CN1195893C - Non-chromated oxide coating for aluminum substrates - Google Patents

Non-chromated oxide coating for aluminum substrates Download PDF

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CN1195893C
CN1195893C CNB931075831A CN93107583A CN1195893C CN 1195893 C CN1195893 C CN 1195893C CN B931075831 A CNB931075831 A CN B931075831A CN 93107583 A CN93107583 A CN 93107583A CN 1195893 C CN1195893 C CN 1195893C
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solution
cobalt
mentioned
conversion coating
mole
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CN1080963A (en
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M·P·施里弗
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Boeing Co
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    • 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
    • C23C22/48—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 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/56—Treatment of aluminium or alloys based thereon
    • 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
    • C23C22/60—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 alkaline aqueous solutions with pH greater than 8
    • C23C22/66—Treatment of aluminium or alloys based thereon
    • 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
    • C23C22/68—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 solutions with pH between 6 and 8

Abstract

A process for forming a cobalt conversion coating on a metal substrate, thereby imparting corrosion resistance and paint adhesion properties, providing a cobalt conversion solution comprising an aqueous solution containing a soluble cobalt-III hexavalent complex, the concentration of the cobalt-III hexavalent complex being from about 0.01 mole per liter of solution to the solubility limit of the cobalt-III hexavalent complex; and contacting the substrate with the solution for a sufficient amount of time, whereby the cobalt conversion coating is formed. The substrate may be aluminum or aluminum alloy, as well as Cd plated, Zn plated, Zn-Ni plated, and steel. The cobalt-III hexavalent complex may be present in the form of Mem(Co(R)6)n, wherein Me is Na, Li, K, Ca, Zn, Mg, or Mn, and wherein m is 2 or 3, n is 1 or 2.

Description

Conversion coating solution and on metal matrix, produce method of oxide film cobalt conversion coating and uses thereof
The present invention payes attention to environmental quality, belongs at metal matrix (as aluminum matrix) to go up the technical field that forms chemical conversion coating.More particularly, one of content of the present invention relates to the new oxide coating of a class (being referred to as " cobalt conversion coating "), and this coating forms by chemical process on metal matrix.The present invention has been owing to protected the quality of empty G﹠W, thereby the improvement of the mankind's environmental quality is played an important role.
In general, chemical conversion coating is to form on the metallic surface that will " transform " a secure adhesion coating with chemical process.The all or part of oxide compound by matrix metal of coating is formed.Chemical conversion coating can provide high corrosion resistance and the strong adhesive power to painting.Industrial metal is used paint (organic finish paint), general requirement is utilized chemical conversion coating, particularly when the serviceability requirement is quite high.
Though aluminium can form a native oxide layer on its surface, itself is not corroded protection, and this protection is incomplete.In the presence of moisture and ionogen, aluminium alloy particularly resembles the aluminium alloy of high-copper 2000 series the alloy 2024-T3, corrodes manyly than fine aluminium is easy.
Generally speaking, for forming effective conversion coating, two kinds of methods of handling aluminium are arranged.First kind is anodic oxidation (anodizing), and the aluminium assembly is immersed in the chemical bath.For example chromic acid or sulfuric acid bath passed through aluminium assembly and chemical bath with electric current then.Can be anticorrosive at the conversion coating that the aluminium assembly surface obtains.And the surface is bonded with the hood finish paint.
Second method is to produce a conversion coating by chemical reaction, is commonly referred to chemical conversion coating.This method is to use a chemical solution, and for example chromic acid solution is handled the aluminium assembly, but this method is without electric current.Using of chemical solution can be passed through methods such as dipping, craft or spraying.Can be anticorrosive at the conversion coating that the aluminium assembly surface forms, and the surface is bonded with the hood finish paint.The present invention just relates to the second method that generates chemical conversion coating.Using of chemical solution can be passed through pickling process, various manual method or spraying method.
United States Patent (USP) 2 at Ostrader etc., 796, the United States Patent (USP) 2 of No. 370 and Ostrader etc., 796, No. 371, narrated in each concrete scheme of military technological standards MIL-C-5541 and Boeing Process Specifica-tion BAC 5 719 a kind of on aluminum matrix the chromic acid method of widely used formation chemical conversion coating.These chromic acid chemical conversions contain sexavalent chrome, fluorochemical and prussiate in bathing, and these materials all have suitable adverse influence to environment and health and safety.A kind of typical chromic acid transforms bathes the composed as follows of (for example ALODINE1200): CrO 3-" chromic acid " (sexavalent chrome), NaF-Sodium Fluoride, KBF 4-potassium tetrafluoroborate, K aZrF 6-Potassium Zirconium Fluoride, K 3Fe (CN) 6-the Tripotassium iron hexacyanide and HNO 3-nitric acid (control pH value is used).
In whole aeronautics and space industry, many constructed of aluminium parts, and plating Cd, plating Zn, plating Zn-Ni and steel part are handled with this kind chromic acid method recently.The chromic acid that forms on aluminum matrix transforms film can satisfy 168 hours anticorrosive standards, but mainly is used as the surface matrix of paint adhesion.Because relatively thinner and low (the 40-150 milligram/foot of coating wt 2), the chromic acid conversion coating can not cause the constructed of aluminium reduction of fatigue lifetime.
Yet, the U.S. (particularly California) and other national environmental legislation sharply reducing hexavalent chromium compound in Metal Processing Factory's draining and the exhaust can the permission level.Therefore, must replace the chemical transformation that uses hexavalent chromium compound.Do not use the present invention of hexavalent chromium compound, just be intended to replace the past in order on aluminum matrix, to form the chromic acid method of chemical conversion coating.
A. on the one hand, the present invention is a kind of method that forms the cobalt conversion coating on metal matrix, and erosion resistance and paint adhesion performance can be provided like this.The present invention can be used for replacing previous chromic acid method.Present method comprises: (a) provide a kind of cobalt to transform solution, as the cobalt that comprises the formation oxide film of a reacting solution transforms solution, this solution is the aqueous solution that contains the hexa-atomic complex compound of solvable cobalt-III, and the concentration of the hexa-atomic complex compound of cobalt-III is by 0.01 mole of saturation limit to the hexa-atomic complex compound of cobalt-III of every liter of solution approximately; (b) make metal matrix carry out the contact of enough time with this solution, thereby as described in making the stromal surface oxidation generate the cobalt conversion coating, as above-mentioned oxide film cobalt conversion coating.Matrix can be aluminium, aluminium alloy, and cadmium plating, zinc-plated, zinc-plated-nickel, and steel.The hexa-atomic complex compound of cobalt-III is preferably with Mem[Co (R) 6] the n form exists, wherein, Me is selected from the group of Na, Li, K, Ca, Zn, Mg and Mn one or more, and as being Na, Li, K, Ca, Zn, Mg or Mn, m is 2 or 3, and n is 1 or 2, and R is the carboxylate radical with 1-6 carbon atom.The pH of preferred described reacting solution is 5.0-9.0.
B. on the other hand, the present invention is the chemical conversion masking liquid that produces the cobalt conversion coating on metal matrix.This solution comprises the aqueous solution that contains solvable cobalt-III hexacarboxylic acid root complex compound.The concentration of cobalt-III hexacarboxylic acid root complex compound is by every liter of about 0.01 mole of saturation limit to cobalt-III hexacarboxylic acid root complex compound of solution.Cobalt transforms the preparation of solution and finishes in proper order by the solution preparation, comprising: (a) dissolving one solubility cobalt-II salt, be preferably Cobaltous diacetate, and (b) dissolving-metal acetate salt, for example sodium-acetate, magnesium acetate or calcium acetate are with the formation conversion coating solution.
C. another aspect of the present invention is to add wetting agent, for example alkyl fluoride RF, fluorocarbon and metal fluoride in conversion coating solution.Add the sealing process of the costliness that these wetting agents just no longer need be after conversion coating forms.
Appended figure is the Photomicrograph of image that the coating on the aluminium alloy test board is obtained with scanning electronic microscope.Fig. 1-4 is the Photomicrograph (scanning electronic microscope is operated) of alloy 2024-T3 test board with cobalt conversion coating that the inventive method makes under 20 kilovolts.Fig. 1-4 is presented at and impregnated in the cobalt conversion coating 410 that formed in 15 minutes in the typical cobalt conversion coating solution under 140 °F.
In conjunction with the accompanying drawings, with reference to following detailed description, can be more readily understood above-mentioned of the present invention several aspects and consequent advantage.Wherein:
Fig. 1 is that the test board of explanation cobalt conversion coating 410 of the present invention amplifies 10,000 times Photomicrograph.This photo is the vertical view of oxide coating 410 upper faces.The top of oxide coating 410 is porous, resembles very much sponge.This test board was dipped in the cobalt conversion coating solution 15 minutes.The length that white rod expression is 1 micron.
Fig. 2 is that Fig. 1 test board amplifies 70,000 times Photomicrograph.This photo is the vertical view of the upper face of oxide coating 410.Fig. 2 is the closeup photograph that a small area height of test board amplifies.White icon is represented 1 micron length.
Fig. 3 is the Photomicrograph of 10,000 times of the amplifications of another test board, shows the high angle side-view of the rupture cross section of cobalt conversion coating 420 of the present invention.The aluminum matrix rupture cross section of test board is pointed out by numeral 422.This test board soaked in coating is molten 15 minutes.For obtaining Photomicrograph, test board is crooked and make it fracture, to expose the cross section of oxide coating 420.White icon is represented 1 micron length.
Fig. 4 is that the used test board of Fig. 3 amplifies 70,000 times Photomicrograph, shows the high angle side-view of the rupture cross section of cobalt conversion coating 420 of the present invention.Fig. 4 is the closeup photograph that the height of test board small area amplifies.The aluminum matrix of test board is pointed out by numeral 422.White 1 micron length of icon representation.
Fig. 5 represent paint adhesion and anticorrosive between growth and decline and the relation of dipping time.
The present invention relates to a kind of new cobalt conversion coating.This cobalt conversion coating erosion resistance is very high, thereby no longer needs traditional sealing process.Its reason is to have added metal fluoride and wetting agent in conversion coating solution, as alkyl fluoride RF and fluorocarbon.It is believed that wetting agent can give the aluminum matrix surface with little etch effect with the metal fluoride combination, this helps coating to form.
With regard to relevant background of the present invention, should address the theme described in the formerly common pending application.To achieve the object of the present invention, carried out a large amount of experimental studies.Inquired into various multivalent compounds, these compounds or use separately, or same alkali, acid or fluorochemical use together.These multivalent compounds are vanadate, molybdate, cerate, ferrate and various borate.When the compound that contains these elements presents thin film deposition on aluminium alloy matrix, both there be not tangible anticorrosive effect, the bounding force of unmatchful paint yet.
Therefore, use some reagent, i.e. Co (NO 3) 6H 2O, CoCl 26H 2O, NH 4NO 3, NH 4Cl and NH 4OH makes cobalt ammonia complex.The coating that generates on aluminum matrix has obviously improved anticorrosive effect than the previous simple salt dipping of discussing.Make a general survey of cobalt complexing chemical developer and obtain following message.
When containing ammonium hydroxide one, in the cobalt-II salts solution of corresponding ammonium salt and activated carbon, be blown into airflow several hours, then obtain six ammonia salt:
(1)
Wherein X=Cl, Br, NO 3, CN, SCN, PO 4, SO 4, C 2H 3O 2And CO 3
As non-activity carbon, then obtain
〔Co(NH 3) 5X〕 2+ (2)
These common reactions are based on the following fact: divalent cobalt has the tendency that intensive is oxidized to the trivalent cobalt complex, that is:
(3)
These reactions are not new, and have been widely studied.In the photographic process industry, generally use cobalt-III complex compound as the sharpness of oxygenant with the raising colour phhotograpy.Yet what astonish is that cobalt complex can form oxide structure on aluminum matrix.The accurate mechanism that this oxide compound forms is not understood fully as yet, but be it is believed that the chemical equilibrium in the reaction formula (3) in action.
It is believed that the reason that forms sull on aluminum matrix is this tendency to oxidize.Utilize following chemical equilibrium, successfully form liquid formulation.
(4)
Ammonium nitrate is used to prevent the initial stage precipitation of reaction product.The sequence number of filing an application in May 17 nineteen ninety in 07/525,800 the formerly common pending application, was once extensively commented on this chemical property.
Yet, illustrate after the examination to reaction (4), in the time of on aluminum matrix, forming the iris coating that limits, need excess of ammonia, i.e. NH 4OH is to promote this reaction.This is because ammonia velocity of evaporation from solution is very high, so be difficult to control the pH value in the bath.And the excess ammonia in the bath has tangible influence to the paint adhesion and the corrosion resistance of the coating that forms with this method.According to ammonia amount in bathing; Paint adhesion and corrosion resistance can be from fabulous to utter failures.
When attempting the complex compound that comprises dentate (the parantheses part of formula (6)) in the cobalt complex partly changed, this technology has had major progress.To the exploitation of reacting the ammonification cobalt complex of (4) being narrated, determined that the body lotion chemical ingredients is 3 valency cobalt ammonia complex, promptly as reaction (1)
〔Co(NH 3) 6〕X 3 (5)
Wherein X=Cl, Br, NO 3, CN, SCN, PO 4, SO 4, C 2H 3O 2, CO 3, the complex compound part that comprises dentate is positively charged, promptly
〔Co(NH 3) 6〕 3+ (6)
Use the nitrite compound substituted ammonium compound, then generate 3 valency cobalt complexs, as
Me 3〔Co(NO 2) 6〕 (7)
Wherein Me=Na, Li, K, the complex compound part that comprises dentate is electronegative, promptly
〔Co(NO 2) 6〕 3- (8)
But this nitrite anions complexing chemistry self is controlled at the pH value in the stable range of 6.8-7.2.The paint adhesion performance also obviously is better than former chromic acidization film.Sequence number be in 07/621,132 the formerly common pending application once extensive discussions cross the chemical property of this respect.Two important features of the conversion film that forms with the nitrite method are, appearance is infused (shallow iris) clearly, and coated membrane weight is up to 90 milligrams/foot 2These two restrictions caused further research with the coating wt of the color characteristic that inquire into to obtain to have intensive and easily discover and Geng Gao (promptly above 90 milligrams/foot 2) possibility.
At last, form following complex compound owing to import acetate
Me 3(Co (C 2H 3O 2) 6) (9) and the prescription of succeeing, the complex compound part that comprises dentate in the formula is also electronegative, promptly
(Co (C 2H 3O 2) 6) 3-(10) coating that forms with this method has the intensive color, and outer appearnce is similar to former chromic acidization coating.Coating wt can reach 350 milligrams/foot 2More than.In this prescription, add nitrate, as NaNO 3, Mg (NO 3) 26H 2O or Ca (NO 3) 26H 2O helps to improve the coating firmness under the high coating wt, thereby has avoided loose powdery deposition.
The result of this research has selected to produce two kinds of liquid formulations of clear thorough coating and color coating for further test.Below two equations determine the chemical transformation of the cobalt conversion coating of clear thorough cobalt conversion coating of fourth and band look.
Clear thorough coating:
Figure C9310758300141
Color coating:
Figure C9310758300143
When producing coating by equation (11) and (12), in the solution of formulated, seal subsequently, when testing, obtain to reach 140 hours the anticorrosive experiment of salt fog by ASTM B117 method.Be in 07/732,568 the formerly common pending application this Chemical Problem on the one hand have been done to discuss widely in series number.
So far the progress of being discussed relates to by divalent cobalt (Co (NO for example 3) 26H 2O) same ammonium acetate (CH 3COONH 4) form the conversion coating that the reaction of trivalent cobalt complex obtains.The determinacy of the coating that produces can reach outstanding, yet, utilize the body lotion life-span of Spirit of Mindererus quite short, promptly about 30-40 days.Wish to prolong this body lotion life-span and be the foundation of the further research work of just having finished.The whole process of this work makes progress, according to coating performance of the present invention improvement is arranged also, will discuss in detail below.
Notice that in test ammonium acetate complex cobalt solution (equation (12)) after the normal groove operation in several weeks, the coating wt on the aluminum matrix can gradually reduce, colour intensity shoals.For this is remedied, need to increase dipping time.Simultaneously notice that also solution appearance changes in time and progressively, from the dun to the red-purple.By analysis, determine at last, a competing reaction takes place in time, at complex compound
(Co (C 2H 3O 2) 6) 3-(13) acetate in is progressively replaced by ammonia and forms complex compound
(Co (NH 3) 6) 3+Notice that (14) valency in these parenthesized ionic species changes.
According to the present invention, in the effort of head it off, find, use metal acetate salt, for example Na (C 2H 3O 2) 3H 2O, Mg (C 2H 3O 2) 24H 2O or Ca (C 2H 3O 2) 2H 2O replaces the NH in the equation (12) 4(C 2H 3O 2) can eliminate same complex compound (13) the above-mentioned competing reaction relevant with (14), and produce strong color coating as initial Spirit of Mindererus.Sodium-acetate is most preferred carboxylic metallic salt.Other carboxylic metallic salt can be worked as zinc acetate, Lithium Acetate, Potassium ethanoate and magnesium acetate, but is not preferred.Typical reaction is
(15)
Carry out these reactions and be by in solution, being blown into air, and without hydrogen peroxide.Acetic acid be not as reagent add but form in solution as part complexing chemical reaction.Compare with the conversion coating solution that reacts generation with equation (11) and (12), carrying out salt-fog test with ASTM B117 method proves that the corrosion resistance of the conversion coating of these acquisitions further is improved.About this point, have been found that the cobalt conversion coating with high-performance feature can obtain with the carboxylate metal reactant salt by the solubility cobalt salt, reaction formula is as follows:
(18) wherein, x can be 1 or 2, and m is 3, and n is 1 or 2, and Me can be by selecting among Na, Li, K, Ca, Zn, Mg and the Mn, and R is the carboxylate radical with 1-5 carbon (C) atom, and this carboxylate radical should dissolve in the reaction soln.
In these solution, also can add a spot of metal fluoride (as MgF 2And CaF 2) and wetting agent (as water miscible alkyl fluoride RF and fluorocarbon), with the improvement preservative property, and make manufacturing processed be easy to carry out (Table III and IV).Specifically, successfully utilized the M ﹠amp of joslyn hi-voltage; Fluorocarbon FC99 or FC95 wetting agent that the MSP-ST alkyl fluoride RF wetting agent that T Harshaw-company produces and the 3M company in Sao Paulo, the Minnesota State produce.The existence of fluorine-containing wetting agent, metal fluoride or its mixture can improve the corrosion resistance of coating so far forth, so that no longer needs in the accessory sealing process these conversion coating sealings.In principle, the arbitrary water-soluble fluorine-containing wetting agent that the surface tension of liquid can be dropped in the scope of 20 ℃ of following every centimetre of 30-40 dyne all can use.The coating that the solution of operation as described in detail below produces has been passed through the method according to Boeing Process Specification BAC5719, the anticorrosive standard tests of salt fog in 168 hours that " chromic acid conversion coating " carries out.One step conversion coating has produced the salt fog corrosion resistance test above 240 hours before any corrosion plaque signal occurring.
Experiment with formula (16), (17) and (18) can know that concerning chemical property and the common coating performance that constitutes of compatible consistence, some parameter is very important.These parameters are solution composition and process sequence, the selection of reactant and body lotion concentration, temperature control and dipping time.It is again emphasized that the reactive system of being founded is very complicated, relate to several simultaneous reversible reactions.Can think that for reaching optimum according to the invention, the entire reaction system should be in or near equilibrium conditions.
Having found to influence the paint adhesion of conversion coating and the most important parameters of corrosion resistance is selection and their concentration in solution of reactant.The bigger variation of temperature and dipping time has been found that what coating performance was had the greatest impact is these parameters, rather than bathes temperature or dipping time, although really can exert an influence.
As everyone knows, with regard to the surface treatment of aluminium, paint adhesion and anticorrosive be opposite character.In other words, best for making paint adhesion, often to sacrifice erosion resistance, vice versa.Find also that now concerning the cobalt conversion coating, this surface treatment behavior also exists.In the research that institute does and discusses in this and above-mentioned formerly common pending application, set up preferred series table about various cobalt compounds and their anti-corrosion effects and paint adhesion performance.
Table I. with the cobalt of acetic acid metal-salt complexing
The performance evaluation of salt
Composition erosion resistance paint adhesion
Cobaltous diacetate+acetic acid metal-salt 12
Xiao Suangu+acetic acid metal-salt 31
Rose vitriol+acetic acid metal-salt 24
Cobalt chloride+acetic acid metal-salt 43
Estimate: 1=is best, and 4=is the worst
Can find out that from Table I the Cobaltous diacetate prescription may be best cooperation, existing outstanding anti-corrosion effects and kept good paint adhesion.Yet be noted that if do not consider anticorrosive this factor, Xiao Suangu or nitrous acid cobalt be obtain in the paint adhesion in these cobalt complexing salts best.
Cobaltous diacetate is most preferred solvable divalent cobalt.Other water soluble cobaltous salt is as Co (NO 3) 2CoSO 4, CoCl 2, CoPO 4, CoCO 3Can replace Cobaltous diacetate, but not be preferred, reason sees Table I.Preferred these cobalt salts react with the solubility carboxylic metallic salt with 1-5 carbon atom, though the acetic acid metal-salt is most preferred.The carboxylate salt of Ca, Mg and Na is preferred, and wherein the carboxylate salt of Na is best, and Zn, Li, K and Mn also can use.The restriction of other carboxylate salt of use except that acetate is the solubleness in water.The example of other carboxylate salt that can work has Sodium Propionate.For producing the required minimum solubleness of an effective coating is that every premium on currency contains 0.01 mole of divalent cobalt approximately under 20 ℃ (68 °F).This salt concn all can be utilized up to its solubility limit.
Though failed call can as discussed abovely add fluorine-containing wetting agent in bath.When having used these wetting agents, resulting conversion coating does not need for showing that satisfied erosion resistance carries out traditional sealing process.
Allied compound concentration, used dissolving divalent cobalt concentration can be by every liter of about 0.01 mole of solubility limit up to used divalent cobalt under 20 ℃ (68) of last solution.The preferred concentration of used divalent cobalt can by every liter of last solution about 0.04 mole up to 0.15 mole of every liter of last solution.
The concentration of trivalent cobalt hexacarboxylic acid root co-ordination complex can be by every liter of about 0.01 mole of solubility limit up to used trivalent cobalt hexacarboxylic acid root co-ordination complex of last solution.The preferred concentration of trivalent cobalt hexacarboxylic acid root co-ordination complex can by every liter of last solution about 0.04 mole up to 0.15 mole of every liter of last solution.
The concentration of dissolved carboxylic metallic salt (preferably acetic acid metal-salt) can be by about 0.03 to 2.5 mole of every liter of last solution, the preferred concentration of used dissolved carboxylic metallic salt can by every liter of last solution about 0.05 mole up to 0.2 mole of every liter of last solution.
If you are using, the concentration of fluorine-containing wetting agent should be able to make the surface tension of solution remain between 20 ℃ of following 0.03-0.04N/m (every centimetre of 30-40 dyne).Metal fluoride, MgF 2And CaF 2Concentration can be 0 to solubility limit.This can be understood as fluorine-containing wetting agent, and metal fluoride or their mixture might not need, but preferred, can be every liter of last solution 2-4 gram as add-on.If without wetting agent and metal fluoride, then conversion coating must carry out encapsulation process to reach high corrosion resistance.Use wetting agent and fluorochemical, just can save sealing process, thereby make the present invention more economical.
Body lotion pH value can be by about 5.0 to 9.0, and 6.0-7.5 is preferred, and 6.5 the bests.Bath temperature can be by about 68 °F to 160 °F.Surpass 160 °F, then trivalent cobalt hexacarboxylic acid root complex compound will decompose gradually.Optimum temperature is 140 ± 5 °F.Dipping time can be by about 3 minutes to 60 minutes, and reasonable is from 5 minutes to 30 minutes.When using sodium-acetate, dipping time can foreshorten to 5 to 8 minutes.Use these parameters, will make coat weight range is 20-240 milligram/foot 2
Preferred body lotion preparation order
For the cobalt liquor of acetate complexing, following body lotion preparation is preferred in proper order:
1. stainless steel tank that is equipped with pneumatic blending and Temperature-controlled appliance.Temperature-controlled appliance can be controlled at temperature ± 5 °F within.(stainless steel tank liner have can anti-150 operate continuouslys inert material).
2. this groove is full of 3/4 with deionized water, and is heated to 120 °F, open pneumatic blending and roll to reach demulcent.
3. the acetic acid metal-salt with institute's consumption adds and dissolving.For larger slot, need be with a fine-structure mesh basket as fixing apparatus to help the dissolving of material.
4. the cobalt salt with institute's consumption adds and dissolving, keeps groove solution demulcent air again and rolls 4 hours, reacts major part therebetween and finishes.An also available set basket is to help dissolving.
5. now solution is heated to 140 °F, a small amount of fluorine-containing wetting agent that adding will be used.Kept pneumatic blending again 2 hours.Then groove is prepared to be used for operation.
Preferred whole processing sequence
Preferred whole processing sequence can be summarized as follows:
1. give purification
2. shelter and shelve
3. alkaline purification
4. rinsing under the room temperature
5. deoxidation
6. rinsing under the room temperature
7. form the oxygenate conversion coating
8. rinsing under the room temperature
9. dry.
After all finishings and completing, just should carry out the cobalt conversion coating and apply.The part of possible trapping solution should not flood alkaline purification or the dipping deoxidation, before carrying out the cobalt conversion processing, should purify by hand with manual deoxidation to obtain the not having water crack surface.No water crack surface is that the surface can keep continuous moisture film at least 30 seconds after temperature is lower than under 100 °F in water purification the dipping rinsing and crosses or spray.
Thoroughly rinsing and draining are necessary in whole processing, because each solution should remove fully, to avoid interference the work of next solution in the operation.The processing of part is answered a step can not delay with connecing a step and part is become dry.Handle wet part if desired, should put on clean emgloves.Behind conversion coating, only contact dried part with clean hand-knitted gloves.The system of processing of clamping part for needs is for suitable machinery supports that required point of contact number and size should keep minimum.
Give purification
Can carry out vapour degreasing according to Boeing Process SpecificationBAC5408.If part has grease, can carry out emulsion by BoeingProcess Specification BAC 5763 and purify, or carry out cleaning by solvent by Boeing Process Specification BAC5750.The part of the band opening composition surface of possible trapping solution or band spot weld after giving purification, should be immersed in cold water (or in hot and cold water) 2 minutes.
Shelter and shelve
Do not need the area applications protective layer of cobalt conversion coating to be sheltered.Insert of different metal (dechromisation, nickel or cobalt-base alloy or outer applying metal plate, corrosion-resistant steel CRES or titanium outer) and the plasma flame inlet zone that scribbles non-aluminium should be sheltered.Then part is contained in fixedly in the basket or is installed in the fixed sturcture.
Alkaline purification
Alkaline purification and rinsing should be undertaken by Boeing Process SpecificationBAC 5749 methods, remove outside the part with opening composition surface or spot weld.Under latter instance, rinsing should be under agitation at least 10 minutes, and repeatedly flood (minimum four times), and manual as requested then flushing is to prevent trapping solution.
Deoxidation
Deoxidation and rinsing should be undertaken by Boeing Process Specifica-tion BAC 5765, but except the part of possibility trapping solution.The method rinsing of discussing during the latter uses superincumbent " alkaline purification ".Foundry goods is with the deoxidation of one of following method:
(a) press Boeing Process SpecificationBAC 5765 Solution 37,38 or 39 and carry out deoxidation
(b) dry grinding air blast cast iron is pressed Boeing ProcessSpecification BAC 5748, Type II, Class1 method and rinsing.
Concrete within the scope of the present invention solution formula is listed in Table II.
The preferred solution formula of Table II
Composition Every liter of composition Span of control
Cobaltous diacetate Co (C 2H 3O 2) 2·4H 2O magnesium acetate Mg (C 2H 3O 2) 2·4H 2O or calcium acetate Ca (C 2H 3O 2) 2·H 2O or sodium-acetate Na (C 2H 3O 2)·H 2O alkyl fluoride RF (MSP-ST) magnesium fluoride MgF 2Or Calcium Fluoride (Fluorspan) CaF 2The service temperature dipping time 33.0 restrain 100 °F of compositions of 85.0 gram 70.0 grams, 125.0 gram 4-5 milliliter 2 grams, 2 grams 30-35 gram 80-90 gram 65-75 gram 120-130 restrains 5-20 minute (Dichlorodiphenyl Acetate sodium is 5-8 minute) of 135-145 °F of operation of 2/ 1-3 gram 1-3 gram
1The coating that forms with this technology does not need sealing with anticorrosive.
2Keep solution surface tension between 0.03-0.04N/m (every centimetre of 30-40 dyne).
Bathing temperature variation and dipping time also has contribution to anticorrosive and paint adhesion performance, but selects compared with the solution reaction thing, and degree is much smaller.Now definite, the variation of bathing gentle dipping time all mainly influences coat-thickness, and reactant mainly influences coating structure and density.Be observed general property influence below:
1. from corrosion and adherent viewpoint, optimum bath temperature is 140 °F ± 5 °F.
2. bathe than optimum warm when high, the thicker and pine of coating then, thus paint adhesion power is reduced and erosion resistance increases.
3. when bathing warm hanging down than optimum, coating is thinner, and to the bounding force increase of paint, and erosion resistance reduces.
4. the optimum time is different with the selection of reactant.
5. to the cobalt salt of nitrite anions complexing, under optimum bath temperature, optimum dipping time is 20-25 minute.
6. the cobalt salt of Dichlorodiphenyl Acetate root complexing, optimum dipping time is with different variation of type of used acetate, promptly
To Na (C 2H 3O 2) @140 of 5-8 Fen Zhong
To Mg (C 2H 3O 2) 2@140 of 15-20 Fen Zhong
To Ca (C 2H 3O 2) 2@140 of 12-15 Fen Zhong
Fig. 5 has described the general behavior about the cobalt conversion coating of erosion resistance and paint adhesion.On behalf of two opposite performances (corrosion and bonding), the intersection point of corrosion and bonding curve all be in optimum body lotion parameter mutually.
Preferably the pH value is between 6.0 and 7.5, although will produce coating between pH5.0 and 9.0.Solution may need to be adjusted to this pH value behind life-time service.
Erosion resistance
As implied above, utilize the basic corrosion resistance of complexing cobalt salt, broad research the Cobaltous diacetate prescription.With sodium-acetate Na (C 2H 3O 2) 3H 2O or magnesium acetate Mg (C 2H 3O 2) 24H 2O and Cobaltous diacetate complexing.The result shows that these prescriptions have outstanding resistance to corrosion and do not need later sealing process.Carried out salt spray corrosion test by ASTMB 117 methods, all samples all are subjected to 168 hours exposing to the open air.The results are shown in Table III and Table IV.Test conditions is multiple again answers twice, and the result of acquisition approaches Table III and IV.These data, basic paint adhesion data and other solution being kept the analysis generation optimal slot composition and the span of control of parameter lists in the Table II.This work has been answered about corrosive nature and irised last problem.This research is clear and definite, why sodium-acetate Na (C 2H 3O 2) 3H 2O is selected as optimum complexing agent, rather than magnesium acetate Mg (C 2H 3O 2) 24H 2O.Reason is that sodium-acetate gives aluminum matrix with many slightly corrosive effects.This is very harmful to corrosive nature.Yet, when sodium-acetate cooperates with wetting agent and metal fluoride chemistry, just have advantage clearly; The bright iris and don't the infringement corrosion resistance that have kept coating.On the other hand, when magnesium acetate or calcium acetate used together with wetting agent and metal fluoride, erosion effect was little, and the color effects of the coating that produces is very weak.
Table III
The salt spray corrosion test of cobalt complex prescription
ASTM B11 7Dipping-nothing the sealing of one step of method
Composition Bathe warm °F Dipping period (minute) The anticorrosive experiment of salt fog (198 hours ASTMB117)
Co(C 2H 3O 2)·6H 2O knows Na (C 2H 3O 2)·3H 2The O complexing adds MgF 2And alkyl fluoride RF (MSP-ST) 120 120 120 120 5 10 15 20 Failure " " edge
140 140 140 140 5 10 15 20 By " " "
150 150 150 150 5 10 15 20 By " (powdery coating) " "
Co(C 2H 3O 2) 2·6H 2O and Mg (C 2H 3O 2) 2·4H 2The O complexing adds MgF 2And alkyl fluoride RF (MSP-ST) 120 120 120 120 5 10 15 20 Failure " " "
140 140 140 140 5 10 15 20 By painted " " " " " "
150 150 150 150 5 10 15 20 By painted " " " " " "
Contrast (ALODINE1200S (nearest chromic salt system) BAC5719 By
Table IV
To BMS10-11 1The paint adhesion test-results of paint system
Composition Bathe temperature Dipping time BMS 10-11 Wet Do
Co(C 2H 3O 2)·6H 2O and Mg (C 2H 3O 2) 2·4H 2O complexing Co (C 2H 3O 2) 2·6H 2O Na(C 2H 3O 2)·3H 2The O complexing 120 120 120 120 20 20 30 30 Type i Lei XingI ﹠II type i Lei XingI ﹠II 10 10 10 9 10 10 10 10
140 140 140 140 20 20 30 30 Type i Lei XingI ﹠II type i Lei XingI ﹠II 10 9 10 9 9 10 10 10
120 120 120 120 10 10 15 15 Type i Lei XingI ﹠II type i Lei XingI ﹠II 10 10 9 9 10 10 10 10
140 140 140 140 10 10 15 15 Type i Lei XingI ﹠II type i Lei XingI ﹠II 10 10 9 9 10 10 9 9
Contrast ALODINE1200S BAC5719OR MIL-C-5541 Type i Lei XingI ﹠II 9 9 10 10
Estimate: 10=is best
1=is the worst
The epoxy resin primer (senior aviation coating) that type i-chromic acid is handled
The Resins, epoxy enamel top layer (senior aviation coating) that Type II-non-chromic acid is handled
1Boeing Material Specification BMS10-11 is a kind of highly cross-linked primer system, and comments the performance requriements of these coatings.
Oxide coating is analyzed
Use-Perkin-Elmer Model 550 surface analyzers and Auger oxide profile use same machine (with different operator schemes) to carry out the ESCA surface analysis, so that identify cobalt conversion coating of the present invention.(ESCA=is used for chemico-analytic electronic spectrum (be also referred to as XPS, or x-ray photoelectron spectroscopy)).These analysis revealeds, the cobalt conversion coating is made up of hopcalite, i.e. aluminium oxide Al 2O 3Account for maximum volume percentage ratio, and oxide compound CoO, the Co of cobalt 3O 4And Co 2O 3" maximum volume percentage ratio " is meant, the volume of this oxide compound surpasses any other oxide compound volume that exists, but " maximum volume percentage ratio " might not refer to that the volume of this oxide compound is higher than 50% volume.
Data show that further in the bottom of oxide coating (promptly adjacent to aluminum matrix), that account for maximum volume percentage ratio is Al 2O 3The middle portion of oxide coating is CoO, Co 2O 3, Co 3O 4And Al 2O 3Mixture.Data show that also that account for maximum volume percentage ratio in the top of oxide coating is Co 2O 3And Co 3O 4Mixture.
Cobalt conversion coating additional features of the present invention can Fig. 1 to Fig. 4 and above Fig. 1 is found in the description of Fig. 4.Fig. 1 shows the cobalt conversion coating 410 and 420 that formed in 15 minutes by dipping in a typical cobalt conversion coating solution to Fig. 4.The upper face of this cobalt conversion coating, resembles sponge, thereby sizable surface-area and vesicularity is provided to shown in Figure 4 as Fig. 1 very much, helps paint adhesion.Under upper face, coating is than comparatively dense and solid (non-porous).
Other application process
Above-mentioned dispensing information apply the cobalt conversion coating of generation by dipping.Same principle also can be by applying and spray the generation conversion coating by hand.
Concerning the people who is familiar with technology of the present invention, it is evident that the present invention can remove above-mentioned concrete form enforcement the present invention disclosed, and can not run counter to spirit of the present invention and essence.Therefore, the specific details of above-mentioned specific embodiments of the present invention and described technology should be regarded explanation rather than restriction in all respects as.Scope of the present invention is pointed out in claims, rather than is limited in the example previously discussed.Should comprise any and whole equivalents in the claim.

Claims (30)

1. method that on matrix, forms oxide film cobalt conversion coating, wherein said matrix is aluminum or aluminum alloy, this method may further comprise the steps:
(a) provide the cobalt of the formation oxide film that comprises a reacting solution to transform solution, this reacting solution contains soluble cobaltic hexa-atomic complex compound, and this complex compound is with Me m[Co (R) 6] nForm exists, and Me is for being selected among Na, Li, K, Ca, Zn, Mg and the Mn one or more, and m is 2 or 3 in the formula, and n is 1 or 2, and R is the carboxylate radical with 1-5 C atom, and the concentration of this complex compound is from 0.01 mole of saturation concentration limit to this complex compound of every liter of solution;
(b) make above-mentioned matrix carry out enough contact for a long time with above-mentioned reacting solution and make described stromal surface oxidation, thereby form above-mentioned oxide film cobalt conversion coating, the pH of wherein said reacting solution is 5.0-9.0.
2. the process of claim 1 wherein that by producing surface tension of liquid be that the required consumption of 0.03-0.04N/m adds water-soluble alkyl fluoride RF or fluorocarbon wetting agent in described reacting solution.
3. claim 1 or 2 method, wherein R is an acetate.
4. claim 1 or 2 method, the concentration of the hexa-atomic complex compound of wherein above-mentioned solvable trivalent cobalt from 0.04 mole of every liter of solution up to 0.15 mole of every liter of solution.
5. according to the method for claim 1 or 2, wherein said cobalt transforms solution by making the solubility carboxylic metallic salt prepared in reaction of a solvable divalent cobalt and 1-5 carbon atom.
6. according to the method for claim 5, the concentration of wherein said solvable divalent cobalt is 0.04 mole to 0.15 mole of every liter of final solution, and the concentration of carboxylic metallic salt is 0.03 to 2.5 mole of every liter of final solution.
7. the method for claim 5, wherein, above-mentioned solvable divalent cobalt be a kind of 20 ℃ down in every premium on currency minimum solubleness be 0.01 mole divalent cobalt.
8. the method for claim 5, wherein, above-mentioned solvable divalent cobalt is a Cobaltous diacetate.
9. the method for claim 5, wherein, above-mentioned cobalt transforms solution and prepares by a kind of body lotion preparation process, comprising:
(a) the above-mentioned carboxylic metallic salt of dissolving; With
(b) add above-mentioned solvable divalent cobalt then.
10. the process of claim 1 wherein that the temperature that above-mentioned cobalt transforms solution is 20-71.7 ℃.
11. the process of claim 1 wherein that above-mentioned matrix transforms 3 minutes to 60 minutes duration of contact of solution with above-mentioned cobalt.
12. the process of claim 1 wherein that above-mentioned cobalt transforms and adds fluorine-containing wetting agent in the solution, to promote on above-mentioned matrix, forming above-mentioned cobalt conversion coating.
13. the method for claim 12, wherein, above-mentioned wetting agent is selected from water-soluble alkyl fluoride RF, fluorocarbon, CaF 2, MgF 2Or their mixture.
14. the method for claim 12, wherein, the consumption of described wetting agent is that 0.03-0.04N/m institute expense is added by producing 20 ℃ of surface tension of liquids.
15. the method for claim 12, wherein, MgF 2, CaF 2Or their mixture is added in the above-mentioned solution, and add-on is every liter of last solution 2-4 gram.
16. be used for producing on metal matrix the chemical conversion coating solution of oxide film cobalt conversion coating, this solution comprises a kind of reacting solution that contains the cobaltic hexa-atomic complex compound of solubility, the hexa-atomic complex compound of this solvable trivalent cobalt is with Me m[Co (R) 6] nForm exists, Me is for being selected among Na, Li, K, Ca, Zn, Mg and the Mn one or more, m is 2 or 3 in the formula, n is 1 or 2, R is the carboxylate radical with 1-5 C atom, the concentration of the hexa-atomic complex compound of this solvable trivalent cobalt is 0.01 mole of saturation concentration limit to the hexa-atomic complex compound of this solvable trivalent cobalt of every liter of solution, and the pH of described reacting solution is 5.0-9.0.
17. the solution of claim 16, wherein R is an acetate.
18. solution according to claim 16, the hexa-atomic complex compound of wherein said solubility trivalent cobalt is a solubility trivalent cobalt carboxylate complexes, by making solvable divalent cobalt and the solubility carboxylic metallic salt prepared in reaction of 1-5 carbon atom arranged, metal M e wherein such as claim 16 definition.
19. according to the solution of claim 18, the concentration of wherein said solvable divalent cobalt is 0.01 mole of saturation concentration limit to used solvable divalent cobalt of every liter of final solution, the concentration of carboxylic metallic salt is 0.03 to 2.5 mole of every liter of final solution.
20. the solution of claim 18, wherein, above-mentioned solvable divalent cobalt be a kind of 20 ℃ down minimum solubleness be 0.01 mole divalent cobalt in every premium on currency.
21. the solution of claim 18, wherein, solvable divalent cobalt is a Cobaltous diacetate.
22. the solution of claim 18, wherein, above-mentioned carboxylic metallic salt is the acetic acid metal-salt.
23. the solution of claim 18, wherein, above-mentioned cobalt transforms solution by the preparation of body lotion preparation process, comprising:
(a) the above-mentioned carboxylic metallic salt of dissolving; With
(b) add above-mentioned solvable divalent cobalt then.
24. the solution of claim 16 is included in above-mentioned cobalt and transforms the fluorine-containing wetting agent that adds in the solution, to promote forming above-mentioned cobalt conversion coating on above-mentioned matrix.
25. the solution of claim 24, wherein, above-mentioned wetting agent is selected from water-soluble alkyl fluoride RF, fluorocarbon, CaF 2, MgF 2Or their mixture.
26. the solution of claim 24, wherein, the consumption of described wetting agent is that the required amount of 0.03-0.04N/m adds by producing 20 ℃ of surface tension of liquids.
27. the solution of claim 24, wherein, MgF 2, CaF 2Or their mixture is added in the above-mentioned solution, and add-on is every liter of last solution 2-4 gram.
28. the solution of claim 16 is used to prepare the purposes of the oxide film cobalt conversion coating on metal matrix.
29. the solution of claim 16 is used to prepare the purposes of the oxide film cobalt conversion coating on metal matrix, wherein, the temperature of above-mentioned solution is 20 ℃-71.7 ℃.
30. the solution of claim 16 is used to prepare the purposes of the oxide film cobalt conversion coating on metal matrix, wherein said matrix is aluminium, aluminium alloy, magnesium, magnesium alloy, cadmium plating matrix or zinc-plated-Ni-based matter.
CNB931075831A 1992-06-25 1993-06-25 Non-chromated oxide coating for aluminum substrates Expired - Fee Related CN1195893C (en)

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WO1996021753A1 (en) * 1995-01-13 1996-07-18 Henkel Corporation Composition and process for forming a solid adherent protective coating on metal surfaces
ZA962178B (en) * 1995-03-22 1996-07-29 Henkel Corp Compositions and processes for forming a solid adherent protective coating on metal surfaces
FR2752851B1 (en) * 1996-09-02 1998-11-13 Cfpi Ind BATH AND METHOD FOR PHOSPHATION OF METAL SUBSTRATES, CONCENTRATE FOR THE PREPARATION OF THIS BATH AND METAL SUBSTRATES TREATED WITH THE BATH AND METHOD
US5873953A (en) * 1996-12-26 1999-02-23 The Boeing Company Non-chromated oxide coating for aluminum substrates
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AU2002361689A1 (en) 2002-01-04 2003-07-30 University Of Dayton Non-toxic corrosion protection pigments based on cobalt
US7235142B2 (en) 2002-01-04 2007-06-26 University Of Dayton Non-toxic corrosion-protection rinses and seals based on cobalt
US7294211B2 (en) 2002-01-04 2007-11-13 University Of Dayton Non-toxic corrosion-protection conversion coats based on cobalt
FR2856079B1 (en) * 2003-06-11 2006-07-14 Pechiney Rhenalu SURFACE TREATMENT METHOD FOR ALUMINUM ALLOY TILES AND BANDS
CN1309864C (en) * 2004-09-29 2007-04-11 广州擎天油漆化工实业有限公司 Environmental protective process for forming transforming film on aluminium and aluminium alloy surface
CN100372972C (en) * 2005-11-03 2008-03-05 复旦大学 Method of growing metal organic compound on solid surface
CN103184445A (en) * 2011-12-28 2013-07-03 上海航天精密机械研究所 Chemical oxidation solution composition for aluminium-alloy surface and chemical oxidation process
CN103266315B (en) * 2013-05-31 2015-05-13 海安县申菱电器制造有限公司 Preparation of aluminum alloy cobalt salt chemical conversion coating treating fluid
CN103266314B (en) * 2013-05-31 2015-05-13 海安县申菱电器制造有限公司 Method for treating aluminum alloy cobalt salt chemical conversion coating
CN104846309A (en) * 2015-05-09 2015-08-19 安徽鼎恒再制造产业技术研究院有限公司 High-strength Co3O4-SiC coating materials and preparation method thereof
CN106868495B (en) * 2017-01-23 2019-06-11 江苏理工学院 A kind of recycling and reusing method of cobalt salt chemical oxidation waste liquid
CN112533756A (en) * 2018-06-28 2021-03-19 尼蓝宝股份有限公司 Simultaneous surface modification and method for producing the same

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