1) | JP3183512B2 (en) |
| CN (1) | CN1049701C (en) |
| AT (1) | ATE115653T1 (en) |
| AU (1) | AU1535392A (en) |
| BR (1) | BR9205679A (en) |
| CA (1) | CA2100168C (en) |
| DE (1) | DE69200922T2 (en) |
| DK (1) | DK0573585T3 (en) |
| ES (1) | ES2068710T3 (en) |
| GR (1) | GR3015377T3 (en) |
| NO (1) | NO308907B1 (en) |
| WO (1) | WO1992014868A1 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100408730C (en) * | 2001-10-04 | 2008-08-06 | 布里格斯斯特拉顿公司 | Anodized magnesium or magnesium alloy piston and method for manufacturing the same |
| CN103088385A (en) * | 2012-12-01 | 2013-05-08 | 江门市华恒灯饰有限公司 | Microarc oxidation electrolyte formula |
| CN105324520A (en) * | 2013-06-19 | 2016-02-10 | 堀金属表面处理工业股份有限公司 | Method for manufacturing magnesium alloy product |
| CN106835227A (en) * | 2016-12-05 | 2017-06-13 | 浙江工业大学 | A kind of method that titanium-base alloy high temperature oxidation resistance is improved based on halide effect and ceramic coating |
| CN106906505A (en) * | 2016-12-31 | 2017-06-30 | 浙江工业大学 | It is a kind of that the method that ceramic coating improves titanium-base alloy high temperature oxidation resistance is obtained based on halide effect and pretreatment |
| CN111321332A (en) * | 2018-12-17 | 2020-06-23 | 佳能株式会社 | Magnesium-lithium alloy member, method for manufacturing same, optical device, and imaging device |
| US11180832B2 (en) | 2018-12-17 | 2021-11-23 | Canon Kabushiki Kaisha | Magnesium-lithium alloy member, manufacturing method thereof, optical apparatus, imaging apparatus, electronic apparatus and mobile object |
| US12134807B2 (en) | 2018-12-17 | 2024-11-05 | Canon Kabushiki Kaisha | Magnesium-lithium alloy member, manufacturing method thereof, optical apparatus, imaging apparatus, electronic apparatus and mobile object |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5266412A (en) * | 1991-07-15 | 1993-11-30 | Technology Applications Group, Inc. | Coated magnesium alloys |
| JP4417106B2 (en) * | 2001-08-14 | 2010-02-17 | ケロナイト・インターナショナル・リミテッド | Magnesium anodizing system and method |
| US7578921B2 (en) | 2001-10-02 | 2009-08-25 | Henkel Kgaa | Process for anodically coating aluminum and/or titanium with ceramic oxides |
| US7569132B2 (en) | 2001-10-02 | 2009-08-04 | Henkel Kgaa | Process for anodically coating an aluminum substrate with ceramic oxides prior to polytetrafluoroethylene or silicone coating |
| US7452454B2 (en) | 2001-10-02 | 2008-11-18 | Henkel Kgaa | Anodized coating over aluminum and aluminum alloy coated substrates |
| US6916414B2 (en) * | 2001-10-02 | 2005-07-12 | Henkel Kommanditgesellschaft Auf Aktien | Light metal anodization |
| JP2007009319A (en) * | 2005-06-01 | 2007-01-18 | Meira Corp | Composition for forming protective film, method for manufacturing metal-molded body, and metal-molded body |
| US8192801B2 (en) * | 2008-04-25 | 2012-06-05 | GM Global Technology Operations LLC | Self-deposited coatings on magnesium alloys |
| US9701177B2 (en) | 2009-04-02 | 2017-07-11 | Henkel Ag & Co. Kgaa | Ceramic coated automotive heat exchanger components |
| JP5595874B2 (en) * | 2010-11-04 | 2014-09-24 | 三井金属鉱業株式会社 | Magnesium alloy surface treatment method |
| KR20170029545A (en) * | 2014-07-17 | 2017-03-15 | 헨켈 아게 운트 코. 카게아아 | Electroceramic coating for magnesium alloys |
| JP6659961B2 (en) * | 2016-08-10 | 2020-03-04 | 富士通株式会社 | Magnesium alloy substrate, electronic device, and method of forming corrosion-resistant coating |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4184926A (en) * | 1979-01-17 | 1980-01-22 | Otto Kozak | Anti-corrosive coating on magnesium and its alloys |
| US4620904A (en) * | 1985-10-25 | 1986-11-04 | Otto Kozak | Method of coating articles of magnesium and an electrolytic bath therefor |
| US4744872A (en) * | 1986-05-30 | 1988-05-17 | Ube Industries, Ltd. | Anodizing solution for anodic oxidation of magnesium or its alloys |
| JPS63277793A (en) * | 1987-05-08 | 1988-11-15 | Ube Ind Ltd | Anodic oxidizing solution for magnesium or alloy thereof |
-
1992
- 1992-02-25 WO PCT/US1992/001495 patent/WO1992014868A1/en active IP Right Grant
- 1992-02-25 DE DE69200922T patent/DE69200922T2/en not_active Expired - Fee Related
- 1992-02-25 JP JP50738392A patent/JP3183512B2/en not_active Expired - Fee Related
- 1992-02-25 DK DK92907909.3T patent/DK0573585T3/en active
- 1992-02-25 BR BR9205679A patent/BR9205679A/en not_active Application Discontinuation
- 1992-02-25 EP EP92907909A patent/EP0573585B1/en not_active Expired - Lifetime
- 1992-02-25 CA CA002100168A patent/CA2100168C/en not_active Expired - Lifetime
- 1992-02-25 AT AT92907909T patent/ATE115653T1/en not_active IP Right Cessation
- 1992-02-25 AU AU15353/92A patent/AU1535392A/en not_active Abandoned
- 1992-02-25 ES ES92907909T patent/ES2068710T3/en not_active Expired - Lifetime
- 1992-06-26 CN CN92105170A patent/CN1049701C/en not_active Expired - Fee Related
-
1993
- 1993-08-25 NO NO933024A patent/NO308907B1/en not_active IP Right Cessation
-
1995
- 1995-03-13 GR GR940404119T patent/GR3015377T3/en unknown
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100408730C (en) * | 2001-10-04 | 2008-08-06 | 布里格斯斯特拉顿公司 | Anodized magnesium or magnesium alloy piston and method for manufacturing the same |
| CN103088385A (en) * | 2012-12-01 | 2013-05-08 | 江门市华恒灯饰有限公司 | Microarc oxidation electrolyte formula |
| CN105324520A (en) * | 2013-06-19 | 2016-02-10 | 堀金属表面处理工业股份有限公司 | Method for manufacturing magnesium alloy product |
| CN105324520B (en) * | 2013-06-19 | 2017-10-27 | 堀金属表面处理工业股份有限公司 | The manufacture method of magnesium alloy product |
| CN106835227A (en) * | 2016-12-05 | 2017-06-13 | 浙江工业大学 | A kind of method that titanium-base alloy high temperature oxidation resistance is improved based on halide effect and ceramic coating |
| CN106906505A (en) * | 2016-12-31 | 2017-06-30 | 浙江工业大学 | It is a kind of that the method that ceramic coating improves titanium-base alloy high temperature oxidation resistance is obtained based on halide effect and pretreatment |
| CN111321332A (en) * | 2018-12-17 | 2020-06-23 | 佳能株式会社 | Magnesium-lithium alloy member, method for manufacturing same, optical device, and imaging device |
| US11180832B2 (en) | 2018-12-17 | 2021-11-23 | Canon Kabushiki Kaisha | Magnesium-lithium alloy member, manufacturing method thereof, optical apparatus, imaging apparatus, electronic apparatus and mobile object |
| US12134807B2 (en) | 2018-12-17 | 2024-11-05 | Canon Kabushiki Kaisha | Magnesium-lithium alloy member, manufacturing method thereof, optical apparatus, imaging apparatus, electronic apparatus and mobile object |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06504815A (en) | 1994-06-02 |
| CA2100168A1 (en) | 1992-08-27 |
| ES2068710T3 (en) | 1995-04-16 |
| CA2100168C (en) | 2004-09-14 |
| EP0573585A1 (en) | 1993-12-15 |
| EP0573585B1 (en) | 1994-12-14 |
| GR3015377T3 (en) | 1995-06-30 |
| DK0573585T3 (en) | 1995-03-06 |
| DE69200922D1 (en) | 1995-01-26 |
| AU1535392A (en) | 1992-09-15 |
| WO1992014868A1 (en) | 1992-09-03 |
| BR9205679A (en) | 1994-06-21 |
| NO933024D0 (en) | 1993-08-25 |
| CN1049701C (en) | 2000-02-23 |
| DE69200922T2 (en) | 1995-05-04 |
| NO933024L (en) | 1993-10-14 |
| JP3183512B2 (en) | 2001-07-09 |
| ATE115653T1 (en) | 1994-12-15 |
| NO308907B1 (en) | 2000-11-13 |
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| C15 | Extension of patent right duration from 15 to 20 years for appl. with date before 31.12.1992 and still valid on 11.12.2001 (patent law change 1993) | ||
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