CN101223302A - Trivalent chromium conversion coating and method of application thereof - Google Patents
Trivalent chromium conversion coating and method of application thereof Download PDFInfo
- Publication number
- CN101223302A CN101223302A CNA2006800258252A CN200680025825A CN101223302A CN 101223302 A CN101223302 A CN 101223302A CN A2006800258252 A CNA2006800258252 A CN A2006800258252A CN 200680025825 A CN200680025825 A CN 200680025825A CN 101223302 A CN101223302 A CN 101223302A
- Authority
- CN
- China
- Prior art keywords
- mol
- ion
- coating compound
- transformation
- goods
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—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
- C23C22/53—Treatment of zinc 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
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
-
- 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
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
The present invention is directed to a high protection, trivalent chromium coating composition that is particularly useful as a conversion coating on substrates in need of corrosion protection. The conversion coating composition comprises chromium (III) ions, cobalt (II) ions, nitrate ions, and sulfate ions. The invention further provides methods of applying a conversion coating to a plated article and articles with a conversion coating applied thereto.
Description
The cross reference of related application
The application requires the rights and interests of No. 60/684,939, the U.S. Provisional Application submitted on May 26th, 2005, by reference its full content is merged to herein.
Invention field
The present invention relates in general to the metal finishing of the erosion resistance that is used to improve metallic surface performance, particularly metallic surface.More specifically, the present invention relates to conversion coating, relate in particular to and can be used for being applied to the coating that is coated with metallic surface.
Background technology
In metal finishing industry, usually use conversion coating to the metallic surface, especially be coated with the performance that metallic surface provides improvement.Usually the other coating of adding with the back is for example painted or the adhesion property of the metal that other finishing agent is relevant is useful especially for the erosion resistance that improvement is provided to metal and for improving to know conversion coating.Polytype conversion coating is known and is used for industry that known especially a kind of favourable type is a chromate treating.
Chromate conversion coatings can be applied to all thickness and corrosion prevention and other performance of different levels can be provided.For example, this coating can contain from extremely thin " Lan Liang (blue-bright) " surface layer to very thick " grass green " surface layer.The surface layer of Lan Liang is the transparence with light blue mediation high gloss.This surface layer is not only given matrix surface erosion resistance coating, and has improved matrix and by its goods that make on aesthetic feeling.The protective of thicker chromate conversion coatings is more much bigger than bright surface layer, but they do not meet the aesthetic feeling standard, and the aesthetic feeling standard is the feature of light coating.These thicker coatings can be picked out well by their yellow, bronze colour or graminaceous surface layer (by general sequence corresponding to cumulative film thickness).
Though chromate conversion coatings is particularly useful for erosion resistance is provided, this coating is always made by hexavalent chromate (being chromium (VI) ion) always.It is unfavorable that this makes that this chromate conversion coatings becomes, because it is generally acknowledged that chromium (VI) is poisonous.For example, National Institute and health institute (NIOSH) think that all chromium (VI) compounds are the potential occupational carcinogenses.Center for Disease Control (CDC) and NIOSH are reported in the risk that verified lung cancer increases among the workman who is exposed to chromium (VI) compound.Other exposes corrosion and the variable color that the relevant influence that is harmful to health comprises chafing, skin ulcer, supersensitivity contact dermatitis, occupational asthma, nose inflammation and ulcer, perforation of nasal septum, rhinitis, nasal bleeding, respiratory inflammation, rhinocarcinoma, hole cancer, inflammatory eye and damage, the perforation of ear drum, injury of the kidney, liver injury, pulmonary congestion and oedema, epigastric pain and tooth with chromium (VI).Under these are found, cause significant environment concern from the refuse of sexavalent chrome based sols, hexavalent chromium bath needed to carry out special processing before disposing.
Processing in order to other type that does not contain chromium that forms passivating coating is well known in the art, but that these are handled usually is unsatisfactory to the erosion resistance that improves the plating matrix, particularly when processed matrix in wet environment condition following time.These processing generally include phosphatizing and dipping polish step, the applying step of the use clear lacquer subsequently.Each step provides the additional barrier to corrosive environment, but is not the adhesive film that forms chemical bond between film forming component and coating matrix as being obtained by the sexavalent chrome method.Correspondingly, phosphatizing provides the porous blocking layer, allows moisture to pass and arrives the coating matrix.Phosphate coating not only outward appearance is brightless, and provide obfuscation, opaque, like the painted finish coat, this finish coat lacks the aesthetic feeling feature of sexavalent chrome conversion coating.
Utilize trivalent chromium (being chromium (III) ion) to develop not chromyl processing.For example, a plurality of United States Patent (USP)s have been described solution or the method that is used for process metal surfaces, and wherein said solution comprises the chromium ion that is three valence states basically and (sees US patent the 4th, 349 usually, No. 392, No. the 4th, 359,345, US patent, US patent the 4th, 359, No. 346, US patent the 4th, 359, No. 348, No. the 4th, 367,099, US patent, US patent the 4th, 384, No. 902, US patent the 4th, 578, No. the 6th, 096,140, No. 122 and US patent).In each United States Patent (USP) of quoting, in not chromyl solution, comprise oxygenant as neccessary composition.As known in the art is that the oxygenant of existence can cause some trivalent chromium conversion during conversion coating forms be sexavalent chrome.This chromic existence can cause the problem of some or all of aforesaid health and processing subsequently.In addition, the oxygenant that comprises can increase extra-pay and form the step of conversion coating.
Therefore, it is useful having the not chromyl conversion coating that provides based on the similar characteristics of chromic conventional conversion coating.In addition, wish that this not chromyl coating does not allow moisture enter basically and excellent anti corrodibility to long-term exposure can be provided.The coating of the non-hexavalent chromium that preferably, makes also should be attractive by giving simultaneously, grind to such an extent that very bright surface layer improves the outward appearance of matrix.
Summary of the invention
The invention provides the trivalent chromium coating composition of high protection, said composition is particularly useful as the conversion coating on the matrix that needs corrosion prevention.The present invention also provides to this matrix and has applied the method for conversion coating and the coated articles that makes according to this method.The trivalent chromium coating composition is particularly useful, because it does not contain sexavalent chrome, and does not contain and can promote that trivalent chromium conversion is chromic component.In addition, described trivalent chromium coating composition is useful, because it provides the non-corrosibility that improves, has particularly prolonged and can will have that matrix according to conversion coating of the present invention is exposed to corrosive environment and time of not producing matrix corrosion.
In one aspect of the invention, provide transformation coating compound.In one embodiment, said composition comprises chromium (III) ion, cobalt (II) ion, nitrate ion and sulfate ion.Preferably, the chromium of existence (III) ionic concentration is at least about 0.1 mol, and the concentration of the nitrate ion of existence is at least about 0.4 mol.In one embodiment, this transformation coating compound comprises at least about cobalt (II) ion of 0.01 mol with at least about the sulfate ion of 0.1 mol.
Preferably, transformation coating compound of the present invention does not contain the component that can reduce by the corrosion resistance of the formed conversion coating of composition of the present invention.For example, in one embodiment, transformation coating compound avoids using the component that free fluorochemical can be provided especially.In another embodiment of the present invention, conversion coating is substantially free of sequestrant, particularly carboxylic acid group's sequestrant (for example diacid).
Transformation coating compound of the present invention also can comprise one or more other components, and this component is useful for giving the goods that are applied with conversion coating on it with desired properties.Can be that the non-limitative example of the other component of usefulness comprises aminocarboxylic acid or its salt or derivative, silicate for example halide derivative or its salt or the ester of clay (particularly nano particle clay) and acetate in composition of the present invention.
Transformation coating compound of the present invention is particularly useful, because it can be made into enriched material.This enriched material provides to be preserved easily and transports, and it can be easy to diluted when being used to transformation coating compound of the present invention is provided.
According to a further aspect in the invention, be provided for conversion coating is applied to method on the goods with exposed surface.In one embodiment, this method comprises that the exposed surface with goods contacts with the transformation coating compound that comprises chromium (III) ion, cobalt (II) ion, nitrate ion and sulfate ion.In one embodiment, the concentration of the chromium ion of existence is at least 0.1 mol, and the concentration of the nitrate ion that exists is at least 0.5 mol.
In the specific embodiments aspect this according to the present invention, the exposed surface of goods is metal-coated, for example zinc or zinc alloy.Correspondingly, method of the present invention can comprise that plated article contacts with transformation coating compound according to the present invention with coating surface with goods.This method can comprise other step, the stage of surface preparation before the plating step for example, or after goods are being contacted with transformation coating compound the flushing and the drying of goods.
The present invention also comprises the goods with the conversion coating that is applied.In one embodiment, the invention provides the goods with exposed surface, described exposed surface has the conversion coating that is applied, and wherein said conversion coating the method according to this invention applies.The anticorrosive protection particularly advantageous of the goods of this coating to providing to goods by the conversion coating that applies.In one embodiment, goods with the conversion coating that is applied show the anticorrosive protection that is produced by conversion coating, make the goods with the conversion coating that is applied can stand salt spray according to ASTM testing method B 117-03 at least about 200 hours before forming the white salt corrosion product.
Detailed Description Of The Invention
Hereinafter the present invention is described more fully with reference to specific embodiments of the present invention.In fact, the present invention is can be many multi-form embodies and should not be construed as the restriction that is subjected to the listed embodiment of this paper; On the contrary, provide these embodiments to make content disclosed herein can satisfy suitable legal requirements.As in the specification sheets and employed in the appended claims, singulative " " and " be somebody's turn to do ", " described " comprise plural object, unless context has in addition and knows and to indicate.
In various embodiments, use term " to be substantially free of " some compound, composition, ion or other similar components herein and describe the present invention.Correspondingly, as employed in this paper describes, " be substantially free of " be intended to represent be, compound, composition, ion or other similar components exist with trace only (being that concentration is very small, so that the compound, composition, ion or other similar components that exist can not have disadvantageous effect to the desired properties of coating) at the most.Preferably, " be substantially free of " and refer to that compound, composition, ion or other similar components stipulated do not exist fully or do not exist with the measurable amount of common technology in any this area.
Transformation coating compound of the present invention is substantially free of chromium (VI) ion.Correspondingly, said composition only comprises chromium (VI) ion of trace at the most, and this chromium (VI) ionic concn is so small, so that chromium (VI) ion that exists can not have the influence that damages and can not have unfavorable health or environment to the coating desired properties.Most preferably, composition of the present invention does not comprise chromium (VI) ion.
Transformation coating compound of the present invention also is substantially free of oxygenant.This oxygenant is understood to include the known trivalent chromium that influences usually to the reagent of chromic conversion for example superoxide and persulphate.Most preferably, not comprise to be chromic oxygenant with trivalent chromium conversion to composition of the present invention.
Transformation coating compound of the present invention comprises chromium (III) ion, cobalt (II) ion and nitrate ion usually.In other embodiments, transformation coating compound also comprises sulfate ion.Particularly all kinds ionic mixture of normality is to being useful having on the goods of exposed surface the conversion coating of formation, thereby the erosion resistance of improvement is provided to goods.
According to certain embodiments of the present invention, the chromium that exists in the transformation coating compound (III) ion can be regarded as existing with Cmin at least.For example, in one embodiment, chromium (III) ion that the amount in the chromium that provides (III) source makes transformation coating compound comprise concentration to be at least about 0.1 mol.Preferably, composition comprises that concentration is at least about 0.15 mol or at least about chromium (III) ion of 0.2 mol.According to the present invention, chromium (III) ion also can be regarded as existing with preferred concentration range.For example, in one embodiment, composition comprises chromium (III) ion that concentration is about 0.1 mol-Yue 0.4 mol.In other embodiments, the chromium of existence (III) ionic concn is about 0.15 mol-Yue 0.35 mol, about 0.30 mol of about 0.15-or about 0.25 mol of about 0.15-.In one embodiment, the chromium of existence (III) ionic concn is about 0.20 mol.
The amount in the cobalt that preferably provides (II) source makes transformation coating compound comprise cobalt (II) ion at least about 0.01 mol concentration.Preferably, composition comprises at least about 0.02 mol, at least about 0.03 mol or at least about cobalt (II) ion of 0.04 mol concentration.Typically, transformation coating compound comprises cobalt (II) ion of about 0.01 mol-Yue 0.10 mol.In other embodiments, transformation coating compound comprises cobalt (II) ion of about 0.02 mol-Yue 0.09 mol, about 0.03 mol-Yue 0.08 mol or about 0.04 mol-Yue 0.08 mol.
Chromium (III) source and cobalt (II) source all can be and anyly can provide free chromium (III) ion and cobalt (II) ionic source in solution.For example, in one embodiment, chromium (III) ion source and cobalt (II) ion source are selected from the various salt of these metals.According to this embodiment, certainly, the ion outside dechromisation (III) ion or cobalt (II) ion also can be introduced in described source.Preferably, chromium (III) source and cobalt (II) source do not comprise the component of the corrosion resistance that can be harmful to transformation coating compound.
In certain embodiments of the invention, concerning conversion coating, it is useful further being included in the ion component that improves or improve the resistance to corrosion of composition in the solution.This useful example of ionic in addition is sulfate radical (SO
4 -2) ion.Not bound by theory, think that sulfate ion works as the film forming matter on the galvanizing surface.Sulfate ion also can serve as buffer reagent, is convenient to the stability of controlling pH value of solution and also improving solution simultaneously.Advantageously, this required other ion component can be joined in the composition of the present invention and do not need additional composition, otherwise this validity that can increase the expense of preparation said composition or be harmful to said composition.Correspondingly, chromium (III) source and cobalt (II) source are usefully comprised such compound, this compound also comprises other desired ion.For example, in one embodiment, chromium (III) source and cobalt (II) source can be respectively Cr
2(SO
4)
3And CoSO
4
Transformation coating compound of the present invention can comprise the sulfate ion that concentration is at least about 0.1 mol.Preferably, the concentration of the sulfate ion of existence is at least about 0.2 mol or about at least 0.3 mol.In other embodiments, the concentration of the sulfate ion of existence can be about 0.2 mol-Yue 1.0 mol.In addition, the sulfate ion concentration that exists in the composition can be about 0.25 mol-Yue 0.90 mol, 0.30 mol-Yue 0.80 mol or about 0.35 mol-Yue 0.80 mol.
Also can for example originating by other, other metal-salt provides chromium (III) ion and cobalt (II) ion.Though the vitriol of chromium (III) and cobalt (II) is particularly useful as described above, can use any chromium (III) salt and cobalt (II) salt, condition is the component that this salt does not provide the corrosion resistance that may be harmful in transformation coating compound.The non-limitative example of spendable other metal-salt comprises for example nitrate or chloride salt and organic salt acetate for example of inorganic salt among the present invention.
Preferably, according to an embodiment, provide nitrate ion source to make composition comprise at least about 0.4 mol nitrate ion.In another embodiment, transformation coating compound comprises at least about 0.5 mol nitrate ion or at least about 0.6 mol nitrate ion.Typically, transformation coating compound comprises the nitrate ion that concentration is about 0.4 mol-1.5 mol.In another embodiment again, transformation coating compound comprises about 0.5 mol-Yue 1.3 mol nitrate ions, perhaps about 0.6 mol-Yue 1.2 mol.
According to the present invention, can use anyly can provide the nitrate ion of enough concentration and not introduce the source of component that other be harmful to composition is given the ability of goods erosion resistance.In addition, this source should not be or should not form and trivalent chromium conversion can be become chromic oxygenant.In one embodiment, use NaNO
3Provide nitrate ion to composition.In other embodiments, can use nitric acid as the source that is used for the nitrate ion of transformation coating compound.Preferably, if nitric acid is added in the solution, the amount of the nitric acid of adding is lower than and causes trivalent chromium to be oxidized to chromic level.Other non-limitative example in spendable nitrate radical source comprises saltpetre, the inferior chromium of nitric acid, Xiao Suangu and ammonium nitrate according to the present invention.
According to the concentration of chromium provided above (III) ion, cobalt (II) ion and nitrate ion, the chromium of available nitrate ion and combination (III) ion and cobalt (II) ionic mol ratio [NO
3 -/ (Cr
+ 3+ Co
+ 2)] specifically limit transformation coating compound of the present invention.In one embodiment, the mol ratio of nitrate ion and total chromic salt and cobalt ion was greater than about 1.5: 1.Preferably, this than be at least about 1.75: 1, more preferably at least about 2: 1 with most preferably at least about 2.5: 1.In other embodiments, the mol ratio of nitrate ion and total chromium ion and cobalt ion is at least about 3: 1, at least about 4: 1, at least about 5: 1, at least about 6: 1 or at least about 7: 1.
Transformation coating compound of the present invention also can comprise, those skilled in the art it has been generally acknowledged that help to improve or improve erosion resistance or help in transformation coating compound, to become useful especially component.For example, can comprise in the composition known to suppressing the useful particular compound of corrosion.The non-limitative example of this corrosion inhibitor comprises aminocarboxylic acid and salt or derivative.An object lesson of this compound is 5-(dimethylamino)-2,2-biphenyl valeric acid, and it is with trade name HALOX
510 are purchased from HALOX (Hammond Group, the department of Inc., Hammond, the state of Indiana).
Other non-limitative example of useful annexing ingredient comprises silicate in transformation coating compound of the present invention.As used herein, silicate is understood to mean and contains silicon, oxygen and one or more metals and have hydrogen or do not have the compound of hydrogen, comprises the formed silicon ester of combination by silicon and oxygen and one or more organic groups.In addition, silicate can comprise and wherein uses for example fluorine compound of replace oxygen (for example, hexafluorosilicate) partly or wholly of one or more not homoatomics.Silicate is as the part of transformation coating compound and can help to improve protection against corrosion when being applied on the goods.Though be not intended to limit the scope of the spendable silicate according to the present invention, especially, useful silicate comprises for example nano particle clay of talcum, mica and clay in conversion coating.For example, composition can comprise one or more LAPONITE
Clay, this clay can derive from Rockwood Additives, Ltd.Particularly, composition can comprise LAPONITE
RD is (by SiO
2, MgO, LiO
2And Na
2O forms) or LAPONITE
RDS is (by SiO
2, MgO, LiO
2, Na
2O and P
2O
5Form).Another example of useful in the present invention silicate comprises magnesium fluosilicate (MgSiF
66H
2O).
The other example of useful silicate is natural or synthetic layered struture silicate clay according to the present invention.Illustration as these materials is for example montmorillonite, nontronite, beidellite, wilkinite, volkonskoite, LAPONITE, hectorite, saponite, sauconite, magadiite (magadite), fibrous morphology crystals (kenyaite), humites (stevensite) etc. of smectic clays mineral, and vermiculite, halloysite, aluminate oxide compound, hydrotalcite etc.These lamellated clays comprise particle usually, and described particle contains a plurality of silicate sheet bodies with about 8-12 thickness that tightly combine with 4 or littler interlamellar spacing, and comprise the exchangeable cation Na for example that is present in interlayer surfaces
+, Ca
+ 2, K
+Or Mg
+ 2
In another embodiment, conversion coating of the present invention also can comprise one or more halogenated carboxylic acids or its salt or its ester, and condition is that this carboxylic acid does not play the sequestrant effect in addition basically.For example, composition can comprise halogenated acetic acids compound or its salt or its ester, for example trifluoroacetic acid (CF
3CO
2H), sodium trifluoroacetate (CF
3CO
2Na), trichoroacetic acid(TCA) (CCl
3CO
2H), sodium trichloroacetate (CCl
3CO
2Na) etc.
Though above described the preferred ingredient of transformation coating compound prevailingly, the feature of coating composition of the present invention is that also it preferably is substantially free of some particular compound, composition, ion etc.In one embodiment, transformation coating compound of the present invention is substantially free of fluorion.Described transformation coating compound is fluoride ion not fully preferably.This preferred for example use of trifluoroacetic acid of fluorochemicals that is not intended to limit usually.But said composition should not comprise the free fluorine ion.
Transformation coating compound of the present invention can comprise other not fluorine-containing halogen component; Yet according to the present invention, these halogen components are not to need especially.For example, in one embodiment, transformation coating compound can comprise concentration and be the chlorion of about 1 mol at the most.In another embodiment, the concentration of the chlorion of existence is about 0.75 mol at the most.In yet another embodiment, the concentration of the chlorion of existence is about 0.5 mol at the most.
Further preferably, transformation coating compound of the present invention is substantially free of sequestrant.It is generally acknowledged in this area that sequestrant is the compound that can form two or more coordinate bonds with central metal atom, this compound often is an organic compound.Sequestrant generally can the coordination metal, perhaps can be more specifically for the metal (for example, divalent cation chelators) of some valence state.According to the present invention, preferably, transformation coating compound is substantially free of sequestrant usually.In a preferred embodiment, transformation coating compound is substantially free of sequestrant, particularly carboxylic acid group's sequestrant.Can think that this carboxylic acid group's sequestrant generally includes carboxylic acid cpd, this carboxylic acid cpd comprises two or more carboxylic acid functionals (for example " diacid ").
Transformation coating compound of the present invention can be prepared into the i.e. suitable dilute form of usefulness.Perhaps, can provide transformation coating compound by conc forms, on described composition paint goods before with the transformation coating compound dilution of described conc forms.In an embodiment of the present invention, enriched material is provided, wherein by suitably dilution (for example water), the enriched material of dilution forms according to transformation coating compound of the present invention.According to a nonrestrictive example, enriched material is provided, wherein the dilution by about 25 volume % (promptly, 25 parts of enriched materials are to 75 parts of thinners), the enriched material of dilution forms the transformation coating compound that comprises about 0.1 mol-Yue 0.4 mol chromium (III) ion, about 0.01 mol-Yue 0.10 mol cobalt (II) ion, about 0.4 mol-Yue 1.5 mol nitrate ions and about 0.2 mol-Yue 1.0 mol sulfate ions.
Transformation coating compound of the present invention is in that to be used for that conversion coating is applied to the goods with exposed surface particularly useful with the method that the goods with erosion resistance are provided.In one embodiment, this method comprises that the exposed surface with goods contacts with transformation coating compound according to the present invention.
The method according to this invention, transformation coating compound is particularly useful for conversion coating is applied on the goods, and the exposed surface of wherein said goods is by the metal-coated coating of galvanic deposit.In a special embodiment, the exposed surface plating of goods has zinc or zinc alloy.The non-limitative example of useful zinc alloy comprises ZnSn alloy, ZnNi alloy, ZnFe alloy and ZnCo alloy when the exposed surface of plated article.
Can come plated article to plating zinc or the useful any solution and coating method of zinc alloy according to it has been generally acknowledged that in this area.For example, can for example prussiate solution and coating method, alkaline non-prussiate solution and coating method, vitriol-galvanized method and chloride galvanizing method be used in combination with coating technology with conversion coating and applying method thereof.
Having the coating that applied and basis (underlying) goods of conversion coating not limited by the present invention.On the contrary, can use those skilled in the art to think in the method for the invention can carry out plating or think any goods that the erosion resistance that is provided by conversion coating of the present invention can be provided.Concrete metal for example iron containing alloy to corrosion responsive especially and therefore at special benefit aspect the erosion resistance in method of the present invention.Correspondingly, though but, the invention is not restricted to these specific embodiments in this article by with reference to bainite article steel work illustration method of the present invention for example.
Handle in the operation in illustrative metal, to bainite article for example steel carry out multistep and handle to prepare and to carry out applying of conversion coating.By clean steel work, randomly the acid treatment steel work to make these goods be that plating is ready.Preferably, rinsing goods after the acid treatment step of cleaning and choosing wantonly.With zinc or zinc alloy these goods are electroplated then.Behind plating, metal lining through rinsing, optional be exposed to demulcent mineral acid (for example nitric acid or sulfuric acid) and come oxidized surface, and rinsing once more.Apply conversion coating according to the present invention, will have the goods rinsing and the drying of the conversion coating that is applied.Certainly, except that the step that applies conversion coating, method of the present invention can only comprise some in the above-mentioned steps.
Can form the useful any method of chemical bond to will be on the solution paint goods making according to it has been generally acknowledged that in this area, on the goods with transformation coating compound paint plating.For example, can apply transformation coating compound by spraying, dip-coating, submergence, roller coat or other similar approach.In one embodiment, goods are immersed in the bath that comprises transformation coating compound of the present invention.
When bath being used for the submergence goods in order to apply conversion coating, certainly, except that transformation coating compound of the present invention, described bath also can comprise the component standard substance (standard) in the other industry, this component standard substance may be essential to forming bath, but may not influence the conversion coating that is applied on the goods.For example, certainly, bath can comprise water.
Particularly, preferably use clean container to prepare the bath of transformation coating compound.Preferably for example polyethylene, polyvinyl chloride (PVC), stainless steel etc. are made by conversion coating being the inert material for described container or container lining.In one embodiment, at first water is added in the container.Then, the transformation coating compound that when stirring, adds the conc forms of appropriate amount.At last, the remaining working volume water of container is filled, make transformation coating compound suitably be diluted and get ready for being applied on the goods.
Preferably under prescribed condition, conversion coating is applied on the goods of plating.For example, in an embodiment of the present invention, the pH that comprises the bath of transformation coating compound is maintained within a certain range.Preferably, the pH of transformation coating compound is acid (that is, less than about 7 and be more preferably less than about 4).In specific embodiments, the pH of coating is about 3 for about 2-, about 2.2-about 2.8 or about 2.4-about 2.8.
According to another embodiment of the present invention, at least about conversion coating being applied on the goods of plating under the room temperature.In a preferred embodiment, with the temperature of transformation coating compound be applied on the goods during bring up to above room temperature.The temperature of this raising is particularly useful, because when finding to apply under the temperature that improves, has improved the final erosion resistance of the conversion coating that is applied on the goods.In certain embodiments, the temperature that applies during the transformation coating compound is about 20 ℃-Yue 70 ℃, about 30 ℃-Yue 60 ℃ or about 40 ℃-Yue 50 ℃.
During this time the time span of conversion coating paint goods be can be depending on other method parameter and change, for example with the dilution of the method on the transformation coating compound paint goods, composition and the temperature of composition.In one embodiment, by being immersed in the bath that comprises transformation coating compound, goods apply composition.According to this embodiment, goods are immersed in about at the most 90 seconds of time span in the bath.Particularly, can with the goods submergence about 15 the second-Yue 75 seconds, about 20 the second-Yue 70 seconds or about 30 the second-Yue 60 seconds.
According to above-mentioned transformation coating compound and method of application thereof, the present invention also provides the goods with exposed surface, and these goods have the conversion coating that is applied to its exposed surface.This goods that are coated with conversion coating of the present invention are particularly useful, because the conversion coating that is applied is effectively for anticorrosive protection is provided, described protection substantially exceeds separately the protection by plating provided.
Be easy to estimate by salt spray (or salt fog) test by the anticorrosive effect that conversion coating of the present invention provided, described test is carried out according to the standard B117-03 of American Society for testing and materials (ASTM) standard (in October, 2003 version).Composition provided by the invention can be estimated and is tending towards providing and can meets or exceed the performance requriements of describing according in one or more different testing method by other known testing method.Yet,, with the testing method of indicating present composition opposing corrosive ability is described in this article for simplification.Correspondingly, only, the material that is coated with at the coating composition within the scope of the invention should be considered as outside scope of the present invention by estimating with the method that is different from ASTM B117-03.
According to ASTM B117-03, test set is by fog chamber, salts solution reservoir, form through the compressed-air actuated feeding mechanism and the atomizing nozzle of suitable adjusting.Use this device, will be sprayed onto for a long time continuously on the sample to cause corrosion by the salts solution that about 5 weight part NaCl in 95 weight parts (pbw) water form.The sample that depends on use can estimate and causes the corrosive time.
Specifically about the present invention, carry out corrosion test on the galvanized steel sample, described galvanized steel sample has applied conversion coating of the present invention.In this test, record the generation of two types of corrosion products: white salt and red rust.The appearance of the white salt of seeing shows the inefficacy and the basic galvanized corrosion of conversion coating.The appearance of the redness rust of seeing shows the corrosion of zinc-plated inefficacy and basic steel sample.For the purpose of the anticorrosive protection of estimating conversion coating of the present invention, utilized the time that forms the white salt corrosion product.
In an embodiment of the present invention, goods with the conversion coating of the present invention that is applied are characterised in that, described conversion coating provides anticorrosive protection, make and carrying out salt fog according to above-mentioned ASTM testing method B117-03 when handling that the formation that conversion coating can be resisted white salt was at least about time of 200 hours.According to other embodiments, the formation that conversion coating can be resisted white salt at least about 250 hours, at least about 300 hours, at least about 350 hours or at least about time of 400 hours.
Except that anticorrosive protection, conversion coating of the present invention is pleasant on aesthetic feeling preferably.For example, in one embodiment, the conversion coating that is applied on the goods according to the present invention is the sapphirine coating.In addition, be exposed to for example mordant dyeing of dyestuff (Mordant) family diazotizing dyes by goods and can obtain coloured chromate coating coating, and the not corrosion prevention of deterioration coating.For example, by using mordant dyeing orange 6 dyestuffs can produce yellow coating.Suitable dyestuff exposure duration be about 5 the second-Yue 40 seconds, dyestuff is in about 20 ℃-Yue 40 ℃ temperature thus.
The present invention is favourable in addition, does not need prebaking goods to be applied to reduce hydrogen embrittlement because can form conversion coating.Other products needed parts are baked before chromate treating, and it also needs reactivate was carried out on the surface of parts before chromate treating.Bake common destruction corrosion prevention.Chromate treating and bake then and greatly simplified the conversion coating processing.
Experiment
By following examples the present invention is described more fully, lists described embodiment various embodiments of the present invention to be described and to should not be construed as limitation ot it.
Embodiment 1
Prepare a series of test components and estimate various chromic salt prescriptions.(deriving from Pavco by 3 ounces/gallon (oz/gal) metallic zinc, 18 ounces/gallon ammonium chlorides, 4% (vol/vol) Smart ZincCarrier, Inc.) and 0.2% (vol/vol) Smart Zinc Toner (derive from Pavco, Inc.) coated parts in the acid of Zu Chenging-muriate electro-galvanizing.At 20 peace/feet
2Down described parts are carried out zinc-plated 25-30 minute to produce the zinc thickness of about 0.3-0.5mm.Behind plating, parts are with water rinse and use the rinsing of 0.5% (vol/vol) salpeter solution then.
With various transformation coating compound paint by on the above-mentioned coated parts that makes.By being that 50 ℃ and pH soak in 2.6 the bath to apply for 60 seconds comprising according to transformation coating compound of the present invention, temperature.As mentioned above, the parts of the transformation coating compound that applies having with regard to erosion resistance according to ASTM B 117-03 are tested.Erosion resistance is defined as forming the time of white salt.The time (in hour) that transformation coating compound composition (in mol), nitrate ion and total chromium (III) ion and cobalt (II) ionic mol ratio is provided in table 1 and has produced white salt.
Table 1
| OK | [Cr +3] ( M) | [Co +2] ( M) | [NO 3 -] ( M) | [SO 4 +2] ( M) | [Cl -] ( M) | Mol ratio NO 3 -/(Cr +3+Co +2) | Produce the time (hrs) of white salt |
| 1 | 0.10 | 0.04 | 1.1 | 0.19 | 0.00 | 7.9 | 402.0 |
| 2 | 0.30 | 0.04 | 1.1 | 0.49 | 0.00 | 3.2 | 402.0 |
| 3 | 0.206 | 0.024 | 1.1 | 0.33 | 0.00 | 4.8 | 334.7 |
| 4 | 0.10 | 0.04 | 1.1 | 0.34 | 0.00 | 7.9 | 481.0 |
| 5 | 0.30 | 0.04 | 1.1 | 0.94 | 0.00 | 3.2 | 439.0 |
| 6 | 0.26 | 0.04 | 1.1 | 0.82 | 0.00 | 3.7 | 434.6 |
| 7 | 0.20 | 0.02 | 0.6 | 0.62 | 0.00 | 2.7 | 324.6 |
| 8 | 0.10 | 0.40 | 1.1 | 0.19 | 1.00 | 7.9 | 301.0 |
| 9 | 0.30 | 0.04 | 1.1 | 0.49 | 1.00 | 3.2 | 395.0 |
| 10 | 0.26 | 0.025 | 0.75 | 0.42 | 0.25 | 2.6 | 502.3 |
| 11 | 0.26 | 0.025 | 1.75 | 0.42 | 0.25 | 6.1 | 463.3 |
| 12 | 0.26 | 0.025 | 1.75 | 0.42 | 0.75 | 6.1 | 440.3 |
| 13 | 0.30 | 0.04 | 1.1 | 0.94 | 1.0 | 3.2 | 398.0 |
| 14 | 0.20 | 0.02 | 1.1 | 0.62 | 0.50 | 5.0 | 351.4 |
| 15 | 0.26 | 0.025 | 1.75 | 0.805 | 0.25 | 6.1 | 392.8 |
| 16 * | 0.26 | 0.025 | 1.2 | 0.805 | 0.25 | 4.2 | ＞555 |
* annotate: the 16th row also comprises the HALOX of 2.5g/L
510[5-(dimethylamino)-2,2-phenylbenzene valeric acid] corrosion inhibitor
As with the contrast of above-mentioned data, also the trivalent chromium base conversion coating that is purchased is tested according to parameter same as described above.Use comprise 14.5% (vol/vol) HyproBlue (derive from Pavco, Inc.), pH be 2.4 and temperature be 40 ℃ bath.With the parts of plating 60 seconds of submergence in this is bathed.Under salt spray, test three independent parts according to ASTM B 117-90.The time that these three parts produce white salt is 135.6 hours, 169.7 hours and 115.7 hours.
Embodiment 2
Various test components and are coated with according to transformation coating compound of the present invention according to preparation described in the embodiment 1, to estimate the resistance to corrosion of coating.By being that 40 ℃ or 50 ℃ and pH soak in 2.6 the bath to apply for 60 seconds comprising transformation coating compound, temperature.As mentioned above, the parts of the transformation coating compound that applies having with regard to erosion resistance according to ASTM B 117-03 are tested.The time (in hour) that transformation coating compound composition (in mol), nitrate ion and total chromium (III) ion and cobalt (II) ionic mol ratio is provided in table 2 and has produced white salt.
Table 2
| OK | [Cr +3] (M) | [Co +2] (M) | [NO 3 -] (M) | [SO 4 -2] (M) | Mol ratio NO 3 -/(Cr +3+Co +2) | Produce the time (hrs) of white salt |
| 17 a | 0.260 | 0.027 | 1.200 | 0.660 | 4.2 | 303 |
| 18 b | 0.200 | 0.040 | 1.206 | 0.040 | 5.0 | 477 |
| 18 c | 0.200 | 0.040 | 1.206 | 0.040 | 5.0 | 608 |
| 20 | 0.200 | 0.040 | 1.000 | 0.340 | 4.2 | 317 |
| 21 | 0.200 | 0.040 | 0.900 | 0.520 | 3.8 | 272 |
| 22 | 0.200 | 0.020 | 1.200 | 0.260 | 5.5 | 300 |
| 23 | 0.200 | 0.060 | 0.600 | 0.780 | 2.3 | 249 |
| 24 d | 0.200 | 0.040 | 0.800 | 0.240 | 3.3 | 417 |
| 25 e | 0.200 | 0.040 | 0.800 | 0.240 | 3.3 | 335 |
| 26 f | 0.200 | 0.040 | 0.800 | 0.240 | 3.3 | 390 |
A-also comprises 7.5g/L LAPONITE
RD
B-also comprises 0.200M CF
3CO
2H
C-also comprises 0.399M CF
3CO
2H
D-also comprises 0.400M CCl
3CO
2H
E-also comprises 0.600M CCl
3CO
2H
F-also comprises 0.018M MgSiF
66H
2O
Of the present invention many distortion of illustrating herein and other embodiment are that those skilled in the art can expect, relative these inventions have the benefit of the instruction that is proposed in the description of front.Therefore, certainly, the present invention is not subjected to the restriction of disclosed specific embodiments, and these distortion and other embodiment are defined as and comprise within the scope of the appended claims.Although use concrete term among the present invention, they only use with general and descriptive sense and are not for the restriction purpose.
Claims (29)
1. transformation coating compound, it comprises:
(a) at least about chromium (III) ion of 0.1 mol;
(b) at least about the nitrate ion of 0.4 mol;
(c) cobalt (II) ion; With
(d) sulfate ion.
2. the transformation coating compound of claim 1, it comprises at least about the chromium of 0.2 mol (III) ion.
3. the transformation coating compound of claim 1, it comprises the nitrate ion at least about 0.6 mol.
4. the transformation coating compound of claim 1, wherein cobalt (II) ionic concentration is at least about 0.01 mol.
5. the transformation coating compound of claim 4, wherein cobalt (II) ionic concentration is at least about 0.02 mol.
6. the transformation coating compound of claim 1, wherein the concentration of sulfate ion is at least about 0.1 mol.
7. the transformation coating compound of claim 6, wherein the concentration of sulfate ion is at least about 0.2 mol.
8. the transformation coating compound of claim 1, wherein said composition is fluoride ion not.
9. the transformation coating compound of claim 1, wherein said composition is substantially free of sequestrant.
10. the transformation coating compound of claim 1, wherein nitrate ion and total chromium (III) ion and cobalt (II) ionic are than greater than 1.5: 1.
11. the transformation coating compound of claim 1, it also comprises one or more and is selected from the other component that contains silicate compound, halogenated carboxylic acid or its salt or ester.
12. the transformation coating compound of claim 11, the wherein said silicate compound that contains is selected from clay and magnesium fluosilicate.
13. the transformation coating compound of claim 12, wherein said clay comprises the nano particle clay.
14. the transformation coating compound of claim 11, wherein said halogenated carboxylic acid are selected from halogenated acetic acids and its salt or ester.
15. the transformation coating compound of claim 14, wherein said halogenated acetic acids comprise trifluoroacetic acid, trichoroacetic acid(TCA) or their salt or ester.
16. the transformation coating compound of claim 1, it also comprises the chlorion of about at the most 1.0 mol.
17. the transformation coating compound of claim 1, wherein chromium (III) ion and cobalt (II) ion provide with metal-salt.
18. the transformation coating compound of claim 17, wherein metal-salt comprises metal sulfate.
19. the transformation coating compound of claim 1, it comprises:
(a) chromium (III) ion of about 0.1 mol-Yue 0.4 mol;
(b) cobalt (III) ion of about 0.02 mol-Yue 0.09 mol;
(c) nitrate ion of about 0.4 mol-Yue 1.5 mol; With
(d) sulfate ion of about 0.2 mol-Yue 1.0 mol; Wherein said composition is fluoride ion and sequestrant not.
20. conversion coating is put on the method for the goods with exposed surface, and described method comprises the exposed surface of goods is contacted with transformation coating compound according to claim 1.
21. the method for claim 20, wherein the exposed surface plating of goods has zinc or zinc alloy.
22. the method for claim 20, wherein the pH of transformation coating compound is about 2.0-about 3.0.
23. the method for claim 20, wherein the temperature of transformation coating compound is about 20 ℃-Yue 70 ℃.
24. the method for claim 20, the time that wherein said contact procedure is carried out is about 90 seconds at the most.
25. the method for claim 20, wherein said contact procedure comprise goods are immersed in the transformation coating compound.
26. have the goods of exposed surface, described exposed surface has the conversion coating that is applied, wherein said conversion coating applies according to the method for claim 20.
27. the goods of claim 26, wherein the exposed surface plating of goods has zinc or zinc alloy.
28. the goods of claim 26, the conversion coating that wherein is applied to exposed surface is effective to anticorrosive protection is provided, make described conversion coating carry out salt spray according to ASTM testing method B117-03 when handling, the formation that can resist the white salt corrosion product was at least about time of 200 hours.
29. the formation that the goods of claim 28, the conversion coating that wherein is applied to exposed surface can be resisted the white salt corrosion product was at least about 300 hours time.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US68493905P | 2005-05-26 | 2005-05-26 | |
| US60/684,939 | 2005-05-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101223302A true CN101223302A (en) | 2008-07-16 |
Family
ID=37004380
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006800258252A Pending CN101223302A (en) | 2005-05-26 | 2006-05-26 | Trivalent chromium conversion coating and method of application thereof |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20060266438A1 (en) |
| CN (1) | CN101223302A (en) |
| BR (1) | BRPI0611418A2 (en) |
| MX (1) | MX2007014838A (en) |
| WO (1) | WO2006128154A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114086168A (en) * | 2021-11-26 | 2022-02-25 | 山西汾西重工有限责任公司 | Passivation solution and preparation method of colorful passivation film |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101384751B (en) * | 2006-02-14 | 2013-01-02 | 汉高股份及两合公司 | Composition and processes of a dry-in-place trivalent chromium corrosion-resistant coating for use on metal surfaces |
| US20070243397A1 (en) * | 2006-04-17 | 2007-10-18 | Ludwig Robert J | Chromium(VI)-free, aqueous acidic chromium(III) conversion solutions |
| KR20090018067A (en) | 2006-05-10 | 2009-02-19 | 헨켈 아게 운트 코. 카게아아 | Improved trivalent chromium-containing composition for use in corrosion resistant coating on metal surfaces |
| ES2361361T3 (en) | 2007-03-05 | 2011-06-16 | Atotech Deutschland Gmbh | PASSIVATION IN BLACK EXEMPT FROM CHROME (VI) FOR SURFACES CONTAINING ZINC. |
| CN104805427A (en) * | 2007-08-03 | 2015-07-29 | 迪普索尔化学株式会社 | Corrosion-resistant trivalent-chromium chemical conversion coating and solution for trivalent-chromium chemical treatment |
| TWI385698B (en) * | 2008-06-17 | 2013-02-11 | Univ Nat Defense | Field emission device and method for fabricating cathode emitter and zinc oxide anode |
| US20110070429A1 (en) * | 2009-09-18 | 2011-03-24 | Thomas H. Rochester | Corrosion-resistant coating for active metals |
| CN103930494B (en) * | 2011-10-19 | 2016-10-19 | 巴斯夫涂料有限公司 | The method forming corrosion-inhibiting coating |
| US10156016B2 (en) | 2013-03-15 | 2018-12-18 | Henkel Ag & Co. Kgaa | Trivalent chromium-containing composition for aluminum and aluminum alloys |
| US20230348733A1 (en) * | 2020-08-28 | 2023-11-02 | Coatings For Industry, Inc. | Corrosion-resistant coatings |
Family Cites Families (29)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3392008B2 (en) * | 1996-10-30 | 2003-03-31 | 日本表面化学株式会社 | Metal protective film forming treatment agent and treatment method |
| US4359346A (en) * | 1981-04-16 | 1982-11-16 | Occidental Chemical Corporation | Trivalent chromium passivate solution and process for yellow passivate film |
| US4349392A (en) * | 1981-05-20 | 1982-09-14 | Occidental Chemical Corporation | Trivalent chromium passivate solution and process |
| CA1228000A (en) * | 1981-04-16 | 1987-10-13 | David E. Crotty | Chromium appearance passivate solution and process |
| US4359348A (en) * | 1981-06-17 | 1982-11-16 | Occidental Chemical Corporation | Stabilized trivalent chromium passivate composition and process |
| US4359345A (en) * | 1981-04-16 | 1982-11-16 | Occidental Chemical Corporation | Trivalent chromium passivate solution and process |
| US4367099A (en) * | 1981-06-15 | 1983-01-04 | Occidental Chemical Corporation | Trivalent chromium passivate process |
| US4384902A (en) * | 1981-06-15 | 1983-05-24 | Occidental Chemical Corporation | Trivalent chromium passivate composition and process |
| US4578122A (en) * | 1984-11-14 | 1986-03-25 | Omi International Corporation | Non-peroxide trivalent chromium passivate composition and process |
| SU1617054A1 (en) * | 1988-02-01 | 1990-12-30 | Днепропетровский химико-технологический институт | Composition for chrome-plating zinc surface |
| US5242714A (en) * | 1991-12-20 | 1993-09-07 | Henkel Corporation | Process for forming protective base coatings on metals |
| DE19615664A1 (en) * | 1996-04-19 | 1997-10-23 | Surtec Produkte Und Systeme Fu | Chromium (VI) free chromate layer and process for its production |
| US6368671B1 (en) * | 1998-06-22 | 2002-04-09 | Mccormick David R. | Treating solid, especially aluminum, surfaces |
| US20040173289A1 (en) * | 2001-01-31 | 2004-09-09 | Yasuhiro Kinoshita | Rustproofing agent for zinc plated steel sheet |
| DE10146559A1 (en) * | 2001-09-21 | 2003-04-10 | Enthone Omi Deutschland Gmbh | Process for the deposition of a zinc-nickel alloy from an electrolyte |
| JP2003147544A (en) * | 2001-11-07 | 2003-05-21 | Nippon Parkerizing Co Ltd | Surface treatment film of zinc plated film, surface treatment solution for zinc plated film, and surface treatment method |
| JP2003171778A (en) * | 2001-12-06 | 2003-06-20 | Nippon Hyomen Kagaku Kk | Method for forming protective film of metal, and protective film of metal |
| DE10162756A1 (en) * | 2001-12-20 | 2003-07-10 | Walter Hillebrand Gmbh & Co | Schwarzpassivierungsverfahren |
| US7029541B2 (en) * | 2002-01-24 | 2006-04-18 | Pavco, Inc. | Trivalent chromate conversion coating |
| JP3774415B2 (en) * | 2002-03-14 | 2006-05-17 | ディップソール株式会社 | A treatment solution for forming a black hexavalent chromium-free conversion coating on zinc and zinc alloy plating and a method of forming a black hexavalent chromium-free conversion coating on zinc and zinc alloy plating. |
| JP3620510B2 (en) * | 2002-04-05 | 2005-02-16 | ユケン工業株式会社 | Substrate, manufacturing method thereof and automobile parts |
| JP4090780B2 (en) * | 2002-04-24 | 2008-05-28 | 日本表面化学株式会社 | Metal anticorrosive film forming agent and forming method |
| JP2004083771A (en) * | 2002-08-28 | 2004-03-18 | Nippon Hyomen Kagaku Kk | Composition for metal-protective film formation |
| US20040156999A1 (en) * | 2003-02-07 | 2004-08-12 | Pavco, Inc. | Black trivalent chromium chromate conversion coating |
| WO2004072320A2 (en) * | 2003-02-07 | 2004-08-26 | Pavco, Inc. | Use of n-allyl substituted amines and their salts as brightening agents in nickel plating baths |
| DE10305450A1 (en) * | 2003-02-11 | 2004-08-26 | Walter Hillebrand Gmbh & Co. | Material mixture for blackening passivating drums and frames comprises an aqueous acidic solution containing chromium (III) ions |
| JP4384471B2 (en) * | 2003-10-27 | 2009-12-16 | ディップソール株式会社 | Method of forming hexavalent chromium-free corrosion-resistant film on zinc-nickel alloy plating |
| JP4508634B2 (en) * | 2003-12-26 | 2010-07-21 | 株式会社タイホー | Metal surface treatment agent, metal surface treatment liquid, corrosion-resistant colored film formed thereby, corrosion-resistant colored part having this corrosion-resistant colored film, and method for producing this corrosion-resistant colored part |
| JP4446233B2 (en) * | 2004-03-03 | 2010-04-07 | ディップソール株式会社 | Covalent friction coefficient reducing agent for trivalent chromate treatment solution, trivalent chromate treatment solution and production method thereof, trivalent chromate coating with reduced overall friction coefficient and production method thereof |
-
2006
- 2006-05-26 US US11/420,570 patent/US20060266438A1/en not_active Abandoned
- 2006-05-26 BR BRPI0611418-0A patent/BRPI0611418A2/en not_active Application Discontinuation
- 2006-05-26 MX MX2007014838A patent/MX2007014838A/en unknown
- 2006-05-26 WO PCT/US2006/020876 patent/WO2006128154A1/en active Application Filing
- 2006-05-26 CN CNA2006800258252A patent/CN101223302A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114086168A (en) * | 2021-11-26 | 2022-02-25 | 山西汾西重工有限责任公司 | Passivation solution and preparation method of colorful passivation film |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2006128154A1 (en) | 2006-11-30 |
| US20060266438A1 (en) | 2006-11-30 |
| MX2007014838A (en) | 2008-02-21 |
| BRPI0611418A2 (en) | 2010-09-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101223302A (en) | Trivalent chromium conversion coating and method of application thereof | |
| EP1394288B1 (en) | Treating solution and treating method for forming protective coating films on metals | |
| US6527841B2 (en) | Post-treatment for metal coated substrates | |
| DE60110470T2 (en) | Corrosion protection coatings for aluminum and aluminum alloys | |
| US7029541B2 (en) | Trivalent chromate conversion coating | |
| JP2003171778A (en) | Method for forming protective film of metal, and protective film of metal | |
| EP1585847A4 (en) | Post-treatment for metal coated substrates | |
| FI70599C (en) | VACCUM CONTAINING ZINC PHOSPHATE BELARGING CONDITIONING FOR FUNGARI VID AND LAOG TEMPERATURE AND OVER ANCHENDER FOR VIDEO CHEMICAL CONVERTIBLE CONVERTIBILITY PAO JARN OCH / ELLER | |
| CN102144042B (en) | Aluminum treatment composition | |
| JP3987633B2 (en) | Metal protective film forming treatment agent and forming method | |
| CA2500801C (en) | Chrome free final rinse for phosphated metal surfaces | |
| JP2011219791A (en) | Coated plated steel material for concrete structure | |
| JP2003313675A (en) | Agent for forming rust preventive film on metal, and forming method | |
| JP3278509B2 (en) | Method for forming hardly soluble chromate film on zinc-containing metal plated steel sheet | |
| JPH0819531B2 (en) | Zinc phosphate treatment method for metal surface | |
| JP2000309879A (en) | Surface treated metallic sheet | |
| KR19990082789A (en) | Composition and process for anti-corrosive treatment of non-ferrous metal | |
| JP3278475B2 (en) | Trivalent chromium compound sol composition and method for producing the same | |
| JP3461741B2 (en) | Pre-coated steel sheet with excellent corrosion resistance | |
| US5641537A (en) | Composition for and method of monitoring dried-in-place non-chrome polyacrylamide based treatments for metals | |
| JP3475908B2 (en) | Method for improving the weather resistance of zinc-based plating materials | |
| US5505792A (en) | Visible dried-in-place non-chrome polyacrylamide based treatment for aluminum | |
| US20040115448A1 (en) | Corrosion resistant magnesium and magnesium alloy and method of producing same | |
| JP3615781B2 (en) | Method for producing trivalent chromium compound sol, surface treatment agent for metal material containing the sol, and surface treatment method | |
| JP2003293156A (en) | Phosphate treated steel sheet excellent in corrosion resistance, adhesion for coating material and corrosion resistance after coating, and production method therefor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20080716 |