CN1090606A - The phosphate conversion coating composition of substantially nickel-free and method - Google Patents

The phosphate conversion coating composition of substantially nickel-free and method Download PDF

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CN1090606A
CN1090606A CN93119949A CN93119949A CN1090606A CN 1090606 A CN1090606 A CN 1090606A CN 93119949 A CN93119949 A CN 93119949A CN 93119949 A CN93119949 A CN 93119949A CN 1090606 A CN1090606 A CN 1090606A
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ion
phosphate coating
composition
forms
dissolved
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CN1092245C (en
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R·W·米勒
M·派特彻尔
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Henkel Corp
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Henkel Corp
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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
    • C23C22/07—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 phosphates
    • C23C22/08—Orthophosphates
    • C23C22/12—Orthophosphates containing zinc cations
    • 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
    • C23C22/07—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 phosphates
    • C23C22/08—Orthophosphates
    • C23C22/12—Orthophosphates containing zinc cations
    • C23C22/13—Orthophosphates containing zinc cations containing also nitrate or nitrite anions
    • 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
    • C23C22/07—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 phosphates
    • C23C22/08—Orthophosphates
    • C23C22/18—Orthophosphates containing manganese cations
    • C23C22/186—Orthophosphates containing manganese cations containing also copper cations
    • 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
    • C23C22/362—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 also zinc cations
    • 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
    • C23C22/368—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 magnesium cations

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  • 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)
  • Paints Or Removers (AREA)
  • Glass Compositions (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

Nickel in the conventional low nickeliferous phosphate conversion coating composition of zinc can be replaced by the obviously little cupric ion of concentration and can not lose quality-advantage, and this advantage was originally impelled and add nickel in low zinc phosphatizing composition; In fact, follow the remarkable decline of cost, can reach alkali resistance and paint adhesion power preferably.

Description

The phosphate conversion coating composition of substantially nickel-free and method
The present invention relates to a kind ofly can on the reactive metal surface, form the composition and the method for phosphate conversion coating, in order that improve treated or on conversion coating, carry out the erosion resistance on follow-up conventional overcoating (forming as paint or varnish) surface afterwards by the organic radical protective layer.Composition of the present invention is particularly suitable for handling various matrix metals, comprises steel and galvanized steel and aluminium and aluminum base alloy at least.
Various phosphate conversion coating compositions and method early have been described in the prior art, it is believed that in general current coating with extra best best is to comprise those of zinc, nickel and at least a other divalent metal such as manganese in the composition.
In this manual, except embodiment and claims and specialize opposite Anywhere, the numeral explanation of all inventories or reaction conditions or purposes all can be regarded as by " approximately " within the scope of the invention and changes, and it is preferred implementing the present invention usually in specified digital scope.
Hinted that in some papers nickel is carcinogens, so that require in metal finishing, to avoid using it for healthy reason.Nickel also is considered to serious pollutent, is that nickel is very big for the cost impact of zinc phosphate conversion coating composition under every liter of 0.5-1.5 gram (hereinafter often being abbreviated as " g/l ") in its concentration commonly used.The objective of the invention is to reduce or eliminate the use of nickel, but can not make conversion coating debase by the composition acquisition that contains zinc, nickel and manganese of routine.
A kind of enforcement composition of the present invention is a kind of aqueous liquid composition, and said composition contains, preferably basically by, form by water and following material better:
(A) 3-50,5-20,13-18g/l dissolved phosphate ion better preferably;
(B) from 0.2 to 3, or with specified order preferably incrementally from 0.45 to 2.0, the Zn of dissolved of 0.57-1.24,0.60-0.95 or 0.71-0.87g/l + 2Ion;
(C) from 1 to 200, or with specified order preferably incrementally from 20 to 100,24-74 or 24-60mg/l be dissolved Cu + 2Ion;
(D) the conventional promotor of the significant quantity except that nitrate ion;
(E) from 5 to 40, or with specified order preferably incrementally from 7-25, the total acid of 13-24,16-22 or 18-21 " value "; With
(F) from-1.0 to+3.0, or with preferred incrementally from-0.5 to+1.5 or-0.5 to+1.0 the free acid value of specified order; To giving non-aluminum base body and the service temperature more than 40 ℃, can be to 0.08 or to be more preferably free acid value be 0.35-0.65; If but when being lower than that 40 ℃ down operation or matrix are aluminium, then scope be-0.5-00, or free better value is-0.5-0.2; And randomly
(G) the highest 2g/l, preferably 0.1-0.8g/l, or the better total Mn of 0.40-0.65g/l + 2And Co + 2Ion;
(H) be up to 2g/l, 0.5-1.0 preferably, or be the Mn of 0.70-0.80g/l better 2+Ion, and randomly,
(J) be up to 5.5, preferably 1.0-4.0 is the free fluorochemical (pressing the sensitive determination of electrode of fluorochemical) of 1.5-2.5g/l better; And randomly,
(K) be not more than 40, or preferably incrementally be not more than 20 or the SO of 11g/l with specified order 4 -2Ion; And randomly
(L) be not more than 4.5, or with the No of specified order preferred incrementally no more than 3.4,2.0,1.8,1.3 or 1.0g/l 3 -
Be appreciated that the explanation of the composition of relevant ionic species has herein hinted that there is the corresponding ion of some opposite charges in maintenance neutral charge fashion ought composition being done as a whole.
For free acid that is used for this paper and total acid " value ", be defined as milliliter (hereinafter " the ml ") number of the required 0.1N NaOH of titration 10ml composition sample solution, for total acidometric titration to phenolphthalein terminal point (pH9.0), it is fixed to bromothymol blue terminal point (pH3.8) then to disappear for free acid, unless pH was just greater than 3.8 when said composition began, free acid value then is defined as the negative value of titration 10ml composition sample to the required 0.1N strong acid solution of pH3.8 ml number at that time.
Thereby a kind of method of the present invention comprises the metallic surface that desire is handled at least contacts the sufficiently long time forms detectable conversion coating on its metallic surface step with the present composition.If necessary at the metal that desire is handled with before the present composition contact, can use common metal cleaning surfaces and/or activation step, and common be preferred with its part as the inventive method.The inventive method can also and be preferably in metallic surface that desire handles usually and contacts with the present composition and comprise the conventional steps that some are follow-up afterwards.These subsequent steps for example can comprise the post-reaction treatment with water rinse, any routine, for example, use USP4,963,596 compositions of being instructed or use chromate-containing solution, and japanning or protect the surface with organic radical solid material external coating (EC).
Another one embodiment of the present invention is a concentrate composition, according to the above-mentioned enforcement composition of this scheme unstable promotor composition of dilute with water or dilute with water and interpolation such as nitrite ion is prepared.
Optimum implementation
The required phosphate ion of the present composition is PO preferably 4 -3Ion or other are because of ortho-phosphoric acid (H 3PO 4) not exclusively ionization and other ion of producing.The phosphoric acid of any free unionization that may exist all is counted as the part of phosphate ion content, its stoichiometry and PO 4 -3The ion unanimity.Other free phosphoric acid such as metaphosphoric acid and condensed phosphoric acid such as tetra-sodium and the ion that all are produced by them all can be used for providing the phosphate ion of necessity.Preferred phosphate ion is that neutrality or the acid salt by the metallic cation of ortho-phosphoric acid and/or above-mentioned part as the present composition produces.
Need preferably produce as the zinc cation of a said composition part by ortho-phosphoric neutrality or acid zinc salt, can be in containing this sour solution and form then and there by solving zinc or zinc oxide or zinc hydroxide.Need can produce as copper sulfate and/or cupric nitrate by salt as the cupric ion of a present composition part, also can in the used phosphoric acid of part, obtain by dissolved oxygen copper.
Required promotion composition preferably comprises a kind of in the following material at least in the present composition: (ⅰ) from 0.01 to 0.2g/l nitrite ion (ⅱ), and the H from 0.5 to 5g/l 2O 2(ⅲ) mononitro-benzene sulfonate ion from 0.05 to 2g/l, (ⅳ) from 0.05 to 2g/l-the nitrobenzoyl acid ion, (ⅴ) from 0.05 to 2g/l right-nitrophenols, (ⅵ) from 0.1 to 10, reasonable from 0.5 to 6, or better from 0.5 to 2.0g/l(by stoichiometric calculation equivalent as azanol) can the aqueous solution, produce the composition of azanol.This promotor is hydroxylamine sulfate (hereinafter often being abbreviated as " HAS ") or similarly safety and the dissolved azanol source that is easy to get best.The promotor of second kind of the best is nitrite ion.
The acidity of the present composition is preferably from phosphoric acid, sulfuric acid and/or nitric acid.
The part or even whole free fluorochemicals all can be from complex fluorides ion such as fluoroborate (BF 4 -2), fluohafnate (HfF 4 -2), silicofluoride (SiF 5 -2), fluotitanate (TiF 6 -2), fluozirconate (ZrF 6 -2) and composition thereof; More preferably scheme is to produce from fluoroborate and silicofluoride and composition thereof.Yet simple fluorochemical such as alkaline metal fluoride cpd also are the free fluoride sources that is entirely satisfactory.
For the various described component that preferably increases progressively with specified order and have independent preferred property, the present composition only contains 0.5,0.2,0.10,0.07,0.03,0.01,0.005 or the various Ni of 0.001g/l + 2, have trivalent or any positively charged ion of high price more, comprise the chloride ion and the chlorate ion of complexing chloride ion.If when the amount of chloride ion is enough measured with analytical procedure at an easy rate, network fluoride ionic concn (g/l) and chloride ion concentration (g/l) ratio were at least 8: 1, or were at least preferably 14: 1.
In the method for the invention, the metallic surface that desire is handled can be by spraying with contacting of the present composition, and dipping or any other ordinary method or combined method are finished.The temperature of handled metallic surface and present composition contact process preferably incrementally is in the scope of 21-85,25-55 or 31-44 ℃ with described order.The present composition be converted the total time that contacts between the coated metal surface, with described order preferably incrementally in the scope of 5 seconds-15 minutes (hereinafter often being abbreviated as " min "), 15 seconds (hereinafter often being abbreviated as " sec ")-10min, 30sec-50min or 90-120sec.Formed phosphate coating quality increased value preferably incrementally is that every square metre of desire surface treated (is " g/m hereinafter at 1.1-5.4,1.6-4.3 or 2.2-3.8 gram with described order 2") scope in, weight of copper per-cent in the coating that is generated is preferably 0.50-10,1.0-8.0,2.0-6.0,3.0-4.1 when preferably increasing progressively with described order.
Can further estimate the present invention according to the following example and Comparative Examples, the intention of these examples is explanation rather than restriction the present invention.
Composition embodiment and Comparative Examples group I
These compositions except a Comparative Examples, all are the uses of explanation HAS promotor.Tabulate down and 1 list special composition.These compositions, except Comparative Examples 13 is by the preparation of the enriched material of commercial compound, all by the preparation of following universal program: use the water yield that approximates the final required volume of water 3/4ths of said composition greatly during beginning, and the primary zinc phosphate of capacity is dissolved in this water in order to be enough to be provided at the final volume required zine ion that contains desired concn.For required phosphate ion ultimate density can be provided in required final volume, 75% positive acid solution of q.s is added with added primary zinc phosphate in advance.For required fluoride ion concentration, required azanol concentration and some vitriol, cupric ion and part of sulfuric acid salt ionic concentration, any required manganese cation concn and any required magnesium ion concentration are provided, can be by Sodium Fluoride, HAS, cupric sulfate pentahydrate, manganous nitrate, magnesium hydroxide or the magnesium nitrate of any order corresponding adding capacity in the previously prepared solution.At last, add sodium hydroxide solution and remaining water and produce the specific free acid and the total acid degree of depth to regulate said composition.
Have group I method for compositions example and Comparative Examples
Use cold-rolled steel, galvanized steel and/or automobile and instrument make in used conventional aluminium alloy experiment sheet material and through following process steps in sequence: (1) is in 43 ℃ of conventional alkali cleaning 120sec down; (2) wash 60sec down in 38 ℃; (3) conventional colloid titanium phosphate activator 30sec under 38 ℃; (4) in 35 ℃ or the 43 ℃ a kind of 120sec that contact that descend and tabulate down among the 1 composition 1-12; (5) in 20-25 ℃ of following cold rinse 60sec; (6) handle 30sec with containing the commercially available post-treatment composition of sexavalence and chromic routine; Use rinsed with deionized water 30sec with 177 down in 20-5 ℃.
Composition and method example set II
The universal method preparation identical with organizing I of these compositions, it is composed as follows: example 14 examples 15 except the nitric hydrate copper that uses Sodium Nitrite to replace HAS to do promotor and to use each cupric ion on average to have 2.5 molecular waters is done the copper source
The g/l of composition composition
Zn(NO 3) 24.74 3.6
75% water-bearing phosphate
(by weight) 12.4 20.4
Cu(NO 3) 2·2 1/2 H 2O 0.44 0.29
NaF 1.1 1.5
NaNO 20.12 0.11
Mn(NO 3) 22.3 -
Total acid value 17.0 18
Free acid value-0.3 0.4
In the process sequence that is being different from group 1 under 33 ℃, example 14 is used to spray phosphatizing, under 57 ℃, example 14 is used for impregnation of phosphoric acid salt with the process sequence that is different from above-mentioned group of I and handles.
Advantage of the present invention
Purpose of the present invention not only is to make cost to reduce and reduces and pollute, and the present invention also produced some unexpected and wonderful benefits, at least in its optimum implementation: improved erosion resistance; Alkaline corrosion particularly; Operate being lower than under the conventional Zn-Ni-Mn phosphatizing temperature condition; At least have much the same and be better quality sometimes; For the paint that is applied on the conversion coating good adhesive force power is arranged; With the coating of improving on surfaces containing zinc such as the galvanized steel.
Figure 931199492_IMG1

Claims (20)

1, a kind of aqueous liquid composition is made up of water and following ingredients substantially, and these compositions are
(A) the dissolved phosphate ion of the about 50g/L of about 3-;
(B) the about 3g/l dissolved of about 0.2-Zn + 2Ion;
(C) the about 200mg/l dissolved of about 1-Cu + 2Ion;
(D) the conventional promotor of the significant quantity except that nitrate ion;
(E) total acid value of about 5-about 40; With
(F) about+3.0 free acid values of pact-1.0-; Randomly,
(G) the total Mn of the highest about 2g/l + 2And Co + 2Ion; Randomly,
(H) Mg of the highest about 2g/L + 2Ion; Randomly,
(J) the highest about 5.5g/l presses the free fluorochemical of the sensitive determination of electrode of fluorochemical; Randomly,
(K) be not more than the SO of about 40g/l 4 -2Ion; Randomly,
(L) be not more than the NO of about 4.5g/l 3 -Ion; Randomly,
(M) be not more than the Ni of about 0.2g/l + 2Ion.
2, a kind of composition by claim 1, wherein:
(A) the about 20g/l of the about 5-of dissolved phosphate ion amount;
(B) dissolved Zn + 2The about 2.0g/l of the about 0.45-of ionic weight;
(C) dissolved Cu + 2The about 100mg/l of the about 20-of ionic weight;
(D) promotor comprises at least a (ⅰ) about 0.01-0.2g/l nitrite ion, (ⅱ) H of the about 5g/l of about 0.5- 2O 2; (ⅲ) the about 2g/l of about 0.05-between-the nitrobenzene-sulfonic acid salt ion, (ⅳ) between the about 2g/l of about 0.05--the nitrobenzoic acid salt ion, (ⅴ) the about 2g/l of about 0.05-right-nitrophenols and (ⅵ) the about 10g/l(of about 0.1-by the stoichiometric calculation equivalent of azanol) can in the aqueous solution, produce the composition of azanol;
(E) the about 7-of total acid " value " about 25;
(F) free acid value pact-0.5-about+1.5;
(G) (ⅰ) Mn + 2And Co + 2The about 0.8g/l of the about 0.1-of total ion concentration; Or (ⅱ) Mg + 2The about 0.5-of ionic concn about 1.0; Or (ⅲ) Mn + 2And Co + 2Two kinds of total ion concentrations and Mg + 2The ion degree of depth is in the scope of each ion defined in part (ⅰ) with (ⅱ);
(J) concentration (pressing fluorine thing sensitive electrode meter) the about 4.0g/l of about 1.0-of free fluorochemical;
(K) SO 4 -2Ionic concn is not more than about 11g/l; With
(L) NO 3 -2Ionic concn is not more than about 3.4g/l.
3, a kind of composition by claim 2, wherein:
(B) dissolved Zn + 2The about 1.24g/l of the about 0.57-of ionic weight;
(C) dissolved Cu + 2The about 74mg/l of the about 24-of ionic weight;
(E) the about 13-of total acid " value " about 24;
(F) free acid value pact-0.5-about+1.0; With
(L) NO 3 -1Ionic concn is not more than about 2.0g/l.
4, a kind of composition by claim 3, wherein:
(B) dissolved Zn + 2The about 0.95g/l of the about 0.60-of ionic weight;
(D) promotor comprises the nitrite ion of the about 0.2g/l of at least a about 0.01-and the about 6g/l(of the about 0.5-stoichiometric quantity by azanol) can in the aqueous solution, produce a kind of composition of azanol;
(E) the about 16-of total acid " value " about 22;
(F) the about 0.0-of free acid value about 0.8; With
(L) NO 3 -Ionic concn is not more than about 1.8g/l.
5, a kind of composition by claim 3, wherein:
(B) dissolved Zn + 2The about 0.95g/l of the about 0.60-of ionic weight;
(D) promotor comprises the nitrite ion of the about 0.2g/l of at least a about 0.01-and the about 6g/l(of the about 0.5-stoichiometric quantity by azanol) can in the aqueous solution, produce a kind of composition of azanol;
(E) the about 16-of total acid " value " about 22;
(F) free acid value pact-0.5-about 0.0; With
(L) NO 3 -Ionic concn is not more than about 1.8g/l.
6, a kind of composition by claim 5, wherein:
(A) the about 18g/l of the about 13-of dissolved phosphate ion amount;
(B) dissolved Zn + 2The about 0.87g/l of the about 0.71-of ionic weight;
(C) dissolved Cu + 2The about 60mg/l of the about 24-of ionic weight;
(D) promotor comprises at least a 0.01-0.2g/l nitrite ion and the about 2g/l(of the about 0.5-stoichiometric calculation equivalent by azanol) HAS;
(E) the about 18-of total acid " value " about 21;
(F) free acid value pact-0.5-about-0.2;
(G) (ⅰ) Mn + 2And Co + 2The about 0.65g/l of the about 0.40-of total ion concentration; Or (ⅱ) Mg + 2The about 0.80g/l of the about 0.70-of ionic concn; Or (ⅲ) Mn + 2And Co + 2Two kinds of total ion concentrations and Mg + 2Ionic concn is in the scope that condition (G) is stipulated already for various ions in (ⅰ) and (ⅱ); With
(L) NO 3 -Ionic concn is not more than about 1.3g/l.
7, a kind of composition by claim 4, wherein:
(A) the about 18g/l of the about 13-of dissolved phosphate ion amount;
(B) dissolved Zn + 2The about 0.87g/l of the about 0.71-of ionic weight;
(C) dissolved Cu + 2The about 60mg/l of the about 24-of ionic weight;
(D) promotor comprises at least a 0.01-0.2g/l nitrite ion and the about 2g/l(of the about 0.5-stoichiometric calculation equivalent by azanol) HAS;
(E) the about 18-of total acid " value " about 21;
(F) free acid value pact-0.5-about-0.2;
(G) (ⅰ) Mn + 2And Co + 2The about 0.65g/l of the about 0.40-of total ion concentration; Or (ⅱ) Mg + 2The about 0.80g/l of the about 0.70-of ionic concn; Or (ⅲ) Mn + 2And Co + 2Two kinds of total ion concentrations and Mg + 2Ionic concn is in the scope that condition (G) has been stipulated for each ion in (ⅰ) and (ⅱ); With
(L) NO 3 -Ionic concn is not more than about 1.3g/l.
8, a kind ofly do not comprising that aluminium makes on the metal base surface of its surface portion to form the method for phosphate coating, wherein the composition with claim 7 contacts matrix surface, the time of contact is in about 90-120sec scope, about 44 ℃ of the about 40-of temperature range, the about 3.8g/m of the about 2.2-of scope that the quality of the phosphate coating of formation increases 2, and weight of copper per-cent is in about 4.1 scopes of about 3.0-in formed phosphate coating.
9, a kind ofly comprising that aluminium makes on the metal base surface of its part surface to form the method for phosphate coating, wherein this matrix surface is contacted with the composition of claim 6, the about 120sec of the about 90-of time range that in the about 44 ℃ of scopes of about 31-, contacts, the about 3.8g/m of the about 2.2-of quality increase scope of formed phosphate coating 2, the weight percent of copper in the phosphate coating that forms is in the scope of about 3.0-about 4.1.
10, a kind ofly comprising the method that forms phosphate coating on aluminium is as the metal base surface of its part surface, wherein the matrix surface and the composition of claim 5 are contacted with the about 55 ℃ of about 5min of the about 30sec-of time range that contact down of about 25-, the about 4.3g/m of the about 1.6-of quality increase scope of formed phosphate coating 2, the weight percent about 2.0-about 6.0 of copper in the phosphate coating that forms.
11, a kind ofly do not comprising the method that forms phosphate coating on aluminium is as the metal base surface of its surface portion, wherein matrix surface is contacted with the composition of claim 4, the about 5min of the about 30sec-of time range that under the about 55 ℃ of temperature ranges of about 40-, contacts, the about 4.3g/m of the about 1.6-of quality increase scope of formed phosphate coating 2, and the weight percent about 2.0-about 6.0 of copper in the phosphate coating that forms.
12, a kind of method that on metal base surface, forms phosphate coating, wherein matrix surface contacts with the composition of claim 3, the about 10min of the about 15sec-of contact in the about 55 ℃ of temperature ranges of about 25-, the about 5.4g/m of the formed about 1.1-of phosphate coating quality increase scope 2, and in the phosphate coating that forms the about 1.0-of weight percentage ranges about 8.0 of copper.
13, a kind of method that on metal base surface, forms phosphate coating, matrix surface is contacted with the composition of claim 2, the about 15min of the about 5sec-of contact in the about 85 ℃ temperature range of about 21-, formed phosphate coating quality increases the about 5.4g/m of about 1.1- 2, the about 0.50-of the weight percentage ranges of copper about 10.0 in formed phosphate coating.
14, a kind of method that on metal base surface, forms phosphate coating, matrix surface is contacted with the composition of claim 1, the about 15min of the about 5sec-of contact in the about 85 ℃ of temperature ranges of about 21-, the about 5.4g/m of the about 1.1-of phosphate coating quality increase scope that is generated 2, and in formed phosphate coating the about 0.50-of the weight percentage ranges of copper about 10.0.
15, a kind of method that on metal base surface, forms supercoat, the step that this method comprises:
(1) clean surface;
(2) surface of cleaning is contacted with the activated compositions that contains colloidal titanium;
(3) method by claim 14 forms phosphate coating on the surface of cleaning and activating; With
(4) on the phosphate coating that step (3) forms, apply the outer SOLID ORGANIC base of one deck coating.
16, a kind of method that on metal base surface, forms supercoat, the step that described method comprises:
(1) clean surface;
(2) surface of cleaning is contacted with the activated compositions that contains colloidal titanium;
(3) method by claim 12 forms phosphate coating on the surface of cleaning and activating; With
(4) on the phosphate coating that step (3) forms, apply the outer SOLID ORGANIC base of one deck coating.
17, a kind ofly do not comprising that aluminium makes on the metal base surface of its surface portion to form the method for supercoat, described method comprises step:
(1) clean surface;
(2) surface of cleaning is contacted with the activated compositions that contains colloidal titanium;
(3) method by claim 11 forms phosphate coating on the surface of cleaning and activating; With
(4) on the phosphate coating that step (3) forms, apply the outer SOLID ORGANIC base of one deck coating.
18, a kind ofly comprising that aluminium makes to form on the surface of auri body of part surface the method for supercoat, the step that described method comprises:
(1) clean surface;
(2) surface of cleaning is contacted with the activated compositions that contains colloidal titanium;
(3) method by claim 10 forms phosphate coating on the surface of cleaning and activating; With
(4) on the phosphate coating that step (3) forms, apply the outer SOLID ORGANIC base of one deck coating.
19, a kind ofly comprising that aluminium makes to form on the metal base surface of primary surface part the method for supercoat, the method comprising the steps of:
(1) clean surface;
(2) surface of cleaning is contacted with the activated compositions that contains colloidal titanium;
(3) method by claim 9 generates phosphate coating on the surface of cleaning and activating; With
(4) on the phosphate coating that step (3) forms, apply the outer SOLID ORGANIC base of one deck coating.
20, a kind ofly do not comprising the method that forms supercoat on aluminium is as the metal base surface of its surface portion, described method comprises step:
(1) clean surface;
(2) surface of cleaning is contacted with the activated compositions that contains colloidal titanium;
(3) method by claim 8 generates phosphate coating on the surface of cleaning and activating; With
(4) on the phosphate coating that step (3) forms, apply the outer SOLID ORGANIC base of one deck coating.
CN93119949A 1992-12-22 1993-12-22 Substantially nickel-free phosphate conversion coating composition and process Expired - Fee Related CN1092245C (en)

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CN104032293A (en) * 2014-06-11 2014-09-10 安徽江南机械有限责任公司 Highly corrosion-resistant environment-friendly black phosphatizing liquid without nickel single component

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CN103924226B (en) * 2014-04-25 2016-06-15 山东大学 A kind of preparation method of hierarchy zinc phosphate chemical composition coating
CN104032293A (en) * 2014-06-11 2014-09-10 安徽江南机械有限责任公司 Highly corrosion-resistant environment-friendly black phosphatizing liquid without nickel single component
CN104032293B (en) * 2014-06-11 2016-02-17 安徽江南机械有限责任公司 One not nickeliferous single component high anti-corrosion environmental protection black phosphating solution

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EP0675972B1 (en) 1999-08-11
DE69326021T2 (en) 1999-12-23
CZ164995A3 (en) 1996-01-17
ATE183247T1 (en) 1999-08-15
WO1994014999A1 (en) 1994-07-07
CN1092245C (en) 2002-10-09
CZ287997B6 (en) 2001-03-14
ES2136726T3 (en) 1999-12-01
SG55084A1 (en) 1998-12-21
EP0675972A4 (en) 1995-11-02
ZA939636B (en) 1994-08-15
PL309404A1 (en) 1995-10-02
JPH08504890A (en) 1996-05-28
CA2150545A1 (en) 1994-07-07

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