CN101580654B - Composition for converting and coating zincous metal base and processing method thereof, and processed zincous metal base and purpose thereof - Google Patents
Composition for converting and coating zincous metal base and processing method thereof, and processed zincous metal base and purpose thereof Download PDFInfo
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- CN101580654B CN101580654B CN2008100965269A CN200810096526A CN101580654B CN 101580654 B CN101580654 B CN 101580654B CN 2008100965269 A CN2008100965269 A CN 2008100965269A CN 200810096526 A CN200810096526 A CN 200810096526A CN 101580654 B CN101580654 B CN 101580654B
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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
- C23C22/34—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
- C23C22/36—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 containing also phosphates
- C23C22/361—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 containing also phosphates containing titanium, zirconium or hafnium compounds
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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
- C23C22/40—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 molybdates, tungstates or vanadates
- C23C22/44—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 molybdates, tungstates or vanadates containing also fluorides or complex fluorides
Abstract
The invention provides a composition for converting and coating a zincous metal base, which is an aqueous chromium-free solution comprising the following components: (a) phosphorous acid, (b) a fluorine titanium complex and (c) a vanadium ion source; each component has the following content: vanadium ions (c) provided by the vanadium ion source have the concentration of 1g/L to 20g/L in the composition, the mol ratio of the vanadium ions (c) to phosphate ions (a) is 1:4 to 1:2, and the mol ratio of the vanadium ions (c) to the fluorine titanium complex (b) is 3:2 to 3:1. The invention also provides a prepared composition for forming the composition through water dilution, a method for forming a conversion coating through the contact of the zincous metal base and the composition, and the converted zincous metal base obtained by the method and a purpose thereof. The composition does not need additional washing or particularly chromate passivation washing after being used for surface conversion processing of the zincous metal base, and thereby, the surface conversion processing steps are simple, and the environment can not be polluted by chromium.
Description
Technical field
The present invention relates to a kind of compsn that is used for the substrate of conversion coated zinc-containing metal, it is an aqueous chromium-free, and contains the vanadium ion source and with vanadium ion the phosphate anion and the fluorine titanium complex of a certain amount of mol ratio are arranged.In addition, the present invention also comprises the method for handling the zinc-containing metal substrate with said composition, and said composition especially is fit to the coating-type cladding process in the coiled material coating industry.The present invention also comprises zinc-containing metal substrate and this zinc-containing metal substrate handled with this method and is producing white goods, household electrical appliance, vehicle and the purposes in construction industry.
Background technology
To containing Zinc material, the short-term corrosionproof protection of the steel band of especially zinc-plated or galvanized alloy normally leans on preservative oil, perhaps carries out conversion processing in case of necessity, like phosphatization or passivation.The term here " conversion processing " refers to the aqueous solution metallic surface handled; Original matallic surface layer changes into a kind of inorganic layer in treating processes, and this inorganic layer comprises the positively charged ion in the base metal of positively charged ion and negatively charged ion and processing in the treating water solution.The scope of metal conversion processing comprises makes metal have the anti-corrosion protection layer, and an articulamentum is provided, with the adhesive power between the organic coating that improves the metallic surface and after this smear.
The surface working that contains Zinc material that is used for buildings, automatic industrial, electronic market or white goods manufacturing will be passed through a plurality of steps usually; Comprise pre-treatment step or deoiling step, with clean metal surface, the residual grease of removal and hard water residue or other organic surface contaminants; Also comprise through conversion processing forming curtain coating and being coated with organic coating, like priming paint, paint or electroplated coating etc.Because substrate and to the particular requirement of coating also will be cleaned through transpassivation after the conversion processing, this can further improve the erosion resistance and the adhesivity of screen layer.Because the cause of metal base also will be carried out chromating afterwards especially and cleaned, and to remove the defective in the phosphate coating, like micropore and crackle, improves the paint adhesion property of inorganic screen layer simultaneously.
In the prior art, realize through chromate conversion treatments about anti-corrosion protection with to the adhesion of the organic coating of coating afterwards.In automatic industrial, forming the effective screen layer of one deck with the phosphatize method has been sophisticated method.But this method itself is the rapid process of the multistep of a complicacy, and it need control a large amount of plating bath parameters, and simultaneously with respect to chromating, the decorative coating that this method obtains still less.Because these chromate coatings contain dangerous sexavalent chrome, a kind of method that can replace chromate conversion is just being sought in surface treatment industry, to meet country and the lex loci rules that come into force in European Union recently.These laws and regulations are the order (2002/95/EC) of discarded electric equipment or electronics being sent with European Union and the order (2000/53/EC of recycling use scrap-car; 2005/673/EC) be foundation.Much making great efforts of people is the phosphatize method of development zinc-containing metal; Make it satisfy the etch-proof requirement of short-term and provide suitable adhesive power to be applied in the suprabasil organic coating of phosphated zinc with adhesion; And do not need extra step, clean (like chromate post treatments) like the activation step before the phosphatize step, extra passivation.Especially, " do not have and clean " or " coating-type " apply and are popular, because they provide a kind of one step process, this method can form screen layer, can also comprise the initial organic layer that one deck can adhere to the metal section and part that will protect.
U.S. Pat 6692583 discloses a kind of compsn that is used for the aqueous chromium-free conversion coated of magnesium substrate, and said composition only comprises a) vanadic acid radical ion source, b) phosphate ion sources and c) nitrate ion source.This patent is also mentioned and can be comprised source of borate ions, fluorion and/or fluoro boron acid ion as the further selectable composition of this coating composition.
U.S. Pat 2007/0068602 discloses a kind of preparation method and a kind of compsn, is coated on the ferrous metal surface with the conversion coatings that contains zirconium or vanadium, and this conversion coatings does not contain component and the tanpic acid that forms organic membrane in essence.According to the content of this invention, most important aspect is to confirm that the ratio of vanadium and phosphate anion is 0.5-2.4, and the consideration to environment makes phosphatic consumption as far as possible little.And another important aspect is, the ratio of zirconium atom and vanadium atom will be 1: 2-2: in 1 the scope.
Summary of the invention
Technical problem to be solved by this invention is the defective that overcomes existing conversion processing complicated steps to the zinc-containing metal substrate, pollution of chromium is arranged; And providing a kind of stable aqueous chromium-free that contains the vanadium ion source to be used for the compsn of conversion coated, it can provide one deck thin inorganic protective layer for the zinc-containing metal surface.The thin inorganic layer that in the zinc-containing metal substrate, forms can provide the short-term protection, prevents corrosion, especially prevents in the formation that applies the preceding white rust of next step protective cover (like organic priming paint and/or paint).And the thin inorganic layer that in the process that applies compsn of the present invention, forms also needs fabulous paint adhesion property.In addition, this aqueous chromium-free compsn that is used for conversion coated is also wanted to be fit to the coating-type cladding process that coiled material coating industry is popular.
As the prerequisite of the present composition, the implication that term " is stablized " is: compsn reaches 60 ℃ in temperature, and keep still keep under at least 24 hours the situation transparent and deposition form.
Among the present invention, the implication of term " Chrome-free " is: in the compsn total amount of chromium less than 1ppm, preferable less than 0.1ppm.Can accumulate in the compsn in this small additions of chromium below total amount, because in the processing at the bottom of containing zinc-base, this contains at the bottom of the zinc-base and the compound inorganic component that can be used as alloy compositions or the pretreated metal base of conduct process of small additions of chromium.
Among the present invention, term " contains zinc " and refers to the metallic surface that is made up of zinc and its alloy.Here in the alloy content of zinc greater than 40%.Therefore, at the bottom of the zinc-containing metal substrate comprises zinc-base, hot-galvanized steel substrate, electrolytic zinc steel base,
and
" vanadium ion " described in the present invention is meant the v element that exists with ionic condition, and its ionic condition can be charged vanadium atom, like V
5+, or the charged atomic group that contains vanadium atom, like VO
3 -, VO
4 3-
The experiment proof; Through compsn conversion coated of the present invention handled contain zinc-base at the bottom of extraordinary short-term erosion resistance and paint adhesion property are arranged; The described compsn that is used for the substrate of conversion coated zinc-containing metal; Be aqueous chromium-free solution, comprise component: (a) phosphoric acid, (b) fluorine titanium complex and (c) vanadium ion source; Said each components contents is respectively: the concentration of vanadium ion (c) in said composition that is provided by the vanadium ion source is 1g/L～20g/L; Vanadium ion (c) is 1: 4～1: 2 with the mol ratio of phosphate anion (a) in said composition that is provided by phosphoric acid, and vanadium ion (c) is 3: 2～3: 1 with the mol ratio of fluorine titanium complex (b) in said composition simultaneously.
The compsn that does not satisfy specific molar ratio between above-mentioned vanadium ion and phosphate anion or the fluorine titanium complex is to solve technical problem that the invention described above mentions.
If the mol ratio of vanadium ion and phosphate anion has surpassed 1: 2 of regulation, the compsn of this aqueous chromium-free conversion coated will become unstable and have deposition to take place.On the other hand, above-mentioned ratio be less than can causing compsn to become muddy at 1: 4, contain zinc-base with this compositions-treated at the bottom of, can obtain relatively poor corrosion test result.Obtain best corrosion resistance, in the said composition mol ratio of vanadium ion and phosphate anion best >=1: 3.
Correspondingly, the ratio of vanadium ion and fluorine titanium complex was greater than 3: 1 o'clock of regulation in the compsn of aqueous chromium-free conversion coated of the present invention, and the corrosion resistance of handling the inorganic layer that obtains after the zinc-containing metal substrate with said composition is not good.Obtain best erosion resistance, in the said composition ratio of vanadium ion and fluorine titanium complex best≤2: 1.
The contriver also finds; If when also comprising one or more the composition (d) in the fluorine mixture that is selected from boron and/or silicon in the compsn of aqueous chromium-free conversion coated of the present invention; Like sodium tetrafluoroborate, ammonium borofluoride, hexafluorosilicic acid and sodium hexafluorisilicate, then help the formation of inorganic layer.Form intensive conversion coating on these fluorine mixtures help at the bottom of containing zinc-base, can also improve adhesive power when especially using silicon compound next step organic coating of smearing.
Yet as the part of the composition of the compsn of the present invention that forms inorganic conversion coating on can be at the bottom of containing zinc-base, most important metal and metalloid element are v element and titanium elements.Therefore, what the mol ratio of the fluorine mixture of vanadium ion and boron and/or silicon was preferable is >=1: 1, and more preferable is >=3: 2.In the compsn of aqueous chromium-free conversion coated, the relative content of the fluorine mixture of boron and/or silicon is unfavorable for the formation of the inorganic conversion coating of passivation when bigger.Vice versa, in the compsn mol ratio of the fluorine mixture of vanadium ion and boron and/or silicon greater than 4: 1 o'clock, its protection against corrosion and just invisible to the beneficial effect of paint adhesion.
In the compsn of the present invention, preferable vanadium ion source is the vanadium atom Oxidation Number greater than the vannadate of+III valency.Thereby these vannadate add the compsn that forms conversion coated of the present invention in the waterborne compositions to as alkaline solution.In addition, preferable vanadium ion source also can be a compound, like vanadium dioxide (IV), Vanadium Pentoxide in FLAKES (V), sodium metavanadate (V) and ammonium meta-vanadate (V).The present invention most preferably vanadium is+the vanadium ion source of V valency.
Compsn of the present invention is used for the preferable vanadium ion consumption of coating-type cladding process and is further defined to≤14g/L, after drying, can form the inorganic layer that approaches so that it for example coats the wet film that the metallic surface forms with the extruding rod.Vice versa, the vanadium ion consumption preferable greater than 6g/L, better can obtain a kind of compsn during greater than 10g/L, it can form uniform inorganic conversion coating after being coated on the wet film drying that the metallic surface forms.
For the compsn that obtains stable aqueous chromium-free conversion coated of the present invention and suitable for containing etch rate at the bottom of the zinc-base, the compsn of water-based conversion coated of the present invention is an acidic solution.What the pH value was preferable is>=1, and better is>=2, and best is>=3, still≤4.3.
Usually, the content of organic polymer is extremely micro-in these compsns of the present invention, is not more than 1ppm.This organic polymer is the silane as in this area, often having, resin or wax etc.More high-load organic polymer can form inorganic-organic mixed coating, the heat impedance of this coating and weldability are all than being that inorganic coating-type coating is poor fully.Contain at the bottom of the zinc-base with after preferred pure inorganic compsn of the present invention contacts, can bear 400 ℃ of peak at least 5 minutes and do not have the variation of any surface color and the reduction of corrosion resistance and paint adhesion.
Compsn of the present invention does not contain nitrate ion source or the nitrite ion source that any content is higher than 1ppm, preferable any nitrate ion source or the nitrite ion source of not containing fully.In the coating-type surface treatment process or in heat-processed; Especially weld in the zinc-containing metal substrate process that the compsn conversion coated that contains a large amount of nitrate ion source or nitrite ion source is crossed, contain these compound compositions and may discharge dangerous nitrogenous gas.
The preparation method of the present composition be this area conventional with each component method of mixing, also can get in addition by following compositions formulated dilute with water.
The invention still further relates to a kind of compositions formulated; Can produce the compsn that above-mentioned aqueous chromium-free is used for the substrate of conversion coated zinc-containing metal through this compositions formulated of dilute with water; Be aqueous chromium-free solution, comprise following component: (a) phosphoric acid, (b) fluorine titanium complex and (c) vanadium ion source; Wherein the vanadium ion concentration that provides of vanadium ion source is no more than 85g/L, but is not less than 20g/L, and this compositions formulated will satisfy:
I) mol ratio of vanadium ion and the phosphate anion that provides by phosphoric acid >=1: 4, preferable >=1: 3, but be not more than 1: 2; With,
The ii) mol ratio of vanadium ion and fluorine titanium complex >=3: 2, but be not more than 3: 1, preferable is not more than 2: 1.
In this compositions formulated, vanadium ion content can not be higher.Because the solubleness of each composition in water is conditional concerning this compositions formulated, wherein the concentration of vanadium is approximately 85g/L.Therefore, according to the present invention, when the concentration of each water composition was higher, it is unstable that said composition becomes, and the deposition of composition can take place.
In another embodiment, this compositions formulated can also directly be applied in and contain at the bottom of the zinc-base.In addition, this compositions formulated of better dilutable water, making the ratio of itself and water is >=1: 10, more preferable is >=1: 4.Concentration such as vanadium is this configuration groups compound of 20g/L, promptly can directly be coated on to contain at the bottom of the zinc-base, also can apply behind the dilute with water, specifically selects any mode to determine according to the actual needs at scene.For the application of this configuration groups compound of other concentration, also be like this.
The preparation method of this compositions formulated also be this area conventional with each component method of mixing.
In a word, the present invention mainly provides a kind of compsn, is aqueous chromium-free solution, comprises component: (a) phosphoric acid, (b) fluorine titanium complex and (c) vanadium ion source; Wherein, The concentration of vanadium ion (c) in said composition that is provided by the vanadium ion source is 1g/L～85g/L; Vanadium ion (c) is 1: 4～1: 2 with the mol ratio of phosphate anion (a) in said composition that is provided by phosphoric acid, and vanadium ion (c) is 3: 2～3: 1 with the mol ratio of fluorine titanium complex (b) in said composition simultaneously.Said composition can directly be used for the substrate of conversion coated zinc-containing metal; Particularly vanadium ion concentration is that the said composition of 1g/L～20g/L directly is used for the substrate of conversion coated zinc-containing metal preferable effect is arranged; Vanadium ion concentration is that the said composition of 20g/L～85g/L can be according to the actual needs at scene, and selecting directly to be used for conversion coated still is conversion coated zinc-containing metal substrate again behind the dilute with water.
The invention also discloses the method that in the zinc-containing metal substrate, forms one deck conversion coating, wherein the zinc-containing metal substrate is contacted with the compsn of aqueous chromium-free conversion coated of the present invention simply.
Usually, the treatment soln in this method, the compsn of aqueous chromium-free conversion coated promptly of the present invention can like immersion, spraying, wiping and rubber roll extrusion and/or roll squeezer application etc., be coated on the metallic surface according to the industrial coating technology of routine.
Use these paint-on techniques, zinc-containing metal surface is with after treatment soln contacts, and the compsn wet film that adheres to the aqueous chromium-free conversion coated of metal base must be dried immediately.Furnace drying method is preferably accomplished under aforesaid middle cleaning step.Such coating method is called the coating-type cladding process and/or does not have the cleaning cladding process with T.T..After the odor component evaporation in the adherent treatment soln in metallic surface, conversion coating has just formed.
The preferable peak of coating-type cladding process is at least 60 ℃, and better is 80 ℃, but preferable can not be above 120 ℃.Under lower peak, drying process is not only consuming time, and technique effect is poor.Therefore on the contrary, under higher peak, the increase of moisture evaporation speed has hindered the formation of conversion coating, can only be settled out less inorganic layer, and can't contain all chemical conversions of zinc-base basal surface with whole.
The present invention also comprises the zinc-containing metal substrate itself of conversion coated according to the method for the invention, and wherein the quality of the desciccator diaphragm of conversion coating (being dry film) is at least 0.15g/m
2, preferable be 0.3g/m at least
2, but can not be greater than 2g/m
2, preferable can not be greater than 1g/m
2, best can not be greater than 0.6g/m
2
The weight of the conversion coating desciccator diaphragm by in the zinc-containing metal substrate, applying slim wet film that pure inorganic water-based paint compositions of the present invention forms is restricted.Because the mechanical stability of pure inorganic coating reduces along with the increase of film thickness.Therefore, in a preferred embodiment, the concentration of organic polymer can not be greater than 1ppm in the coating composition of the present invention, and the weight of desciccator diaphragm is no more than 1g/m
2
The zinc-containing metal substrate of handling according to the present invention can be used to coated with multiple layer coating above that in the Industrial Metal field of surface treatment.Layered coating comprises one deck organic coating at least, and it is as last top layer coating or paint, or as primer base.Wherein, these coating are the existing coating in the metal finishing industry.
Of the present invention by conversion coated the purposes of zinc-containing metal substrate mainly be but be not limited to produce white goods, household electrical appliance, vehicle and in building industry.The present invention is natural comprises that also erosion resistance and paint adhesion property are basic prerequisites and contain other similar purposes at the bottom of the zinc-base by what the compsn of inorganic conversion coated of the present invention was given.
Each raw material described in the present invention or reagent are all commercially available to be got.
Than prior art, beneficial effect of the present invention is following: in the compsn of the present invention the content of organic polymer extremely trace be not more than 1ppm, make coating have excellent heat impedance and weldability; Also do not contain any nitrate ion source or the nitrite ion source that may discharge dangerous nitrogenous gas fully; Need not pass through extra cleaning after being used to contain the surface conversion treatment of Zinc material, particularly need not carry out chromating and clean, so the conversion processing step be simple, can not cause pollution of chromium simultaneously yet environment.
Embodiment
Further specify the present invention with embodiment below.The experimental technique of unreceipted actual conditions in the following example, usually according to normal condition, or the condition of advising according to manufacturer.Concerning the technician of field of metal surface treatment, obviously, the number of chemical reaction can take place in the compound in the prescription of combinations thing, and therefore should not be understood that to analyze said composition can detected composition.
Embodiment 1 compsn of the present invention and compositions formulated
Compsn A of the present invention, B, C, D, H, I, J and K, compositions formulated L, M and N press table 1,3,4 each component are mixed, and use water dissolution then.Wherein the component Vanadium Pentoxide in FLAKES is with containing 3.17wt%V
2O
5, the amount that the alkaline solution adding of 3.65wt%NaOH needs.The component vanadium dioxide is with containing 3.17wt%VO
2, the amount that the alkaline solution adding of 5.32wt%NaOH needs.Other components are simple the mixing.The mol ratio of special element is seen table 2 and 5 in each compsn.Compositions formulated L and the M compsn that is used for the substrate of conversion coated zinc-containing metal of the present invention that 10 times and 4 times of dilute with waters can be stable respectively.Compositions formulated N need not dilute, and can directly be used for the substrate of conversion coated zinc-containing metal.Compsn A of the present invention, B, C, D, H, I, J and K and compositions formulated L, M and N are the stable aqueous solution, and wherein the total content of chromium is all less than 0.1ppm, and do not contain organic polymer, nitrate radical or nitrite ion source fully.The concentration of vanadium ion is respectively 12.4g/L, 11.5g/L, 10.6g/L, 11.5g/L, 1.4g/L, 14g/L, 6.3g/L, 19.7g/L, 84g/L, 43.5g/L and 20g/L in each compsn.
Table 1. compsn A of the present invention, B, C and D
The mol ratio of special element among table 2. compsn A of the present invention, B, C and the D
The component of table 3. compsn H of the present invention, I, J, K and compositions formulated L, M, N
The component concentration of table 4. compsn H of the present invention, I, J, K and compositions formulated L, M, N
The mol ratio of special element among table 5. compsn H of the present invention, I, J, K and compositions formulated L, M, the N
The method of embodiment 2 zinc-containing metal substrates and conversion coating
To contain zinc steel base (HDG, hot dip galvanization steel plate respectively; EG, the electrogalvanizing steel plate; GL, Galvalume
) contact (seeing table 6) with compsn A-D of the present invention.After the contact,, the compsn wet film that adheres to this zinc-containing metal substrate surface is dried immediately without middle cleaning step.Drying used peak is as follows.Wherein, represent the HDG substrate that first is handled with compsn A like " A-HDG-1 ".The dry film quality of the zinc-containing metal substrate conversion coating that forms is seen table 6.
60℃：A-HDG-1，B-GL-1，B-EG-1，C-HDG-2，D-EG-1。
80℃：B-HDG-1，B-GL-2，B-EG-2，C-EG-1。
100℃：A-HDG-2，C-EG-2，D-EG-2。
120℃：B-HDG-3，D-HDG-1。
Compositions formulated L and M respectively behind dilute with water 10 and 4 times gained solution and compositions formulated N stoste apply as stated above respectively and contain zinc steel base HDG, wherein peak is 80 ℃, the dry film quality of gained conversion coating is respectively 0.15,1 and 2g/m
2
Further specify beneficial effect of the present invention through Test Example below.
Effect embodiment 1
(HDG, EG GL) white rust (seeing table 6) occurs with undressed steel base to the various steel base that apply with neutral salt spraying experiment (NSST) compsn A-D more of the present invention.In the neutral salt spray testing, being used in the different white rusts that form on containing at the bottom of the zinc-base is (according to the ASTM B117-03) that bibliographical information is arranged as the erosion-resisting index of short-term.
Visible from table 6, the prescription of table 1-2 obviously can provide anti-corrosion protection.Behind the hot dip galvanization steel plate one hour, the area that undressed galvanized steel sheet surface forms white rust reaches 100%.Even and all types of steel plate galvanizeds of handling with the present invention expose a couple of days in the NSST experiment after, the formation of surface white rust still receives significantly and suppressing.
The comparison that white rust appears in various steel base that table 6. applies with compsn A-D of the present invention in neutral salt spraying experiment and undressed steel base
With the similar compositions-treated of present composition type, but the content of phosphate anion or fluorine titanium complex exceeds the molar ratio range of the present invention's regulation in the said composition with these steel plates.These compsns similar with present composition type are E, F, G.The composition of these non-compsns of the present invention except that shown in the table 7 is with present composition C.Table 8 shown these processing steel plate galvanized in the neutral salt spray testing, form the result of white rust.
The non-2.06wt%V that contains of the present invention of table 7.
2O
5Compsn E, F and G in the mol ratio of special element
The middle generation that is coated with different steel base white rusts with non-present composition E-G of table 8. neutral salt spray testing (NSST)
Visible from table 8, when too high, compsn is not only muddiness, opaque to phosphorus acid ion concentration with the ratio of vanadium ion concentration, and the neutral salt spray testing result relatively poor (seeing the Comparative Examples E-HDG-1 of table 8) who obtains when being coated with said composition according to the method for the invention.When the mol ratio of vanadium ion in the compsn of water-based conversion coated and fluorine titanium complex surpasses the scope of the present invention's regulation, also obtained similar result (seeing Comparative Examples F-HDG-1 and G-HDG-1).
Those skilled in the art can predict the modification to above-mentioned disclosed embodiment in context of the present invention.Therefore, the present invention does not receive the restriction of disclosed embodiment, and covers all modifications within the scope of the present invention.
Claims (28)
1. a compsn that is used for the substrate of conversion coated zinc-containing metal is characterized in that, it is an aqueous chromium-free solution, comprises component: (a) phosphoric acid, (b) fluorine titanium complex and (c) vanadium ion source; Said each components contents is respectively: the concentration of vanadium ion (c) in said composition that is provided by the vanadium ion source is 1g/L～20g/L; Vanadium ion (c) is 1: 4～1: 2 with the mol ratio of phosphate anion (a) in said composition that is provided by phosphoric acid, and vanadium ion (c) is 3: 2～3: 1 with the mol ratio of fluorine titanium complex (b) in said composition simultaneously.
2. compsn as claimed in claim 1, wherein, described vanadium ion (c) is 1: 3～1: 2 with the mol ratio of phosphate anion (a).
3. compsn as claimed in claim 1 is characterized in that, described vanadium ion (c) is 3: 2～2: 1 with the mol ratio of fluorine titanium complex (b).
4. compsn as claimed in claim 1 is characterized in that, also contains composition (d), and it is selected from the fluorine mixture of boron and/or silicon.
5. compsn as claimed in claim 4 is characterized in that, the fluorine mixture of described boron and/or silicon is sodium tetrafluoroborate, ammonium borofluoride, hexafluorosilicic acid or sodium hexafluorisilicate.
6. compsn as claimed in claim 4 is characterized in that, vanadium ion (c) is 1: 1～4: 1 with the mol ratio of the composition (d) of the fluorine mixture that is selected from boron and/or silicon.
7. compsn as claimed in claim 6 is characterized in that, vanadium ion (c) is 3: 2～4: 1 with the mol ratio of the composition (d) of the fluorine mixture that is selected from boron and/or silicon.
8. compsn as claimed in claim 1 is characterized in that, described vanadium ion source is the vanadium atom Oxidation Number greater than the vannadate of+III valency.
9. compsn as claimed in claim 1 is characterized in that, described vanadium ion source is selected from vanadium dioxide, Vanadium Pentoxide in FLAKES, sodium metavanadate and ammonium meta-vanadate.
10. compsn as claimed in claim 1 is characterized in that, the concentration of the described vanadium ion that is provided by the vanadium ion source (c) in said composition is 6g/L～14g/L.
11. compsn as claimed in claim 10 is characterized in that, the concentration of the described vanadium ion that is provided by the vanadium ion source (c) in said composition is 10g/L～14g/L.
12. compsn as claimed in claim 1 is characterized in that, the pH of described compsn is 1～4.3.
13. compsn as claimed in claim 12 is characterized in that, the pH of described compsn is 2～4.3.
14. compsn as claimed in claim 13 is characterized in that, the pH of described compsn is 3～4.3 for the best.
15. thereby a compositions formulated of passing through water with its each described compsn of dilution formation claim 1～14 is characterized in that it is an aqueous chromium-free solution, comprises component: (a) phosphoric acid, (b) fluorine titanium complex and (c) vanadium ion source; Above-mentioned each components contents is respectively: the concentration of vanadium ion (c) in this compositions formulated that is provided by the vanadium ion source is 20g/L～85g/L; Vanadium ion (c) is 1: 4～1: 2 with the mol ratio of phosphate anion (a) in this compositions formulated that is provided by phosphoric acid, and vanadium ion (c) is 3: 2～3: 1 with the mol ratio of fluorine titanium complex (b) in this compositions formulated simultaneously.
16. compositions formulated as claimed in claim 15 is characterized in that, the mol ratio of vanadium ion and phosphate anion is 1: 3～1: 2, and the mol ratio of vanadium ion and fluorine titanium complex is 3: 2～2: 1 simultaneously.
17. compositions formulated as claimed in claim 15 is characterized in that, the Dilution ratio of this compositions formulated and water is >=1: 10.
18. compositions formulated as claimed in claim 17 is characterized in that, the Dilution ratio of this compositions formulated and water is >=1: 4.
19. a method that in the zinc-containing metal substrate, forms conversion coating is characterized in that, each described compsn in zinc-containing metal substrate and a kind of claim 1～14 is contacted.
20. method as claimed in claim 19 is characterized in that, described zinc-containing metal substrate is dried the compsn wet film that adheres to this zinc-containing metal substrate surface with after described compsn contacts immediately.
21. method as claimed in claim 20 is characterized in that, the method for described oven dry is for directly drying described zinc-containing metal substrate without middle cleaning step.
22. method as claimed in claim 21 is characterized in that, in the method for described oven dry, the zinc-containing metal substrate is with 60 ℃～120 ℃ dryings of peak.
23. method as claimed in claim 22 is characterized in that, the peak of described zinc-containing metal substrate is 80 ℃～120 ℃.
24. the zinc-containing metal substrate with each described method conversion coated in the claim 19～23 is characterized in that the dry film quality of conversion coating is 0.15～2g/m
2
25. zinc-containing metal substrate as claimed in claim 24 is characterized in that, the dry film quality of said conversion coating is 0.15～1g/m
2
26. zinc-containing metal substrate as claimed in claim 25 is characterized in that, the dry film quality of said conversion coating is 0.3～0.6g/m
2
27. the described zinc-containing metal substrate of claim 24 is used for the purposes of coating multiple coating in this zinc-containing metal substrate in the metal finishing of industry.
28. white goods, household electrical appliance, vehicle and the purposes in construction industry are being produced in the described zinc-containing metal substrate of claim 24.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100965269A CN101580654B (en) | 2008-05-12 | 2008-05-12 | Composition for converting and coating zincous metal base and processing method thereof, and processed zincous metal base and purpose thereof |
| PCT/CN2009/071731 WO2009138022A1 (en) | 2008-05-12 | 2009-05-11 | A composition for conversion coating a zinciferous metal substrate, a method for treating a zinciferous metal substrate, a treated zinciferous metal substrate and its use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100965269A CN101580654B (en) | 2008-05-12 | 2008-05-12 | Composition for converting and coating zincous metal base and processing method thereof, and processed zincous metal base and purpose thereof |
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| Publication Number | Publication Date |
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| CN101580654A CN101580654A (en) | 2009-11-18 |
| CN101580654B true CN101580654B (en) | 2012-04-18 |
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| CN2008100965269A Expired - Fee Related CN101580654B (en) | 2008-05-12 | 2008-05-12 | Composition for converting and coating zincous metal base and processing method thereof, and processed zincous metal base and purpose thereof |
Country Status (2)
| Country | Link |
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| CN (1) | CN101580654B (en) |
| WO (1) | WO2009138022A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107868548A (en) * | 2017-12-06 | 2018-04-03 | 立邦（上海）化工有限公司 | Antiseptic treating agent and its production method for alumina-base material |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102212813B (en) * | 2010-04-12 | 2013-11-06 | 富准精密工业(深圳)有限公司 | Magnesium alloy forming solution and preparation method thereof |
| CN108796584B (en) * | 2017-04-28 | 2020-08-25 | 宝山钢铁股份有限公司 | Flexible control method for surface passivation film structure of tinned product |
| US11293104B2 (en) * | 2017-06-27 | 2022-04-05 | Bulk Chemicals, Inc. | Inorganic non-chrome aqueous treatment composition and process for coating metal surfaces |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101103139A (en) * | 2005-01-14 | 2008-01-09 | 亨克尔两合股份公司 | Stable, non-chrome, thin-film organic passivates |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3977877B2 (en) * | 1995-10-04 | 2007-09-19 | ディップソール株式会社 | Electrochemical conversion solution for metal surface treatment and electrolytic conversion treatment method |
| US6027579A (en) * | 1997-07-07 | 2000-02-22 | Coral Chemical Company | Non-chrome rinse for phosphate coated ferrous metals |
| US7815751B2 (en) * | 2005-09-28 | 2010-10-19 | Coral Chemical Company | Zirconium-vanadium conversion coating compositions for ferrous metals and a method for providing conversion coatings |
-
2008
- 2008-05-12 CN CN2008100965269A patent/CN101580654B/en not_active Expired - Fee Related
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2009
- 2009-05-11 WO PCT/CN2009/071731 patent/WO2009138022A1/en active Application Filing
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101103139A (en) * | 2005-01-14 | 2008-01-09 | 亨克尔两合股份公司 | Stable, non-chrome, thin-film organic passivates |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107868548A (en) * | 2017-12-06 | 2018-04-03 | 立邦（上海）化工有限公司 | Antiseptic treating agent and its production method for alumina-base material |
| CN107868548B (en) * | 2017-12-06 | 2020-03-17 | 立邦（上海）化工有限公司 | Anticorrosion treating agent for aluminum-based material and production method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101580654A (en) | 2009-11-18 |
| WO2009138022A1 (en) | 2009-11-19 |
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