CN1090338A - The non-chromate oxide membranous layer of aluminum substrate - Google Patents

The non-chromate oxide membranous layer of aluminum substrate Download PDF

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CN1090338A
CN1090338A CN93101737A CN93101737A CN1090338A CN 1090338 A CN1090338 A CN 1090338A CN 93101737 A CN93101737 A CN 93101737A CN 93101737 A CN93101737 A CN 93101737A CN 1090338 A CN1090338 A CN 1090338A
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cobalt
solution
rete
iii
salt
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CN1138873C (en
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M·P·施里弗
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Boeing Co
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Boeing Co
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Priority claimed from US07/903,853 external-priority patent/US5411606A/en
Application filed by Boeing Co filed Critical Boeing Co
Priority to CNB931017378A priority Critical patent/CN1138873C/en
Priority to MX9303745A priority patent/MX9303745A/en
Priority to EP93914728A priority patent/EP0646187B1/en
Priority to DK93914728T priority patent/DK0646187T3/en
Priority to ES93914728T priority patent/ES2152950T3/en
Priority to CA002138790A priority patent/CA2138790C/en
Priority to RU94046218A priority patent/RU2135637C1/en
Priority to AU45008/93A priority patent/AU687740B2/en
Priority to SG1996004772A priority patent/SG43169A1/en
Priority to JP50204994A priority patent/JP3345010B2/en
Priority to BR9306602A priority patent/BR9306602A/en
Priority to DE69329853T priority patent/DE69329853T2/en
Priority to PCT/EP1993/001630 priority patent/WO1994000619A1/en
Priority to AT93914728T priority patent/ATE198631T1/en
Priority to NZ253699A priority patent/NZ253699A/en
Priority to ZA934544A priority patent/ZA934544B/en
Priority to CNB931075831A priority patent/CN1195893C/en
Publication of CN1090338A publication Critical patent/CN1090338A/en
Priority to NO19945026A priority patent/NO315522B1/en
Priority to GR20010400395T priority patent/GR3035554T3/en
Publication of CN1138873C publication Critical patent/CN1138873C/en
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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

The present invention relates to a kind ofly can form solution that cobalt chemical oxidation rete uses on the metallic matrix, on metallic matrix, form the method that cobalt transforms rete with this solution, with the goods that make with this method.The present invention is intended to substitute existing chromic acid chemical oxidation process, to satisfy strict day by day legislations of environmental protection.Solution of the present invention is a kind of aqueous solution, wherein contains cobalt (III) hexa-valent complex of 0.01mol/l to saturation limit; Also contain acetate.This solution in use, temperature is 20-72 ℃, pH is 5.0-9.0, the time that contacts with matrix is 3-60 minutes.Gained cobalt of the present invention transforms rete and has good corrosion resistance and paint tackiness.

Description

The non-chromate oxide membranous layer of aluminum substrate
The field that the invention belongs to formation chemical conversion rete on metallic matrix such as aluminum substrate of environment protection level.More particularly, one aspect of the present invention is a kind of new oxide rete (inventor is referred to as " cobalt conversion rete ") that chemically forms on metallic matrix.The present invention has improved the human environment quality because of the quality that has kept empty G﹠W.
Generally speaking, the chemical conversion rete chemically changes into all or part of rete of being made up of the oxidation state of matrix metal of combining closely with the metallic surface and forms.The chemical conversion rete can provide high anti-corrosion and the strong tackiness to painting.Industrial to washing paint (organic coating), generally all require to adopt the chemical conversion rete, especially when performance requriements is high, all the more so.
Although aluminium prevents self corrosion because of forming the natural oxidation rete, this kind protection is not thorough.Under the situation that has moisture and ionogen to exist, aluminium alloy, especially 2000 serial high X alloy such as 2024-T3 corrode more fasterly than fine aluminium.
In general, handle aluminium and two classes are arranged with the processing method that forms useful conversion film layer.The first kind is an anonizing, wherein the aluminum component is dipped in the chemical electrolysis liquid, for example: be dipped in chromic acid or the sulfuric acid electrolyte, and aluminum component and chemical electrolysis liquid are passed to electric current.The conversion rete that produces on the aluminum component surface provides to have corrosion resisting property and organic coating is had fusible surface.
Second class methods are chemically to form one deck to transform rete, are referred to as the chemical conversion rete usually, and this method is to make the aluminum component be subjected to the effect of certain chemical solution such as chromic acid solution, but does not pass to electric current in treating processes.Described chemical solution can impregnation method, and manual painting way or spray mode are used.The conversion rete that produces on the aluminum component surface, providing has corrosion resisting property and to the surface that bounding force is arranged of organic coating.The present invention relates to second class methods of this kind generation chemical conversion rete.Described chemical solution can impregnation method, and all kinds of manual methods of application or spray mode are used.
The 2nd of people such as Ostrander, 796, the 2nd of people such as No. 370 United States Patent (USP)s and Ostrander, 796, in the different embodiments of No. 371 United States Patent (USP)s, in military specification sheets MIL-C-5541,, recorded and narrated the processing method that forms the chemical conversion rete on a kind of widely used aluminum substrate with chromic acid with in Boeing instruction for process BAC 5719.These chromic acid chemical conversion solutions contain sexavalent chrome, fluorochemical, and prussiate.All these components all exist significant environment protection, so that the problem of health and safety aspect.The component of chromic acid conversion fluid commonly used such as ALODINE 1200 is as follows: CrO 3-" chromic acid " (sexavalent chrome); The NaF-Sodium Fluoride; KBF 4-potassium tetrafluoroborate; K 2ZrF 6-Potassium Zirconium Fluoride; K 3Fe(CN) 6-the Tripotassium iron hexacyanide; And HNO 3-nitric acid (control PH uses).
The many constructed of aluminium spares that spread all over aircraft and space industry are so that cadmium plating, zinc-plated, zinc-plated-nickel and steel components also all use this chromic acid processing method to handle at present.When the chromic acid conversion film forms, can reach 168 hours solidity to corrosion standard on aluminum substrate, but they are mainly as the surperficial substrate in conjunction with paint.Because they are quite thin, and the little (40-150mg/ft of rete weight 2), so transforming rete, chromic acid do not cause that descend to the fatigue lifetime in the constructed of aluminium.
Yet in the U.S., especially California, and other national pollution regulation reduces chromic permission discharging content in waste water, waste gas and the discharge of metal surface treatment process just sharp.So, adopt the chemical conversion technology of hexavalent chromium compound to be replaced.The present invention does not adopt hexavalent chromium compound, and it is intended to replace the previous used chromic acid technology that forms the conversion rete on aluminum substrate.
On the one hand, the present invention relates to a kind of cobalt conversion rete that forms on metallic matrix makes matrix have processing method anti-corrosion and adhesion paint property.The present invention is that development replaces existing chromic acid technology.The step that technology of the present invention comprises is: a kind of cobalt conversion fluid (a) is provided, and this liquid is a kind of certain solubility cobalt (III) sexavalence coordination compound (content is the saturation limit of every liter of about 0.01mol of solution to this cobalt (III) hexa-valent complex) and acetate (CH of containing 3COOH) the aqueous solution; (b) make matrix contact the enough time, to form the cobalt conversion film with above-mentioned solution.Described matrix can be aluminum or aluminum alloy, also can be the matrix and the steel of cadmium plating, zinc-plated, zinc-nickel alloy.Described cobalt (III) hexa-valent complex is with [Co(NH 3) 6] X 3Form exist, wherein X is Cl, Br, NO 3, CN, SCN, PO 4, SO 4, C 2H 3O 2, perhaps CO 3
On the other hand, the present invention relates to produce on the metallic matrix cobalt and transform the chemical conversion coating solution that rete is used.This solution is a kind of hexa-valent complex (its concentration is the saturation limit of about 0.01mol/L to the hexa-valent complex of this cobalt (III)) and acetate (CH that contains certain solubility cobalt (III) 3COOH) the aqueous solution.Described cobalt conversion fluid can prepare smoothly by the solution preparation that comprises the following steps: (a) dissolve a kind of cobalt (II) salt; (b) dissolve a kind of metal nitrate such as Mg(NO then 3) 26H 2O, Ca(NO 3) 26H 2O, NaNO 3, KNO 3Perhaps LiNO 3; And (c) add the acetate ammonium salt again.
On the one hand, the present invention relates to a kind of plated film goods with solidity to corrosion and paint adhesion again, these goods comprise: (a) a kind of metallic matrix; And one deck cobalt that (b) on matrix, forms conversion rete, described cobalt transforms rete and comprises aluminium oxide Al 2O 3Oxide compound CoO, the Co of (accounting for maximum volume per-cent) and cobalt 3O 4And Co 2O 3
Each accompanying drawing in this specification sheets is the Photomicrograph that rete produces image in the aluminium alloy test piece with scanning electron microscope.Fig. 1-the 8th is covered with by the present invention and is prepared into the micro-photograph (scanning electron microscope of operating) that cobalt transforms the aluminium alloy 2024-T3 test piece of rete under 30KV.Fig. 1 and Fig. 2 show that the cobalt that dipping formed in 25 minutes in the typical cobalt conversion film liquid under 140 transforms rete 310.Fig. 3 and Fig. 4 show that the cobalt that dipping formed in 15 minutes in the typical cobalt conversion film liquid under 140 transforms rete 320.Fig. 5-8 shows that the cobalt that dipping formed in 20 minutes in the typical cobalt conversion film under 140 transforms rete 330.Rete 310,320 and 330 seems there is no remarkable difference.
Fig. 1 is that 10,000 of test piece shows little photo, and photo shows that bright cobalt of the present invention transforms rete 310.This Photomicrograph is the elevation angle top view of the upper face of oxide membranous layer 310.The end face porous crack of oxide film 310 looks like one deck fried flour.This sample has flooded 25 minutes in cobalt conversion film solution.White ribbon is the length mark of 1 μ m.Round thing shown in the label 312 is a undetermined impurity on the oxide film laminar surface.
Fig. 2 is that 50,000 of test piece shown in Figure 1 shows little photo.This Photomicrograph is the elevation angle top view of the upper face of oxide membranous layer 310.Fig. 2 is the close-up view of small area under bigger magnification of sample.White ribbon is the length of 1 μ m.
Fig. 3 is that 10,000 of another test piece shows little photo, and this photo illustrates the elevation angle side-view that cobalt of the present invention transforms rete 320 fracture transverse section.The fracture transverse section of the aluminum substrate of test piece is indicated by label 322.This test piece has been flooded 15 minutes in cobalt conversion film solution.For taking this Photomicrograph, test piece is bent to fracture to expose the cross section of oxide membranous layer 320.White ribbon is the length of 1 μ m.
Fig. 4 be among Fig. 3 used sample 50,000 show little photo, this photo shows the elevation angle side-view of bright cobalt conversion film fault rupture cross section of the present invention.Fig. 4 is the close-up view under the high-amplification-factor more on the small area of sample.The aluminum substrate of sample is marked by label 322.White ribbon is the length of 1 μ m.
Fig. 5 is that 10,000 of another sample shows little photo, and this photo shows that bright another kind of cobalt of the present invention transforms rete 330.This Photomicrograph is the elevation angle top view on oxide membranous layer 330 upper faces.The end face porous crack of oxide membranous layer 330 looks like one deck fried flour.This sample has flooded 20 minutes in cobalt conversion film solution.White ribbon is the length of 1 μ m.Circle thing 332 is oxide membranous layer 330 lip-deep uncertain impurity.
Fig. 6 be among Fig. 5 used test piece 50,000 show little photo.This Photomicrograph is the elevation angle top view of the upper face of oxide membranous layer 330.Fig. 6 is the close-up view of high-amplification-factor more on the small area of sample.White ribbon is the length of 1 μ m.
Fig. 7 is that 10,000 of another test piece shows little photo, and this photo shows that bright cobalt of the present invention transforms the elevation angle side-view in rete 330 fracture transverse section.The aluminum substrate of this test piece is indicated by label 332.This test piece has been flooded in coating liquid 20 minutes.For taking this Photomicrograph, test piece is bent to disconnection to expose the transverse section of oxide membranous layer 330.White ribbon is the length of 1 μ m.
Fig. 8 be among Fig. 7 used test piece 50,000 show little photo, this photo shows the elevation angle side-view in bright cobalt conversion film fault rupture of the present invention transverse section.Fig. 8 is the close-up view than high-amplification-factor on the small area of this test piece.The aluminum substrate of test piece is marked by label 332.White ribbon is the length of 1 μ m.
I have invented two class cobalts and have transformed rete.The first kind is that the cobalt by the oxide structure of closed state not transforms rete and constitutes, and is applicable to the use occasion that paint adhesion power is particularly important.Second class is that a kind of cobalt of the oxide structure by closed state transforms rete and constitutes, and it is applicable to the use occasion that requires the bare metal corrosion resisting property.
To achieve the object of the present invention.Carried out a large amount of experimental study work.Various multivalent compounds is studied, or used these compounds separately, or they are used with alkali, acid or fluorochemical.Vanadate, molybdate, cerate, ferrate and various borate are arranged in these compounds.Although on alloy matrix aluminum, made the film settled layer of the compound that contains these elements, there is not a kind of rete that suitable Corrosion Protection can be provided, or the paint clinging power.
But, be immersed in the simple cobalt-II (Co that is heated to 180 when aluminum substrate 2+) in the salt brine solution, but observe Corrosion Protection and significantly improve.This has caused many cobalts-II Co 2+And cobalt-III (Co 3+) reaction research, especially to await the reply the application No07/525,800(1990 applied for May 17) described in repercussion study.
In that invention, air is flow through in a kind of following aqueous solution several hours, this solution contains cobalt (II) salt such as CoX 2(wherein X=Cl, Br, NO 3, CN, SCN, PO 4, SO 4, C 2H 3O 2, CO 3) with corresponding ammonium salt NH 4X, the hexa-valent complex of formation six cobaltammines (III) in the presence of ammonium hydroxide (ammoniacal liquor).For example:
Above-mentioned reaction expression (1) is at the application No.07/525 that just awaits the reply of May 17 nineteen ninety application, given detailed record in 800.Use ammonium hydroxide (ammoniacal liquor) to produce the trivalent amine complex.Since this application since day, further research is when with ammonium acetate (CH 3COONH 4) when replacing ammonium hydroxide, six hydrogen close cobalt (III) title complex can produce significant technology superiority, is:
X=Cl, Br, NO in the formula 3, CN, SCN, PO 4, SO 4, C 2H 3O 2, CO 3
System did not need to carry out continually PH and regulates during this acetate was slow, and not resembling in the ammonium hydroxide system must interpolation NH because the ammoniacal liquor velocity of evaporation is high 4OH.In addition, acetate buffered cobalt amine complex solution is preferably in PH6.0 to 7.0 scope and uses.The oxide membranous layer that is generated more increases in paint film clinging power and solidity to corrosion direction ratio ammonium hydroxide system.The weight of oxide membranous layer can obtain 20 easily to 240mg/ft 2To produce the angle of suitability, not having the ammonia flavor fully is another obvious advantage.Be to be noted that X-reagent cited in reaction equation (2) all successfully through overtesting, on aluminum substrate, all produce and effectively transform rete.Yet nitrate all produces optimum to the performance and the outward appearance of rete.From the viewpoint of environmental protection, prussiate and thiocyanate-and inadvisable usefulness.
An importance of cobalt chemical reaction is: cobalt-II title complex has and is oxidized to cobalt-III title complex tendency by force, that is:
Find that when alloy matrix aluminum (for example 2024-T3 alloy) when impregnated in the aqueous solution that contains above-mentioned cobalt-III title complex, then form bright colored rete on aluminium alloy, this rete has splendid corrosion resistance nature.These retes can transform rete with conventional chromic acid and compare favourably aspect lightness of colour.
Above-mentioned cobalt complex is not a novel substance.The main application of cobalt-III title complex is industrial as the oxygenant that improves the chromophotograph sharpness in photographic process.For example, the United States Patent (USP) 4,088,486 of Bissonette has been informed the purposes of photograph aspect of cobalt (III) title complex of ammonia:
Yet amazing is that these six cobaltammine (III) title complexs can form oxide structure on aluminum substrate.The definite reaction mechanism that oxide compound forms at present and imperfectly understand; Although do not wish to be retrained by specific theory, can believe this oxide compound formation and top shown in chemical equation (3) relation is arranged.The oxidation capacity of six cobaltammines (III) title complex can be believed and plays a major role to form viewed oxide film (I am referred to as " cobalt conversion rete ") on aluminum substrate.The instrumental analysis (auger analysis and electron microscope) that rete is carried out has confirmed to have the formation of oxide structure.The Photomicrograph of Fig. 1-8 shown that cobalt of the present invention transforms the outward appearance of rete.
Relevant ammonium salt NH in reaction formula (2) 4X metal nitrate such as Mg(NO 3) 26H 2O, Ca(NO 3) 26H 2O, NaNO 3, KNO 3Or LiNO 3During replacement, can further improve, be the color stability of this oxide membranous layer:
X=Cl, Br, NO in the formula 3, CN, SCN, PO 4, SO 4, C 2H 3O 2, CO 3
Yet preferred reaction is considered to the following reaction that has Xiao Suangu to participate in:
When experimentizing,, there are many parameters very important from best solution chemistry and the even angle that forms of oxide membranous layer with this initial action composition.These parameters are the selection of chemical reaction agent, chemical reaction agent concentration, solution preparation order, PH control, temperature and dipping time.
Select chemical reaction agent
About the selection of reagent, various cobalt salts can be used for the ligand compound of cobalt.Can be used for having among cobalt (II) salt of the aqueous solution: Xiao Suangu Co(NO 3) 26H 2O; Cobalt chloride CoCl6H 2O; Rose vitriol CoSO 4; Cobaltous acetate Co(CH 3COO) 24H 2O, and cobaltous dihydroxycarbonate 2CoCO 3Co(OH) 2H 2O.Above-mentioned every kind of cobalt (II) salt all can with ammonium acetate and a kind of metal nitrate [as Mg(NO 3) 6H 2O, Ca(NO 3) 26H 2O, NaNO 3, KNO 3Or LiNO 3] reaction.
Should also be noted that for aluminium and aluminium alloy the reagent of preferentially selecting usefulness is Co(NO 3) 26H 2O, Mg(NO 3) 26H 2O and CH 3COONH 4, because the cobalt amine complex that forms with nitrate can produce best film performance.
In addition, other cobalt (II) salt also can use as long as have certain minimal solubility in water.Required minimal solubility is the every premium on currency of 0.01mol/ when 20 ℃ (68 °F).
The chemical additive of preferentially selecting usefulness is a kind of oxygenant, preferably hydrogen peroxide H 2O 2The effect of oxygenant is that the cobalt in the solution (II) ion-oxygen is changed into cobalt (III) ion.The airflow that flows in the tank liquor plays a part oxygenant, so for operation, the existence of hydrogen peroxide is not essential.Hydrogen peroxide can improve cobalt in the solution (II) ion-oxygen and change into cobalt (III) ionic speed because solution just can operate in the short time, thereby hydrogen peroxide practical in industry be useful when of the present invention.
Therefore, preferred chemical reaction agent and additive are:
Xiao Suangu CO(NO 3) 26H 2O
Ammonium acetate CH 3COONH 4Also make NH 4C 2H 3O
Magnesium nitrate Mg(NO 3) 26H 2O
Hydrogen peroxide (oxygenant) H 2O 2
Chemical reaction agent concentration, pH value control, temperature and dipping time
Can be about 0.01mol/L(final solution about the concentration after the dissolving of chemical concentrations, used cobalt (II) salt) the saturation limit concentration of used cobalt (II) salt extremely.Preferably, used dissolved cobalt (II) salt concn is about 0.04mol/L(final solution) to the 0.15mol/L(final solution).The concentration of six cobaltammines (III) title complex can be about 0.1mol/L(final solution) to the saturation limit concentration of used six cobaltammines (III) title complex.Preferably, the concentration of six cobaltammines (III) coordination compound can be about 0.04mol/L(final solution) to the 0.15mol/L(final solution).
Dissolved metal nitrate concentration can be about 0.03mol/L to 2.5mol/L of final solution.Preferably, used dissolved metal nitrate concentration can be about 0.05mol/L to 0.2mol/L of final solution.
The concentration of ammonium acetate can be about 0.06-6.0mol/L(final solution).Preferably, the used ammonium acetate of dissolved concentration can be about 0.15-0.7mol/L(final solution); Superstoichiometric ammonium acetate is unharmful.The acetic acid concentration that is produced can be about 0.05-5.0mol/L(final solution).Preferably, the acetic acid concentration that is produced can be about 0.125mol/L to 0.6mol/L of ultimate density.
The pH value of solution can wherein be better with 6.0-7.0, again with 6.5 the bests from about 5.0 to 9.0.The temperature of solution can be from 68 °F to 160 °F; Surpass 160 °F, then six cobaltammines (III) title complex decomposes gradually.Optimum temps is 140 ± 5 °F.Dipping time can be best dipping time with 20 ± 5 minutes wherein from about 3 minutes to 6 minutes.
Preferred solution preparation is in proper order:
1, will be equipped with and add 3/4 68-90 deionized water in the stainless steel liquid bath of pneumatic blending pipe fitting and heating coil.Pneumatic blending begins to produce bubble slowly.(this liquid bath can be equipped with filtration unit, to remove any solid impurity (dust, aluminium mud dregs etc.) in the course of processing.
2, add a certain amount of cobalt (II) salt and (preferably use Co(NO 3) 26H 2O) and fully dissolve.When dissolving, can be used on the cobalt salt that suspends in the stainless steel basket basket water.Cobalt salt is seen the reaction formula (4) of above-listed stoichiometric balance to the optimum mole ratio of ammonium acetate for about 1-6(.The optimum concn of cobalt salt is about 0.077mol/L(final solution).This consumption is that cobalt salt is counted for base the ammonium acetate mol ratio according to can prepare the oxide membranous layer with high paint adhesion performance the time.
3, then, add a certain amount of metal nitrate and (be preferably Mg(NO 3) 26H 2O).The concentration of this additive can add to the 2.5mol/L(final solution from 0), and concerning the maximum colours that transforms rete, optimum quantity is the 0.10mol/L(final solution).
4, at this moment, add ammonium acetate and make it dissolving.When using about 0.077mol/L(final solution) best cobalt salt concentration the time, then the optimum concn of ammonium acetate is about 35.6mg(0.46mol)/the L(final solution).This ammonium acetate concentration obtains the cobalt salt optimum mole ratio of cobalt salt to ammonium acetate about 1 to 6.Keep the pneumatic blending of suitable degree.
5, use deionized water in the liquid bath.Add to the arrival final volume.At room temperature keep pneumatic blending 2-3 hour to solution.Then, add a certain amount of hydrogen peroxide H 2O 2, be preferably (30 volume percent).The about 0.03-0.1mol H of preferable consumption 2O 2[the H of about 3-10ml 2O 2(30% volume percent)] every liter of final solution.
6, solution is kept 2 hours at least again being preferably under 68-90 °F, so that cobalt produces cooperationization reaction (for example above-listed reaction formula (4)), but cobalt (III) title complex to obtain minimum operational ton, this can be indicated by burgundy look to the red-brown of solution.Preferably, under 68-90 °F, solution was kept 8 hours again,, be convenient to implement effectively cobalt conversion film technology to make relatively large cobalt (III) title complex.Then, solution is heated to 140 ± 5 °F, this is an optimum operating temperature.In forming cobalt conversion film technological process, to the pneumatic blending of solution suitable intensity.
What 7, can select to carry out is second stainless steel liquid bath (being used for oxide compound sealing step) to be equipped with pneumatic blending pipe fitting and heating coil, and to add 3/4 deionized water.This follow-up formation cobalt conversion film step is used for improving corrosion resisting property.This liquid bath will not heat when adding required pharmaceutical chemicals.
8, with a certain amount of single nickel salt NiSO 46H 2O and a certain amount of magnesium nitrate Mg(NO 3) 26H 2O adds in the enclosed slot, and makes it dissolving.The preferable consumption of single nickel salt is about 20g(0.076mol)/the L(final solution).The preferable consumption of magnesium nitrate is about 20g(0.078mol)/the L(final solution).When dissolving whenever necessary, stir.
9, then, liquid bath is added to final volume, and be heated to 200 ± 5 °F with deionized water.No longer need to continue to stir.
Preferred overall process order can be summarized as follows:
Obtain the adhesive process sequence schema of maximum paint
When (1) needing, carry out pre-washing
When (2) needing, shelter and shelve
(3) alkali solution cleans and washing
(4) oxide film dissolving and washing
(5) form oxide membranous layer: 140 ± 5 °F; 15-20 minute
(6) dipping washing: 68-140
(7) dry-the highest 140 °F
Obtain maximum corrosion proof processing sequence schema
When (1) needing, carry out pre-washing
When (2) needing, shelter and shelve
(3) alkali solution cleans and washing
(4) oxide film dissolving and washing
(5) form oxide membranous layer: under 140 ± 5 °F: 15-20 minute
(6) dipping washing: 68-140
When (7) needing, seal
(8) under the washing-room temperature, at least 3 minutes
(9) dry-the highest 140 °F
General attention point for above-mentioned schema
Cobalt conversion rete just carries out after should and processing in all finishings and all having finished.To holding back the part of solution, must not carry out cleaning of alkaline solution dipping or the processing of dipping oxide film dissolving; Labor cleaning and manual oxide film dissolving step should be used for before using the cobalt conversion processing, and obtaining moisture film does not have broken surface.Moisture film does not have broken surface and is meant a kind of like this surface, and it is being lower than under 100 the temperature, and behind spray or dipping clean water, this surface keeps successive moisture film to reach for 30 seconds at least.
For fear of the interference to following a kind of treatment solution performance in the process sequence, every kind of treatment solution all must be from handling Ex-all on the workpiece surface, so thorough washing and drip-dry must be carried out in the entire treatment process.Part should not have one step of the ground of pause to be handled with connecing a step, does not allow the part drying.If must be used to contact when wetting part, then need put on clean latex rubber gloves.Form after the conversion film, only worn the fabric gloves of cleaning and could take dry part with hand.For the system for handling of need with the part clamping, possessing under the necessary mechanics holding power condition, contact point number and size should remain to minimum degree.
Pre-washing
If grease or oil are arranged on the pending part, then carry out the gas phase oil removing by Boeing instruction for process BAC 5048, carry out emulsion by Boeing instruction for process BAC 5763 and clean, or carry out solvent cleaning by Boeing instruction for process BAC 5750.In the time of may holding back outer junction surface of being exposed to of solution or spot welding seam for the part band, this part should after the pre-washing at cold water 1 or formerly in hot water and the back cold water) dipping 2 minutes.
Shelter and shelve
The surface that does not need cobalt to transform rete should be sheltered with protective layer.The plasma flame spraying plating surface of different metal inserts (chromium, nickel or cobalt-base alloy or coating, CRES are perhaps except the titanium) and non-aluminium plating should be sheltered.
Alkali lye cleans
Alkali lye is cleaned and is washed and can be undertaken by Boeing instruction for process BAC 5749, but outside the component that have junction surface being exposed to or spot welding seam.In the case, washing should be carried out manual spray washing with carrying out at least 10 minutes under the condition of stirring subsequently with impregnation method (at least four times) repeatedly, and this is needed as preventing that solution is trapped.
The oxide film dissolving layer
Oxide film dissolving and washing can be undertaken by Boeing instruction for process BAC 5765, but for except the component that might hold back solution because these in addition parts can wash with above-mentioned " alkali lye cleaning " method.Foundry goods can come oxide film dissolving with one of following method:
A. carry out oxide film dissolving by solution among the Boeing instruction for process BAC 5,765 37,38 or 39.
B. by the Boeing instruction for process BAC 5748 II type first kind material spray to cast of dry grinding, and washing.
Particular solution in the scope of the invention is composed as follows:
Every liter of final solution control limit of component
The preparation consumption
Cobaltous nitrate hexahydrate Co (NO 3) 26H 2O 22.5g (about 0.077mol) 20-25g/L
Magnesium nitrate hexahydrate Mg (NO 3) 26H 2O 26.4g (about 0.10mol) 24-28g/L
Ammonium acetate NH 4C 2H 3O 2(35.6g about 0.46mol) 33-38g/L
Hydrogen peroxide H 2O 2[30% (volume)] 5ml (about 0.05mol)
Water surplus
140 ± 5 of temperature
PH??6.0-7.0
Should be noted that: the hydrogen peroxide (H in the above-mentioned composition 2O 2) be to be used for divalent cobalt is changed into six cobaltammines (III) title complex.Though itself just be enough to cobalt (II) salt is changed into cobalt (III) title complex to solution air-blowing bubble (blowing air), this step is very time-consuming, needs a couple of days to transform fully.
Transform rete (when pressing ASTM B117 test, salt spray corrosion resistance is 168 hours) as the above-mentioned cobalt that needs preparation to have maximum corrosion resisting property, be necessary that cobalt is transformed rete carries out sealing treatment.Found that for this reason many confining liquids are available.These lock solution await the reply the application NO.07/621,132(1990 applied for November 30) in put down in writing.The stability of solution and the simplification of solution composition have been done further improvement from that time, specific as follows:
Every liter of final solution control limit of component
The preparation consumption
Six hydration nickel sulfate NiSO 46H 2O 20g (about 0.076mol) 18-22g/L
Magnesium nitrate hexahydrate Mg (NO 3) 26H 2O 20g (about 0.078mol) 18-22g/L
Water surplus
PH??5.0-6.5
200 ± 5 ℃ of working temperatures
PH control, temperature and dipping time
These three parameters of PH control, temperature and dipping time are vital for the performance that cobalt transforms rete.
Although rete has produced when PH5.0-9.0, preferable PH control is to maintain between the PH6.0-7.0.Preferable pH value scope is by regularly adding small amount of N H 4C 2H 3O 2Keep.PH is lower than at 5.0 o'clock, and rete loses colour, until near colorless appearance.PH is 6.5 o'clock, and rete has good corrosion resisting property and qualified paint adhesive performance.
140 ± 5 working temperatures that continue produce the performance of rete and the optimum of outward appearance.
Dipping time tends to be subjected to the influence of temperature and PH control, and is not subjected to the influence of strength of solution.Under 120-130 °F, form satisfied conversion rete and then need surpass 30 minutes transformation time.Under 130-140 °F, in 15-20 minute with regard to producing unanimity the good conversion rete of performance.Improve PH(greater than 7.0) also can make dipping time drop to 5-10 minute, but best rete then forms about PH=6.5.
The oxide film layer analysis
Carried out the ESCA surface analysis with Perkin-Elmer 550 type surface analyzers, and done Auger oxide compound distribution curve with same instrument with different operator schemes, it has characterized the character that cobalt of the present invention transforms rete.(the ESCA=Electron Spectroscopic Chemical Analysis also claims XPS or x-ray photoelectron spectroscopy.) these analysis revealeds, cobalt transforms rete and is made of multiple hopcalite, is the aluminium oxide Al that accounts for maximum volume per-cent 2O 3, and cobalt oxide CoO, Co 3O 4With Co 2O 3, the volume that " maximum volume per-cent " means this kind oxide compound surpasses the volume of any other existing oxide compound, but the volume that might not mean this kind oxide compound is greater than the 50%(volume).
These data are further illustrated in the lower position (promptly being close to the position of aluminum substrate) of oxide membranous layer, and that account for maximum volume per-cent is Al 2O 3The middle part of oxide membranous layer is by CoO, Co 3O 4, Co 2O 3And Al 2O 3The mixture of forming.And these data to be further illustrated in what account for maximum volume per-cent in the top of oxide membranous layer be by Co 3O 4And Co 2O 3The mixture of forming.
The other feature that cobalt of the present invention transforms rete can also reach top to finding out in Fig. 1-8 illustration by Fig. 1-8.Fig. 1 and Fig. 2 are illustrated in a kind of representative cobalt and transform 25 minutes formed cobalt conversion retes 310 of dipping in the coating liquid.Fig. 3 and Fig. 4 show that 15 minutes formed cobalts of dipping transform rete 320 in a kind of representative cobalt conversion coating liquid.Fig. 5 to Fig. 8 indicates at a kind of representative cobalt and transforms 20 minutes formed cobalt conversion retes 330 of dipping in the coating liquid.Comparison diagram 1 is to Fig. 8, and rete 310,320 and 330 seems there is no significant textural difference.Shown in Fig. 1,2,5 and 6, cobalt transforms the upper face of rete look the same fried flour, provides good paint tackiness thus, suitable surface-area and porosity.The rete finer and close solid imporosity that becomes under upper face.
Method of application
Top prescription has been illustrated to transform rete with the cobalt that the dipping application method produces.Same principle also is suitable for by hand, and application method produces this conversion rete with the spray application method.
The patent of above mentioning, specification sheets and other publication are incorporated herein by reference together at this.
As professional domain personnel involved in the present invention can see significantly, the present invention can implement except that the mode the form that exemplifies above, but can not depart from outside essence of the present invention and the principal character scope.Specific specific embodiments of the present invention recited above and described concrete process detail are the present invention as an illustration and non-limiting all respects of the present invention.Described in scope of the present invention such as this explanation appending claims, and be not subjected to the foregoing description limit not.Any He all equivalent substituents all mean included by these claims.

Claims (34)

1, on a kind of metallic matrix, form the method that cobalt transforms rete, the following step that this method comprises:
(a) provide a kind of cobalt conversion fluid that contains solubility cobalt (III) hexa-valent complex and acetic acid water solution, the saturation limit concentration of the concentration of described cobalt (III) hexa-valent complex from about 0.01mol/L to this cobalt (III) hexa-valent complex; And
(b) make described matrix contact the sufficiently long time, form described cobalt thus and transform rete with described solution.
2, the described method of claim 1, wherein said cobalt (III) hexa-valent complex are six oxygenate cobalt (III) title complexs.
3, the described method of claim 2, wherein said cobalt (III) hexa-valent complex is with [Co(NH 3) 6] X 3Form exist, X is one or more Cl, Br, NO of being selected from the formula 3, CN, SCN, PO 4, SO 4, C 2H 3O 2And CO 3Group.
4, the described method of claim 1-3, the concentration of wherein said cobalt (III) hexa-valent complex is from about 0.04mol/L to about 0.15mol/L.
5, the described method of claim 1-4, the PH of wherein said cobalt conversion fluid is about 5.0 to 9.0.
6, the described method of claim 1-5, the temperature of wherein said cobalt conversion fluid is about 20-72 ℃ (68-160 a °F).
7, the described method of claim 1-6, wherein said matrix and described cobalt conversion fluid about 3-60 duration of contact minute.
8, the described method of claim 1-7, wherein said cobalt conversion fluid is to prepare by cobalt (II) salt is reacted with metal nitrate and ammonium acetate, the concentration of wherein said cobalt (II) salt is from about 0.04mol/L of final solution to about 0.15mol/L, the concentration of described metal nitrate is from about 0.03mol/L to 0.2mol/L of final solution, and the concentration of ammonium acetate is from about 0.15mol/L to 0.7mol/L of final solution.
9, the described method of claim 8, wherein said cobalt (II) salt are a kind ofly to have minimal solubility to be about every premium on currency when 20 ℃ (68 °F) 0.01mol cobalt (II) salt is arranged.
10, claim 8 or 9 described methods, wherein said cobalt (II) salt is CoX 2, X is for being selected from Cl, Br, NO in the formula 3, CN, SCN, PO 4, SO 4, C 2H 3O 2Or CO 3One or more groups.
11, the described method of claim 8-10, wherein said metal nitrate is selected from Mg(NO 3) 26H 2O, Ca(NO 3) 26H 2O, NaNO 3, KNO 3Or LiNO 3
12, the described method of claim 8-11, wherein said cobalt conversion fluid is prepared in proper order by following solution preparation:
(a) dissolve described cobalt (II) salt;
(b) dissolve described metal nitrate then; And
(c) add ammonium acetate again.
13, the described method of claim 8-12 is wherein added a kind of oxygenant, so that the cobalt in the solution (II) ion-oxygen is changed into cobalt (III) ion in described cobalt conversion fluid.
14, the described method of claim 13, wherein said oxygenant is hydrogen peroxide H 2O 2
15, the described method of claim 1-14 is being covered matrix and a kind of single nickel salt NiSO that contains that conversion film is arranged comprising making 46H 2O and magnesium nitrate Mg(NO 3) 6H 2The additional step of the water base confining liquid contact of O.
16, the described method of claim 1-15, wherein said metallic matrix is an aluminum or aluminum alloy.
17, a kind of cobalt that produces on metallic matrix transforms the chemical conversion coating liquid that rete is used, this solution comprises a kind of solubility cobalt (III) hexa-valent complex and acetic acid water solution of containing, and the concentration of described cobalt (III) hexa-valent complex is from about 0.01mol/L(solution) to the saturation limit concentration of this cobalt (III) hexa-valent complex.
18, the described solution of claim 17, wherein said cobalt (III) hexa-valent complex are a kind of six cobaltammines (III) title complexs.
19, claim 17 or 18 described solution, wherein said cobalt (III) hexa-valent complex is with [Co(NH 3) 6] X 3Form exist, X is for being selected from Cl, Br, NO in the formula 3, CN, SCN, PO 4, SO 4, C 2H 3O 2Or CO 3One or more groups.
20, the described solution of claim 17-19, wherein said solution is to prepare by a kind of cobalt (II) salt is reacted with a kind of metal nitrate and ammonium acetate, the saturation limit concentration of the concentration of wherein said cobalt (II) salt from the 0.01mol/L of final solution to used cobalt (II) salt, the concentration of described metal nitrate is from about 0.03mol/L(final solution) to the 2.5mol/L(final solution), and the concentration of ammonium acetate is from the 0.06mol/L(final solution) to the 6.0mol/L(final solution).
21, the described solution of claim 20, wherein said cobalt (II) salt are a kind ofly to have minimal solubility to be about every premium on currency when 20 ℃ (68 °F) 0.01mol cobalt (II) salt is arranged.
22, claim 20 or 21 described solution, wherein said cobalt (II) salt is CoX 2, X is for being selected from Cl, Br, NO in the formula 3, CN, SCN, PO 4, SO 4, C 2H 3O 2Or CO 3One or more groups.
23, the described solution of claim 20-22, wherein said metal nitrate is selected from Mg(NO 3) 26H 2O, Ca(NO 3) 26H 2O, NaNO 3, KNO 3Or LiNO 3
24, the described solution of claim 17-23, the preparation of wherein said cobalt conversion fluid preparation comprises in proper order:
(a) dissolve described cobalt (II) salt;
(b) dissolve described metal nitrate then; And
(c) add ammonium acetate.
25, the described solution of claim 17-24, the PH of wherein said solution is about 5.0 to 9.0.
26, the described solution of claim 17-25, the temperature of wherein said solution are about 20-72 ℃ (68-160 °F).
27, the described solution of claim 17-26 wherein adds a kind of oxygenant to described solution, so that cobalt (II) ion-oxygen is changed into cobalt (III) ion.
28, the described solution of claim 27, wherein said oxygenant is hydrogen peroxide H 2O 2
29, use the described chemical conversion coating solution of claim 17-26 on the aluminum or aluminum alloy matrix, to produce cobalt and transform rete.
30, a kind of goods that transform rete on metallic matrix and this metallic matrix with claim 1-16 cobalt that described method is formed that comprise.
31, a kind of have adhesive goods that coating is arranged of solidity to corrosion and paint and paint, and described goods comprise:
(a) a kind of metallic matrix; And
(b) cobalt that forms on described metallic matrix transforms rete, and described cobalt transforms rete and comprises the aluminium oxide Al that accounts for maximum volume per-cent 2O 3; And by CoO, Co 3O 4And Co 2O 3One or more cobalt/cobalt oxides in this group cobalt/cobalt oxide of forming.
32, the described goods of claim 31, wherein said cobalt transform rete and have about 20-240mg/ft 2Rete weight.
33, claim 31 or 32 described goods, wherein said cobalt transforms the porous crack, top layer of rete, and has outward appearance like the fried flour shown in Fig. 1,2,5 and 6.
34, the described goods of claim 31-33, wherein said matrix is an aluminum or aluminum alloy.
CNB931017378A 1992-06-25 1993-01-18 Non-chromated oxide coating for aluminum substrates Expired - Fee Related CN1138873C (en)

Priority Applications (19)

Application Number Priority Date Filing Date Title
CNB931017378A CN1138873C (en) 1992-06-25 1993-01-18 Non-chromated oxide coating for aluminum substrates
MX9303745A MX9303745A (en) 1992-06-25 1993-06-22 PROCESS TO FORM A COBALT CONVERSION COATING ON A METAL SUBSTRATE AND SOLUTION USED THEREIN.
BR9306602A BR9306602A (en) 1992-06-25 1993-06-23 Non-chrome oxide coating for aluminum substrates
AT93914728T ATE198631T1 (en) 1992-06-25 1993-06-23 NON-CHROMATED OXIDE COATINGS FOR ALUMINUM SUBSTRATES
ES93914728T ES2152950T3 (en) 1992-06-25 1993-06-23 UNCROMATED OXIDE COATING FOR ALUMINUM SUBSTRATES.
CA002138790A CA2138790C (en) 1992-06-25 1993-06-23 Non-chromated oxide coating for aluminum substrates
RU94046218A RU2135637C1 (en) 1992-06-25 1993-06-23 Method of formation of coating from oxide of conversion cobalt, product, chemical solution for application of coating from conversion cobalt and coated article
AU45008/93A AU687740B2 (en) 1992-06-25 1993-06-23 Non-chromated oxide coating for aluminum substrates
SG1996004772A SG43169A1 (en) 1992-06-25 1993-06-23 Non-chromated oxide coating for aluminium substrates
JP50204994A JP3345010B2 (en) 1992-06-25 1993-06-23 Chromium-free oxide coating for aluminum support
EP93914728A EP0646187B1 (en) 1992-06-25 1993-06-23 Non-chromated oxide coating for aluminum substrates
DE69329853T DE69329853T2 (en) 1992-06-25 1993-06-23 NON-CHROMATED OXIDE COATINGS FOR ALUMINUM SUBSTRATES
PCT/EP1993/001630 WO1994000619A1 (en) 1992-06-25 1993-06-23 Non-chromated oxide coating for aluminum substrates
DK93914728T DK0646187T3 (en) 1992-06-25 1993-06-23 Non-chromated oxide coating for aluminum substrates
NZ253699A NZ253699A (en) 1992-06-25 1993-06-23 A cobalt conversion coating for metal substrates, comprising a soluble cobalt-iii hexavalent complex
ZA934544A ZA934544B (en) 1992-06-25 1993-06-24 Non-chromated oxide coating for aluminum substrates
CNB931075831A CN1195893C (en) 1992-06-25 1993-06-25 Non-chromated oxide coating for aluminum substrates
NO19945026A NO315522B1 (en) 1992-06-25 1994-12-23 Process for preparing a cobalt-based coating on an aluminum substrate, as well as dissolving and using it in the manufacture of a cobalt-based coating
GR20010400395T GR3035554T3 (en) 1992-06-25 2001-03-09 Non-chromated oxide coating for aluminum substrates.

Applications Claiming Priority (2)

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US07/903,853 US5411606A (en) 1990-05-17 1992-06-25 Non-chromated oxide coating for aluminum substrates
CNB931017378A CN1138873C (en) 1992-06-25 1993-01-18 Non-chromated oxide coating for aluminum substrates

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CN1138873C CN1138873C (en) 2004-02-18

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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
CN103266315A (en) * 2013-05-31 2013-08-28 海安县申菱电器制造有限公司 Preparation method of aluminum alloy cobalt salt chemical conversion coating treating fluid
CN106868495A (en) * 2017-01-23 2017-06-20 江苏理工学院 A kind of recycling method of cobalt salt chemical oxidation waste liquid
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ATE173513T1 (en) * 1991-07-19 1998-12-15 Boeing Co NON-CHROMATED OXIDE COATINGS FOR ALUMINUM SUBSTRATES
WO1996021753A1 (en) * 1995-01-13 1996-07-18 Henkel Corporation Composition and process for forming a solid adherent protective coating on metal surfaces
US5948178A (en) * 1995-01-13 1999-09-07 Henkel Corporation Composition and process for forming a solid adherent protective coating on metal surfaces
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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
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RU94046218A (en) 1996-10-20
CA2138790A1 (en) 1994-01-06
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SG43169A1 (en) 1997-10-17
BR9306602A (en) 1998-12-08
JP3345010B2 (en) 2002-11-18
ATE198631T1 (en) 2001-01-15
GR3035554T3 (en) 2001-06-29
JPH07508311A (en) 1995-09-14
ES2152950T3 (en) 2001-02-16
CA2138790C (en) 2004-10-19
DE69329853D1 (en) 2001-02-15
WO1994000619A1 (en) 1994-01-06

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