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CN1316067C - Method for purifying and decontaminating surface of light metal alloy - Google Patents

Method for purifying and decontaminating surface of light metal alloy Download PDF

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Publication number
CN1316067C
CN1316067C CNB021248060A CN02124806A CN1316067C CN 1316067 C CN1316067 C CN 1316067C CN B021248060 A CNB021248060 A CN B021248060A CN 02124806 A CN02124806 A CN 02124806A CN 1316067 C CN1316067 C CN 1316067C
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China
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solution
phosphoric acid
light metal
metal alloy
alcohol
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Expired - Fee Related
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CNB021248060A
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Chinese (zh)
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CN1397667A (en
Inventor
沃尔夫·迪特尔·弗朗斯
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Enton Co.
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ENTON Co
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25FPROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F1/00Electrolytic cleaning, degreasing, pickling or descaling
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25FPROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F1/00Electrolytic cleaning, degreasing, pickling or descaling
    • C25F1/02Pickling; Descaling
    • C25F1/04Pickling; Descaling in solution

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Chemical Treatment Of Metals (AREA)
  • ing And Chemical Polishing (AREA)

Abstract

The present invention provided a novel method for cleaning and passivating a surface of a light alloy having a relatively high Al or Mg content. This method is suitable for preparing the surface for a subsequent coating operation.

Description

The method of purification and decontaminating surface of light metal alloy
The present invention relates to handle a kind of novel method of light metal surface.The purpose of handling is the surface that purifies and keep process to purify to a certain extent.The present invention at light metal alloy contain main component aluminium and/or main component magnesium.
The disclosed method that a large amount of purification surface of light metal alloy are arranged.These shortcomings that disclose the method part are to want the continuous treatment step of larger amt, need quite high expense thus.These another part that disclose method are not reach enough decontamination effect improvings for certain material, and for example the separating agent residue is got rid of effectively reliably as polymerization silane (Polysilane).
Well-known in addition, the surface passivation of light metal alloy can be able to kept thus in some sense through behind the cleaning section of oxide treatment.The notion of oxidation is here understood on the meaning of chemistry at large, except comprise with high aluminium component alloy in the oxygen reaction that will consider, also comprise with high magnesium component alloy in fluorochemical react.
These disclosed purifications and passivating method partly have defective, are an impediment to healthy material because they contain, as discharging the nitric acid of nitrous gases.In addition, conventionally also be difficult to passivation step with purify combine pass through purification before must making passivation the surface no longer in its variation qualitatively.
The present invention provides a kind of on its conversion characteristic on the whole at this technical problem in a word, on its insensitivity to alloying constituent, and the effective purification of considering economically and the method for decontaminating surface of light metal alloy.
What the present invention is directed to is a kind of method that purifies surface of light metal alloy, in the method the surface carry out passivation by oxidation step, it is characterized in that, by a kind of contain phosphoric acid and alcohol solution in treatment step anode is connected on the surface.
Fact proved, utilize according to anode cleaning method of the present invention to reach very basic while decontamination effect improving very widely again.The anode cleaning step of carrying out in the solution that contains phosphoric acid and alcohol is that surperficial degreasing or surface etching all have good effect, can remove in addition as the deleterious residue of this class of polymerization silane separating agent.
Because anode operation, have certain restraining effect according to the method for purification of the present invention, the oxygen reaction by light metal surface prevents bigger spillage of material.It both had been applicable to the light metal alloy of higher aluminum composition, also was applicable to the light metal alloy of higher magnesium component.
Specifically, can regulate decontamination effect improving, particularly etch effect by the electrical parameter of selecting the anode cleaning operation, and depend on that thus the alloy of special consideration is optimized.For example can utilize certain anodic current density operation.Therefore can grasp the optimum parameter that does not change solution composition.Thus can also a kind of with a kind of solution in adopt different alloys to carry out optimum operation.Certainly, also can make the solution composition optimizing, although the inventor can not determine important dependence here according to alloy.
Alcohol can be considered common alcohol, as methyl alcohol, and ethanol, propyl alcohol, butanols and high-valency alcohol and derivative thereof are as Virahol.In addition, also can be glycol, polyethers and other alcohol.Useful selection is butanols and Virahol.Certainly, also can be that two or more alcohol mix.
In another expansion of foundation the inventive method, used fluorochemical, to reach surface passivation.This fluorochemical is used for containing in addition the solution of phosphoric acid, also is that anode is connected on the surface in this treatment step.In addition, this step also can match with the treatment step of having introduced in the solution that contains phosphoric acid and alcohol, at this, except containing phosphoric acid, outside the alcohol, also contains fluorochemical in the solution.But these steps also can separately be carried out, and the step that contains fluoride aqueous solution is finished after the step of at first introducing in time.In after a while the step, for making its conversion characteristic optimizing, except phosphoric acid and fluorochemical, this solution can also contain this or another is pure (and mixture this or that another is pure) on this time.
Fluorochemical can exist in a different manner, as alkaline fluorochemical, and Neutral ammonium fluoride (bi) or hydrofluoric acid.
Adopt fluorochemical to handle and at first be used for the light metal alloy that main component is a magnesium, then therein MgF 2Form passivation layer or be formed in the passivation layer.If the light metal alloy magnesium component is 50 weight percents and is higher than this value, so especially preferably contains the step of fluorochemical.
In addition, the fluorine ionization steps is preferred for the light metal alloy of siliceous composition, is 0.1 if be preferably it, particularly 0.5 or 1 or 2 weight percents and be higher than the words of this value.Would rather select little fluoride concn if silicon concentration is less.That is to say, even the trace or do not have in the light metal alloy of magnesium component, the fluorine ionization steps also is useful.
Be to end at alkaline rinse step according to purification of the present invention and deactivation method advantage, as being 10 in preferred pH value and being higher than the alkalization water of this value.If this alkalescence rinse step is at MgF 2If particularly advantageous under the dominant passive surface situation is and AL 2O 3Preponderate, but not too favourable under said high pH value situation.
If main component is an aluminium, particularly weight percent is 60 and is higher than under the situation of aluminium of this value, preferably after the treatment step in the solution of phosphoric acid and alcohol, with may be after the treatment step in the solution of fluoride, and afterwards in case of necessity, in oxidizing aqueous dose, finish an additional passivation step at other treatment step (but these steps are according to the present invention and not preferred).This oxygenant for example can be peroxy-disulfuric acid solution or permonosulphuric acid (Caro ' s acid).In this case, the passivation step in this oxygenant should be finished by possible treatment step in fluoride aqueous solution afterwards.
On the surface of the fluorochemical coating of high magnesium component light metal alloy, do not need oxidation step.If it is to carry out in acid range, it also can cause damage to the fluorochemical passivation (as pH6 and be lower than under this value situation).
Following quantitative scope proves has advantage: the fluorion composition lower limit in relevant total solution can be a numerical value between 0.1,0.3 or 0.5 weight percent, and the upper limit can be a numerical value between 30,20 or 10 weight percents.
Anodic current density on the anodic polarization surface of light metal alloy is preferably in 10,30 or 50A/m 2Between as lower limit, 500A/m 2As the upper limit, and as the by the agency of of front, depend on alloying constituent, the spillage of material that may occur and the decontamination effect improving of requirement use as the optimizing parameter.
The favourable temperature of anode cleaning step solution is between 10 and 40 degree.
The overall treatment time of anode cleaning step (under a plurality of step situations in the sum) for example can be between 10 seconds and 5 minutes, and depend on the current density of being adjusted, the spillage of material that may occur and pollution level to a great extent.
Phosphoric acid proportion in the anode cleaning step solution is 30-90 volume %, and the phosphoric acid within this bulk specific gravity can be the 50-95 weight percent.This point especially at be the solution that contains pure composition, except the phosphoric acid bulk specific gravity of said 30-90 volume %, all the other mainly are made up of alcohol (mixture), by situation under in addition fluorochemical form.
According to the decontamination effect improving of the inventive method very basic and and extensively, thereby before the solution that contains phosphoric acid and alcohol of packing into, can exempt Chemical Pretreatment, and preferably also it should be cancelled for economic reasons.Therefore, institute surface to be processed can directly and dryly be dropped into.
In addition, special advantage of the present invention is, also can obtain good result on the regenerated light metal alloy, settling particularly do not occur.The metallic impurity of twice-laid stuff are if adopt traditional method to bring very serious problem to purification, and usually serious the obstruction purifies and follow-up good coat.Even under the higher situation of aluminium component, the surface still can keep metal glossy according in the anodic dissolution of the present invention, thereby the oxidation of carrying out subsequently also can be finished when no nitric acid.
Useful application of the present invention is that surface of light metal alloy is the preparation aspect that the coating of any type is subsequently done.For the quality of coating, mainly depend on and surperficial cleanliness factor, and should consider optical characteristics, also to consider the withstand load of coating.In this regard, the present invention is especially at the metallization that is connected, and it at first should realize not having foreign current.Thus, the present invention also is at the purification of being introduced and passivation and follow-up coating, particularly metallized total method.
Introduce the present invention with two embodiment below, wherein disclosed individual characteristics also might be among other combination of the present invention.
As the exemplary of higher magnesium component alloy, choose AZ91, wherein also consider AM50 or AZ31.The AZ91 alloy is without other chemical purification, and drying is packed into and contained 60% phosphoric acid (H of 40 volume % butanols 3PO 4) in, and anodic polarization.Current density is 20A/m in temperature 25 degree and treatment time when being 30 seconds for example 2
After this AZ91 alloy is dropped in second kind of solution, this solution has the composition identical with said composition, but contains the fluoride amine of 2 weight percents in addition.Further anode cleaning continues to finish in 20 seconds under same current density.
After this AZ91 parts are washed in alkaline water (pH is a little more than 10).Also can metallize by traditional way by the fluorinated layer passivation now in the AZ91 surface.In this embodiment, select a kind of zinc that contains, nickel or copper or a kind of conversion coating of alloy wherein for this reason.
Second embodiment at be high aluminium component alloy, just industrial aluminum, i.e. GdAlSi8Cu3.Because this alloy is siliceous, so also use the fluoride aqueous solution of being mentioned among first embodiment here.Can select identical quantitative factor, but cancel the rinse step in the alkaline water.What replace it is with neutral water (pH about 7) flushing, uses the extra oxidation of peroxy-disulfuric acid solution subsequently, so that strengthen passivation layer.This processing also is applicable to GdAlSi9Cu3.
Then can be zinc-plated again through the parts of this processing, nickel plating or copper facing, or with wherein alloy coat.When chemical conversion coating, passivation layer fusion or transform so that produce between the metal good with directly contact.
A special advantage is, the sealing oxidation of aluminium alloy can not have nitric acid and finishes, because there is the surface of a metal polish.Therefore can not produce the nitrous gases in the traditional method, thereby exempt the technical fee of air draft and waste-gas cleaning on the one hand, not have the obligation that obtains permission (is BlmschG in Germany) by relevant regulations on the other hand yet.
If light metal alloy source and for example casting die, they can be infected with the moulding separating agent so in principle.Even this alloy also can reliably and fully be got rid of in the method for purification of being introduced.

Claims (16)

1. the method that purifies of a surface of light metal alloy, utilize oxidation step that passivation is carried out on described surface, it is characterized in that, treatment step carries out in the solution that contains phosphoric acid and alcohol, wherein in described treatment step, anode is connected on described surface, and described alcohol is to comprise a kind of in the group of methyl alcohol, ethanol, propyl alcohol, butanols, Virahol or derivatives thereof.
2. by the described method of claim 1, be included in the treatment step in the solution that contains phosphoric acid and fluorochemical, connect anode on surface described in this step.
3. by claim 1 or 2 described methods, comprise last alkaline rinse step.
4. by the described method of claim 2, wherein light metal alloy contains the silicon of at least 0.1 weight percent.
5. by the described method of claim 2, wherein light metal alloy contains the magnesium of at least 50 weight percents.
6. by the described method of claim 2, contain phosphoric acid and alcoholic solution and contain phosphoric acid and fluoride aqueous solution in treatment step comprehensively be a treatment step that contains in phosphoric acid, the pure and mild fluoride aqueous solution.
By the method shown in the claim 2 at first carry out contain phosphoric acid and alcohol solution in treatment step, then carry out the treatment step in the solution that contains phosphoric acid and fluorochemical respectively.
8. by the described method of claim 7, the solution that wherein contains phosphoric acid and fluorochemical contains alcohol in addition.
9. by the described method of claim 1, wherein light metal alloy contains the aluminium of at least 60 weight percents, and finishes another treatment step in the water oxygenant after the treatment step in the solution that contains phosphoric acid and alcohol.
10. by claim 1 or 2 described methods, wherein during the single or multiple treatment steps in the single or multiple solution that contain phosphoric acid, the light metal alloy anodizing, the temperature of solution is between 10 degree and 40 degree.
11. by claim 1 or 2 described methods, wherein the residue of solution is made up of at least a alcohol and/or at least a fluorochemical basically.
12. by the described method of claim 11, wherein, the phosphoric acid in described volume ratio is the 50-95 weight percent.
13., wherein will contain in the solution of phosphoric acid and alcohol without the light metal surface input of Chemical Pretreatment by claim 1 or 2 described methods.
14. by aforementioned claim 1 or 2 described methods, described light metal alloy is made up of twice-laid stuff.
15. surface of light metal alloy is carried out the method for coating, wherein utilizes a described method among the claim 1-14 that surface of light metal alloy is purified and passivation earlier, then coating.
16. by the described method of claim 15, wherein coating process is the metallization process of no foreign current.
CNB021248060A 2001-06-20 2002-06-20 Method for purifying and decontaminating surface of light metal alloy Expired - Fee Related CN1316067C (en)

Applications Claiming Priority (2)

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EP01114981A EP1270767B1 (en) 2001-06-20 2001-06-20 Process for cleaning and passivating light metal alloy surfaces
EP01114981.2 2001-06-20

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CN1316067C true CN1316067C (en) 2007-05-16

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EP (1) EP1270767B1 (en)
JP (1) JP3839362B2 (en)
KR (1) KR100502863B1 (en)
CN (1) CN1316067C (en)
AT (1) ATE256770T1 (en)
DE (1) DE50101194D1 (en)
DK (1) DK1270767T3 (en)
SI (1) SI1270767T1 (en)

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US7578921B2 (en) * 2001-10-02 2009-08-25 Henkel Kgaa Process for anodically coating aluminum and/or titanium with ceramic oxides
AU2002338880A1 (en) * 2002-10-09 2004-05-04 Wolf-Dieter Franz Method for cleaning and passivating light alloy surfaces
US20050221007A1 (en) * 2003-11-20 2005-10-06 Bae Systems Plc Surface preparation
CN101591799B (en) * 2008-05-30 2011-04-20 比亚迪股份有限公司 Electrolytic polishing solution of magnesium alloy and magnesium alloy surface polishing processing method
CN101591797B (en) * 2008-05-30 2012-08-08 中芯国际集成电路制造(上海)有限公司 Al pad electrochemical etching method
JP6557984B2 (en) * 2015-02-06 2019-08-14 栗田工業株式会社 Aluminum or aluminum alloy sealing method and sealing device
CN105603409B (en) * 2016-01-15 2018-10-09 华南理工大学 A kind of Aluminum Alloy Room Temperature alkalinity chromium-free passivation liquid and passivating method
DE102017109739A1 (en) * 2017-05-05 2018-11-08 Fischer Oberflächentechnik GmbH Aqueous solution and method for removing acid residues from metal surfaces
CN107829122A (en) * 2017-11-24 2018-03-23 绩溪山合机械有限公司 A kind of chain inactivating treatment liquid and its passivation process

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CN1039677A (en) * 1988-07-06 1990-02-14 皮奇尼铅公司 Be used to make the method for the continuously enamelling wire of aluminium alloy of electrician's coil
US5997721A (en) * 1994-12-19 1999-12-07 Alcan International Limited Cleaning aluminum workpieces
CN1049259C (en) * 1994-12-29 2000-02-09 华中理工大学 Electrochemical Polishing Method for Aluminum and Aluminum Alloy Welding Wire

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Publication number Publication date
SI1270767T1 (en) 2004-06-30
EP1270767B1 (en) 2003-12-17
US20030056807A1 (en) 2003-03-27
JP2003049299A (en) 2003-02-21
DE50101194D1 (en) 2004-01-29
CN1397667A (en) 2003-02-19
DK1270767T3 (en) 2004-04-13
JP3839362B2 (en) 2006-11-01
EP1270767A1 (en) 2003-01-02
KR20020097002A (en) 2002-12-31
KR100502863B1 (en) 2005-07-25
ATE256770T1 (en) 2004-01-15

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